PHYSICAL EQUILIBRIA

Chapt.－13, Page-513
1. Types of Solutions
We can distinguish six types of solutions, depending on the original
states (solid, liquid, or gas) of the solution components.
A saturated solution contains the maximum amount of a solute
that will dissolve in a given solvent at a specific temperature.

An unsaturated solution contains less solute than it has the

capacity to dissolve.
A third type, a supersaturated solution, contains more solute
than is present in a saturated solution. Supersaturated solutions
are not very stable. In time, some of the solute will come out
of a supersaturated solution as crystals.

Crystallization is the process in which dissolved solute comes

out of solution and forms crystals.
We normally think of precipitates as being made up of small
particles, whereas crystals may be large and well formed.
2. A molecular View of the Solution
Process
The ease with which a solute particle replaces a solvent
molecule depends on the relative strengths of three types of
interactions:
• solvent-solvent interaction
• solute-solute interaction
• solvent-solute interaction
The heat of solution ΔHsoln is given by
The solution process, like all physical and chemical processes, is
governed by two factors.
One is energy, which determines whether a solution process is
exothermic or endothermic.
The second factor is an inherent tendency toward disorder in all
natural events.
The saying “like dissolves like” is helpful in predicting the
solubility of a substance in a given solvent.
（Two substances with intermolecular forces of similar type
and magnitude are likely to be soluble in each other. ）
For example: carbon tetrachloride (CCl4) and benzene (C6H6)
Two liquids are said to be miscible if they are completely
soluble in each other in all proportions.
In general, we predict that ionic compounds should be much
more soluble in polar solvents, such as water, liquid ammonia,
and liquid hydrogen fluoride, than in nonpolar solvents, such as
benzene and carbon tetrachloride.

For example: NaCl dissolves in water, the ions are stabilized in

solution by hydration, which involves ion-dipole interaction.
 Example: Predict the relative solubilities in the following cases:
(a) Bromine (Br2) in benzene (C6H6, μ = 0 D) and in water (μ =
1.87 D), (b) KCl in carbon tetrachloride (CCl4, μ = 0 D) and in
liquid ammonia (NH3, μ = 1.46 D), (c) formaldehyde (CH2O) in
carbon disulfide (CS2, μ = 0 D) and in water.
Solution
(a) Br2 is a nonpolar molecule and therefore should be more
soluble in C6H6, which is also nonpolar, than in water. The only
intermolecular forces between Br2 and C6H6 are dispersion forces.

(b) KCl is an ionic compound. For it to dissolve, the individual K+

and Cl- ions must be stabilized by ion-dipole interaction. Because
CCl4 has no dipole moment, KCl should be more soluble in liquid
NH3, a polar molecule with a large dipole moment.
(c) Because CH2O is a polar molecule and CS2 (a linear molecule)
is nonpolar,

the forces between molecules of CH2O and CS2 are dipole-

induced dipole and dispersion. On the other hand, CH2O can
form hydrogen bonds with water, so it should be more soluble in
that solvent.
3. Concentration Units
Types of Concentration Units
1. Percent by Mass

The percent by mass is a unitless number because it is a

ratio of two similar quantities.
Example: A sample of 0.892 g of potassium chloride (KCl) is
dissolved in 54.6 g of water. What is the percent by mass of KCl
in the solution?
2. Mole Fraction (X)

The mole fraction is also unitless, because it too is a ratio of

two similar quantities.

3. Molarity (M)

Thus, the units of molarity are mol/L.

 4. Molality (m)

Example: Calculate the molality of a sulfuric acid solution

containing 24.4 g of sulfuric acid in 198 g of water. The molar
mass of sulfuric acid is 98.09 g.
Solution: The definition of molality (m) is
First, we find the number of moles of sulfuric acid in 24.4 g of
the acid, using its molar mass as the conversion factor.

