Chemistry, The Central Science, 11th edition

Theodore L. Brown; H. Eugene LeMay, Jr.;

and Bruce E. Bursten

Chapter 13
Properties of Solutions

Adapted by SA Green from:

John D. Bookstaver
St. Charles Community College
Solutions
St. Peters, MO
 2006, Prentice Hall, Inc.
 Solutions

• Solutions are homogeneous mixtures of two or

more pure substances.
• In a solution, the solute is dispersed uniformly
throughout the solvent.

Solutions
 Solutions

How does a solid dissolve

into a liquid?

What ‘drives’ the dissolution

process?

What are the energetics of

dissolution?

Solutions
 How Does a Solution Form?
1. Solvent molecules attracted to surface ions.
2. Each ion is surrounded by solvent molecules.
3. Enthalpy (DH) changes with each interaction broken or
formed.

Ionic solid dissolving in water

Solutions
 How Does a Solution Form?
1. Solvent molecules attracted to surface ions.
2. Each ion is surrounded by solvent molecules.
3. Enthalpy (DH) changes with each interaction broken or
formed.

Solutions
How Does a Solution Form
The ions are solvated
(surrounded by
solvent).
If the solvent is water,
the ions are hydrated.
The intermolecular force
here is ion-dipole.

Solutions
 Energy Changes in Solution
To determine the enthalpy
change, we divide the
process into 3 steps.
1. Separation of solute
particles.
2. Separation of solvent
particles to make ‘holes’.
3. Formation of new
interactions between
solute and solvent.

Solutions
 Enthalpy Changes in Solution

The enthalpy change

of the overall process
depends on DH for
each of these steps.

Start

End
Solutions
Start End
Enthalpy changes during dissolution
DHsoln = DH1 + DH2 + DH3
The enthalpy of
solution, DHsoln, can be
either positive or
negative.

DHsoln (MgSO4)= -91.2 kJ/mol --> exothermic

DHsoln (NH4NO3)= 26.4 kJ/mol --> endothermic Solutions
 Why do endothermic processes
sometimes occur spontaneously?
Some processes, like
the dissolution of
NH4NO3 in water, are
spontaneous at room
temperature even
though heat is
absorbed, not
released.

Solutions
 Enthalpy Is Only Part of the Picture
Entropy is a measure of:
• Dispersal of energy in the
system.
• Number of microstates
(arrangements) in the
system.

b. has greater entropy,

 is the favored state

(more on this in chap 19) Solutions

 Entropy changes during dissolution
Each step also involves a
change in entropy.
1. Separation of solute
particles.
2. Separation of solvent
particles to make ‘holes’.
3. Formation of new
interactions between
solute and solvent.

Solutions
SAMPLE EXERCISE 13.1 Assessing Entropy Change
In the process illustrated below, water vapor reacts with excess solid sodium
sulfate to form the hydrated form of the salt. The chemical reaction is

Does the entropy of the system increase or decrease?

Solutions
 Dissolution vs reaction

dry
Ni(s) + HCl(aq) NiCl2(aq) + H2(g) NiCl2(s)

• Dissolution is a physical change—you can get back the original

solute by evaporating the solvent.
• If you can’t, the substance didn’t dissolve, it reacted.
Solutions
Degree of saturation
• Saturated solution
 Solvent holds as much
solute as is possible at
that temperature.
 Undissolved solid
remains in flask.
 Dissolved solute is in
dynamic equilibrium
with solid solute
particles.

Solutions
 Degree of saturation

• Unsaturated Solution
 Less than the maximum
amount of solute for that
temperature is dissolved
in the solvent.
 No solid remains in flask.

Solutions
 Degree of saturation

• Supersaturated
 Solvent holds more solute than is normally possible at
that temperature.
 These solutions are unstable; crystallization can often
be stimulated by adding a “seed crystal” or scratching
the side of the flask. Solutions
 Degree of saturation

Unsaturated, Saturated or Supersaturated?

 How much solute can be dissolved in a solution?

More on this in Chap 17

(solubility products, p 739) Solutions
 Factors Affecting Solubility

• Chemists use the axiom

“like dissolves like”:
 Polar substances tend to
dissolve in polar solvents.
 Nonpolar substances tend to
dissolve in nonpolar
solvents.

Solutions
 Factors Affecting Solubility

The stronger the

intermolecular
attractions between
solute and solvent,
the more likely the
Example: ethanol in water solute will dissolve.
Ethanol = CH3CH2OH
Intermolecular forces = H-bonds; dipole-dipole; dispersion
Solutions
Ions in water also have ion-dipole forces.
 Factors Affecting Solubility

Glucose (which has

hydrogen bonding) is
very soluble in water.
Cyclohexane (which only
has dispersion forces)
is not water-soluble.

