Chemistry, The Central Science, 10th 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 (H) 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 (H) 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 H for
each of these steps.
Start

End
Solutions
Start End
Enthalpy changes during dissolution
Hsoln = H1 + H2 + H3
The enthalpy of
solution, Hsoln, can
be either positive or
negative.

Hsoln (MgSO4)= -91.2 kJ/mol --> exothermic

Hsoln (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
to dissolve. a 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
 Chap 13:
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
Ma
ss/
Ma
ss
s
o le
/M
les
Mo

s /L M
ole
ole
M s/M
aSolutions
ss
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
Tb is added to the normal
boiling point of the solvent.
The change in boiling
point is proportional to
the molality of the
solution:
Tb = Kb  m
where Kb is the molal
boiling point elevation
constant, a property of
the solvent.
Solutions
 Freezing Point Depression
• The change in freezing
point can be found
similarly:
Tf = Kf  m

• Here Kf is the molal

freezing point
depression constant of
the solvent.
Tf is subtracted from the normal
freezing point of the solvent. Solutions
Boiling Point Elevation and
Freezing Point Depression
In both equations,
T does not depend
Tb = Kb  m
on what the solute
is, but only on how
many particles are
dissolved. Tf = 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

Tf = 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