The mass of water is 198 g, or 0.198 kg. Therefore,

Comparison of Concentration Units
Suppose we want to express the concentration of a 0.396 m
glucose (C6H12O6) solution in molarity.
First, we calculate the mass of the solution from the molar
mass of glucose:

The next step is to experimentally determine the density of the

solution, which is found to be 1.16 g/mL. We can now calculate
the volume of the solution in liters by writing
Example: The density of a 2.45 M aqueous solution of methanol
(CH3OH) is 0.976 g/mL. What is the molality of the solution?
The molar mass of methanol is 32.04 g.
Solution

Our first step is to calculate the mass of water in one liter of the
solution, using density as a conversion factor. The total mass of
1 L of a 2.45 M solution of methanol is
Because this solution contains 2.45 moles of methanol, the
amount of water (solvent) in the solution is

The molality of the solution can be calculated by converting

898 g to 0.898 kg:
Example: Calculate the molality of a 35.4 percent (by mass)
aqueous solution of phosphoric acid (H3PO4). The molar mass
of phosphoric acid is 97.99 g.
Solution From the known molar mass of phosphoric acid, we
can calculate the molality in two steps. First we calculate the
number of moles of phosphoric acid in 35.4 g of the acid

The mass of water is 64.6 g, or 0.0646 kg. Therefore, the

molality is given by
4. The Effect of Temperature on Solubility
Solid Solubility and Temperature

Temperature dependence of
the solubility of some ionic
compounds in water.
 Fractional crystallization is the separation of a mixture of
substances into pure components on the basis of their differing
solubilities.

The solubilities of KNO3 and

NaCl at 0°C and 60°C. The
difference in temperature
dependence enables us to
isolate one of these
compounds from a solution
containing both of them,
through fractional
crystallization.
Suppose we have a sample of 90 g of
KNO3 that is contaminated with 10 g
of NaCl.
Thus, (90 - 12) g, or 78 g, of KNO3
will crystallize out of the solution, but
all of the NaCl will remain dissolved
Gas Solubility and Temperature

The solubility of gases in water usually decreases with

increasing temperature
5. The Effect of Pressure on the
Solubility of Gases
Henry’s law, which states that the solubility of a gas in a liquid
is proportional to the pressure of the gas over the solution:

c is the molar concentration (mol/L) of the dissolved gas;

P is the pressure (in atm) of the gas over the solution at
equilibrium;
For a given gas, k is a constant that depends only on temperature.
The constant k has the units mol/L  atm.
A molecular interpretation of Henry’s law. When the partial
pressure of the gas over the solution increases from (a) to (b),
the concentration of the dissolved gas also increases according
to Equation c = kP.
Example: The solubility of nitrogen gas at 25°C and 1 atm is
6.8 × 10-4 mol/L. What is the concentration (in molarity) of
nitrogen dissolved in water under atmospheric conditions? The
partial pressure of nitrogen gas in the atmosphere is 0.78 atm.
Solution
The first step is to calculate the quantity k in Equation c =kP

The decrease in solubility is the result of lowering the pressure

from 1 atm to 0.78 atm.
Exceptions:
For example, if the dissolved gas reacts with water, higher
solubilities can result.

Another interesting example is the dissolution of molecular

oxygen in blood.
 The Killer Lake

Deep waters in Lake Nyos

are pumped to the surface to
remove dissolved CO2 gas.
6. Colligative Properties of
Nonelectrolyte Solutions
Colligative properties (or collective properties) are properties
that depend only on the number of solute particles in solution
and not on the nature of the solute particles.
The colligative properties are vapor-pressure lowering, boiling-
point elevation, freezing-point depression, and osmotic pressure.

Vapor-Pressure Lowering
Raoult’s law, which states that the vapor pressure of a
solvent over a solution, P1, is given by the vapor pressure
of the pure solvent, P°1, times the mole fraction of the
solvent in the solution, X1
In a solution containing only one solute, X1 = 1 - X2, where X2 is
the mole fraction of the solute. Equation can therefore be
rewritten as

or

so that
We see that the decrease in vapor pressure, ΔP, is directly
proportional to the solute concentration (measured in mole
fraction).
Example: Calculate the vapor pressure of a solution made by
dissolving 218 g of glucose (molar mass = 180.2 g/mol) in 460
mL of water at 30°C. What is the vapor-pressure lowering?
The vapor pressure of pure water at 30°C is 31.82 mmHg.
Assume the density of the solution is 1.00 g/mL.
The vapor pressure of water at 30°C to be 31.82 mmHg.
Therefore, the vapor pressure of the glucose solution is