Solutions
 Factors Affecting Solubility
• Vitamin A is soluble in nonpolar compounds (like
fats).
• Vitamin C is soluble in water.

Solutions
Which
vitamin is
water-soluble
and which is
fat-soluble?

Solutions
 Gases in Solution

• In general, the solubility

of gases in water
increases with
increasing mass.
Why?
• Larger molecules have
stronger dispersion
forces.

Solutions
Gases in Solution

QuickTime™ and a
TIFF (LZW) decompressor
are needed to see this picture.

Solutions
 Gases in Solution

• The solubility of
Increasing liquids and solids
pressure does not change
above
solution
appreciably with
forces pressure.
more gas • But, the solubility of a
to dissolve. gas in a liquid is
directly proportional
to its pressure.
Solutions
 Henry’s Law
Sg = kPg
where
• Sg is the solubility of the
gas;
• k is the Henry’s law
constant for that gas in
that solvent;
• Pg is the partial pressure
of the gas above the
liquid. Solutions
 Henry’s Law

k for N2 at 25°
=6.8 x 10-4 mol/L atm

Sg = kPg
Solutions
Temperature

Generally, the
solubility of solid
solutes in liquid
solvents increases
with increasing
temperature.

Solutions
 Temperature
• The opposite is true of
gases. Higher
temperature drives gases
out of solution.

 Carbonated soft drinks

are more “bubbly” if
stored in the refrigerator.
 Warm lakes have less O2
dissolved in them than
cool lakes.

Solutions
Ways of Expressing
Concentrations of
Solutions
Solutions
 Mass Percentage

mass of A in solution
Mass % of A =  100
total mass of solution

Solutions
 Parts per Million and
Parts per Billion
Parts per Million (ppm)
mass of A in solution
ppm =  106
total mass of solution

Parts per Billion (ppb)

mass of A in solution
ppb =  109
total mass of solution
Solutions
 Mole Fraction (X)
moles of A
XA =
total moles in solution

• In some applications, one needs the mole

fraction of solvent, not solute—make sure
you find the quantity you need!

Solutions
 Molarity (M)

mol of solute
M=
L of solution

• You will recall this concentration measure

from Chapter 4.
• Because volume is temperature dependent,
molarity can change with temperature.

Solutions
 Molality (m)

mol of solute
m=
kg of solvent

Because neither moles nor mass change

with temperature, molality (unlike
molarity) is not temperature dependent.

Solutions
Solutions
SAMPLE EXERCISE 13.4 Calculation of Mass-Related Concentrations

(a) A solution is made by dissolving 13.5 g of glucose (C 6H12O6) in 0.100 kg of water. What is the mass
percentage of solute in this solution? (b) A 2.5-g sample of groundwater was found to contain 5.4 g of Zn2+
What is the concentration of Zn2+ in parts per million?

PRACTICE EXERCISE
(a) Calculate the mass percentage of NaCl in a solution containing 1.50 g of NaCl in 50.0 g of water. (b) A
commercial bleaching solution contains 3.62 mass % sodium hypochlorite, NaOCl. What is the mass of NaOCl
in a bottle containing 2500 g of bleaching solution?

PRACTICE EXERCISE
A commercial bleach solution contains 3.62 mass % NaOCl in water. Calculate (a) the molality and (b) the mole
fraction of NaOCl in the solution.

Solutions
 Colligative Properties
• Colligative properties depend only on the
number of solute particles present, not on
the identity of the solute particles.
• Among colligative properties are
Vapor pressure lowering
Boiling point elevation
Melting point depression
Osmotic pressure
Solutions
 Vapor Pressure

As solute molecules are

added to a solution, the
solvent become less
volatile (=decreased
vapor pressure).
Solute-solvent interactions
contribute to this effect.

Solutions
 Vapor Pressure

Therefore, the vapor

pressure of a solution is
lower than that of the
pure solvent.

Solutions
 Raoult’s Law

PA = XAPA
where
• XA is the mole fraction of compound A
• PA is the normal vapor pressure of A at that
temperature

NOTE: This is one of those times when you want

to make sure you have the vapor pressure of
the solvent. Solutions
SAMPLE EXERCISE 13.8 Calculation of Vapor-Pressure Lowering

Glycerin (C3H8O3) is a nonvolatile nonelectrolyte with a density of 1.26 g/mL at 25°C. Calculate the vapor
pressure at 25°C of a solution made by adding 50.0 mL of glycerin to 500.0 mL of water. The vapor pressure of
pure water at 25°C is 23.8 torr (Appendix B).