Finally, the vapor-pressure lowering is (31.82 - 30.4) mmHg,

or 1.4 mmHg.
If both components of a solution are volatile (that is, have
measurable vapor pressure), the vapor pressure of the solution is
the sum of the individual partial pressures. Raoult’s law holds
equally well in this case:

The total pressure is given by Dalton’s law of partial pressure

For example, benzene and toluene are volatile components that
have similar structures and therefore similar intermolecular
forces:

“ideal solution”

The dependence of the partial

pressures of benzene and toluene on
their mole fractions in a benzene-
toluene solution
( Xtoluene = 1 - Xbenzene ) at 80°C.
This solution is said to be ideal
because the vapor pressures obey
Raoult’s law.
Most solutions do not behave ideally in this respect. Designating
two volatile substances as A and B, we can consider the
following two cases:

Nonideal solutions. (a) Positive deviation occurs when PT is greater than that
predicted by Raoult’s law (the solid black line). (b) Negative deviation. Here,
PT is less than that predicted by Raoult’s law (the solid black line)
Fractional Distillation (分馏)
Solution vapor pressure has a direct bearing on fractional
distillation, a procedure for separating liquid components of a
solution based on their different boiling points.
 Boiling-Point Elevation
The boiling point of a solution is the temperature at which its
vapor pressure equals the external atmospheric pressure.
Because the presence of a nonvolatile solute lowers the vapor
pressure of a solution, it must also affect the boiling point of the
solution.

Phase diagram illustrating the boiling-

point elevation and freezing-point
depression of aqueous solutions. The
dashed curves pertain to the solution,
and the solid curves to the pure solvent.
As you can see, the boiling point of the
solution is higher than that of water,
and the freezing point of the solution is
lower than that of water.
 The boiling- point elevation (ΔTb) is defined as the boiling
point of the solution (Tb) minus the boiling point of the pure
solvent (T°b):

The value of ΔTb is proportional to the vapor-pressure

lowering, and so it is also proportional to the concentration
(molality) of the solution. That is,

Where m is the molality of the solution and Kb is the molal

boiling-point elevation constant. The units of Kb are °C/m.
Molal Boiling-Point Elevation and Freezing-Point Depression
Constants of Several Common Liquids
Freezing-Point Depression
The freezing point depression (ΔTf) is defined as the freezing
point of the pure solvent (T°f) minus the freezing point of the
solution (Tf):

ΔTf is proportional to the concentration of the solution:

where m is the concentration of the solute in molality units,

and Kf is the molal freezing-point depression constant. Like
Kb, Kf has the units °C/m.
Example: Ethylene glycol (EG), CH2(OH)CH2(OH), is a
common automobile antifreeze. It is water soluble and fairly
nonvolatile (b.p. 197°C). Calculate the freezing point of a
solution containing 651 g of this substance in 2505 g of water.
Would you keep this substance in your car radiator during the
summer? The molar mass of ethylene glycol is 62.01 g.
Solution

To solve for the molality of the solution, we need to know the

number of moles of EG and the mass of the solvent in
kilograms. We find the molar mass of EG, and convert the mass
of the solvent to 2.505 kg, and calculate the molality as follows:
Because pure water freezes at 0°C, the solution will freeze at
(0 - 7.79)°C or -7.79°C. We can calculate boiling-point
elevation in the same way as follows:

Because the solution will boil at (100 + 2.2)°C, or 102.2°C,

it would be preferable to leave the antifreeze in your car
radiator in summer to prevent the solution from boiling.
Osmotic Pressure(渗透压)

The osmotic pressure (p) of a solution is the pressure required

to stop osmosis.
A semipermeable membrane (半透膜)allows the passage of
solvent molecules but blocks the passage of solute molecules.
where M is the molarity of solution, R is the gas constant
(0.0821 L  atm/K  mol), and T is the absolute temperature.
The osmotic pressure, π, is expressed in atm.
Osmotic pressure is directly proportional to the concentration
of solution, because all colligative properties depend only on
the number of solute particles in solution.
If two solutions are of equal concentration and, hence, have
the same osmotic pressure, they are said to be isotonic.
If two solutions are of unequal osmotic pressures, the more
concentrated solution is said to be hypertonic.
Example：The average osmotic pressure of seawater, is about
30.0 atm at 25°C. Calculate the molar concentration of an
aqueous solution of sucrose (C12H22O11) that is isotonic with
seawater.
Solution
A solution of sucrose that is isotonic with seawater must have
the same osmotic pressure, 30.0 atm.
Using Colligative Properties to Determine Molar Mass
Example: A 7.85-g sample of a compound with the empirical
formula C5H4 is dissolved in 301 g of benzene. The freezing
point of the solution is 1.05°C below that of pure benzene.
What are the molar mass and molecular formula of this
compound?
Solution The sequence of conversions for calculating the molar
mass of the compound is

Our first step is to calculate the molality of the solution.

Because there is 0.205 mole of the solute in 1 kg of solvent, the
number of moles of solute in 301 g, or 0.301 kg, of solvent is

Thus, the molar mass of the solute is

Now we can determine the ratio

Therefore, the molecular formula is (C5H4)2 or (naphthalene).

Example：A solution is prepared by dissolving 35.0 g of
hemoglobin (Hb) in enough water to make up 1 L in volume. If
the osmotic pressure of the solution is found to be 10.0 mmHg
at 25°C, calculate the molar mass of hemoglobin.
Solution The sequence of conversions is as follows:

First we calculate the molarity

The volume of the solution is 1 L, so it must contain 5.38 × 10-4
mol of Hb. We use this quantity to calculate the molar mass:
7. Colligative Properties of Electrolyte
Solutions
van’t Hoff factor

Consequently, the equations for colligative properties must be

modified as
An ion pair is made up of one or more cations and one or more
anions held together by electrostatic forces.

(a) Free ions and (b) ion pairs in solution. Such an ion pair
bears no net charge and therefore cannot conduct electricity
in solution.
 Example: The osmotic pressure of a 0.010 M potassium iodide
(KI) solution at 25°C is 0.465 atm. Calculate the van’t Hoff
factor for KI at this concentration.
Strategy Note that KI is a strong electrolyte, so we expect it to
dissociate completely in solution. If so, its osmotic pressure would be
2(0.010 M)(0.0821 L  atm/K  mol)(298 K) = 0.489 atm
However, the measured osmotic pressure is only 0.465 atm. The
smaller than predicted osmotic pressure means that there is ion-pair
formation, which reduces the number of solute particles (K+ and I-
ions) in solution.
Solution We have
8. Colloids(胶体)
A colloid is a dispersion of particles of one substance (the
dispersed phase) throughout a dispersing medium made of
another substance.
Colloidal particles are much larger than the normal solute
molecules; they range from 1 × 103 pm to 1 × 106 pm.
One way to distinguish a solution from a colloid is by the
Tyndall effect

Three beams of white light, passing through a Sunlight scattered by

colloid of sulfur particles in water, change to dust particles in the air.
orange, pink, and bluish-green. The colors
produced depend on the size of the particles
and also on the position of the viewer. The
smaller the dispersed particles, the shorter
(and bluer) the wavelengths.
Hydrophilic and Hydrophobic Colloids
Among the most important colloids are those in which the
dispersing medium is water. Such colloids are divided into two
categories called hydrophilic, or water-loving, and hydrophobic,
or water-fearing.

Hydrophilic groups on the

surface of a large molecule
such as protein stabilizes the
molecule in water. Note that
all these groups can form
hydrogen bonds with water.
A hydrophobic colloid normally would not be stable in water.

They can be stabilized, however, by adsorption of ions on

their surface.

Diagram showing the stabilization of hydrophobic colloids. Negative

ions are adsorbed onto the surface and the repulsion between like
charges prevents the clumping of the particles.
Another way hydrophobic colloids can be stabilized is by the
presence of other hydrophilic groups on their surfaces.

(a) A sodium stearate molecule. (b) The simplified

representation of the molecule that shows a hydrophilic head
and a hydrophobic tail.
The cleansing action of soap.
(a) Grease (oily substance) is not soluble in water.
(b) When soap is added to water, the nonpolar tails of soap
molecules dissolve in grease.
(c) Finally, the grease is removed in the form of an emulsion. Note
that each oily droplet now has an ionic exterior that is hydrophilic.