PRACTICE EXERCISE
The vapor pressure of pure water at 110°C is 1070 torr. A solution of ethylene glycol and water has a vapor
pressure of 1.00 atm at 110°C. Assuming that Raoult’s law is obeyed, what is the mole fraction of ethylene
glycol in the solution?

Solutions
 Boiling Point Elevation and
Freezing Point Depression
Solute-solvent
interactions also cause
solutions to have higher
boiling points and lower
freezing points than the
pure solvent.

Solutions
 Boiling Point Elevation
The change in boiling point
is proportional to the
molality of the solution:
DTb = Kb  m

where Kb is the molal

boiling point elevation
constant, a property of the
solvent.
DTb is added to the normal
Solutions
boiling point of the solvent.
 Freezing Point Depression
• The change in freezing
point can be found
similarly:
DTf = Kf  m

• Here Kf is the molal

freezing point depression
constant of the solvent.

DTf is subtracted from the normal

freezing point of the solvent. Solutions
 Boiling Point Elevation and
Freezing Point Depression
In both equations, DT
does not depend on
DT b = K b  m
what the solute is, but
only on how many
particles are dissolved.
DTf = Kf  m

Solutions
 Colligative Properties of
Electrolytes
Because these properties depend on the number of particles
dissolved, solutions of electrolytes (which dissociate in
solution) show greater changes than those of
nonelectrolytes.
e.g. NaCl dissociates to form 2 ion particles; its limiting van’t
Hoff factor is 2.

Solutions
 Colligative Properties of
Electrolytes
However, a 1 M solution of NaCl does not show twice
the change in freezing point that a 1 M solution of
methanol does.
It doesn’t act like there are really 2 particles.

Solutions
van’t Hoff Factor

One mole of NaCl in

water does not really
give rise to two moles
of ions.

Solutions
van’t Hoff Factor

Some Na+ and Cl−

reassociate as
hydrated ion pairs, so
the true concentration
of particles is
somewhat less than
two times the
concentration of NaCl.

Solutions
 The van’t Hoff Factor

• Reassociation is more
likely at higher
concentration.
• Therefore, the
number of particles
present is
concentration
dependent.

Solutions
 The van’t Hoff Factor

We modify the
previous equations by
multiplying by the van’t
Hoff factor, i

DTf = Kf  m  i

i = 1 for non-elecrtolytes
Solutions
 Osmosis
• Semipermeable membranes allow some
particles to pass through while blocking
others.
• In biological systems, most semipermeable
membranes (such as cell walls) allow water
to pass through, but block solutes.

Solutions
 Osmosis
In osmosis, there is net
movement of solvent
from the area of higher
solvent concentration
(lower solute
concentration) to the
are of lower solvent
concentration (higher
solute concentration).

Water tries to equalize the concentration on

both sides until pressure is too high.

Solutions
 Osmotic Pressure
• The pressure required to stop osmosis,
known as osmotic pressure, , is

n
=( ) RT = MRT
V
where M is the molarity of the solution

If the osmotic pressure is the same on both sides

of a membrane (i.e., the concentrations are the Solutions
same), the solutions are isotonic.
 Osmosis in Blood Cells

• If the solute
concentration outside
the cell is greater than
that inside the cell, the
solution is hypertonic.

• Water will flow out of

the cell, and crenation
results.
Solutions
 Osmosis in Cells

• If the solute
concentration outside
the cell is less than that
inside the cell, the
solution is hypotonic.

• Water will flow into the

cell, and hemolysis
results.
Solutions
Solutions
 Molar Mass from
Colligative Properties
We can use the effects
of a colligative property
such as osmotic
pressure to determine
the molar mass of a
compound.

Solutions
 Colloids:
Suspensions of particles larger than individual
ions or molecules, but too small to be settled out
by gravity.

Solutions
Tyndall Effect
• Colloidal suspensions can
scatter rays of light.
• This phenomenon is
known as the Tyndall
effect.

Solutions
 Colloids in Biological Systems

Some molecules have a

polar, hydrophilic (water-
loving) end and a
nonpolar, hydrophobic
(water-hating) end.

Solutions
Colloids in Biological Systems

Sodium stearate is
one example of
such a molecule.

Solutions
 Colloids in Biological Systems

These molecules can

aid in the
emulsification of fats
and oils in aqueous
solutions.

Solutions
END Chap 13

Solutions