Solutions

Chapter 13
Properties of Solutions
Solutions
Solutions
Solutions are homogeneous mixtures of two or
more pure substances.
In a solution, the solute is dispersed uniformly
throughout the solvent.
The intermolecular forces
between solute and solvent
particles must be strong enough
to compete with those between
solute particles and those
between solvent particles.
Solutions
How Does a Solution Form?
As a solution forms, the solvent pulls solute
particles apart and surrounds, or solvates, them.
If an ionic salt is soluble in water, it is because the
ion-dipole interactions are strong enough to
overcome the lattice energy of the salt crystal.
Side note - Just because a substance disappears when it comes in contact with a solvent, it doesnt
mean the substance dissolved.
Dissolution is a physical changeyou can get back the original solute by evaporating the solvent.
If you cant, the substance didnt dissolve, it reacted.
Solutions
Energy Changes in Solution
Three processes affect the
energetics of the process:
Separation of solute particles
Separation of solvent particles
New interactions between solute
and solvent
The enthalpy change of the
overall process depends on
AH for each of these steps.
Solutions
Why Do Endothermic
Processes Occur?
Things do not tend to occur
spontaneously (i.e., without
outside intervention) unless the
energy of the system is
lowered.

Yet we know that in some
processes, like the dissolution
of NH
4
NO
3
in water, heat is
absorbed, not released.
Solutions
Enthalpy Is Only Part of the Picture
The reason is that increasing the
disorder or randomness (known as
entropy) of a system tends to
lower the energy of the system.

So even though enthalpy may
increase, the overall energy of the
system can still decrease if the
system becomes more disordered.
Solutions
Types of Solutions
Saturated
Solvent holds as much solute
as is possible at that
temperature.
Dissolved solute is in dynamic
equilibrium with solid solute
particles.
Unsaturated
Less than the maximum
amount of solute for that
temperature is dissolved in the
solvent.
Solutions
Types of Solutions
Supersaturated
Solvent holds more solute than is normally possible at
that temperature.
These solutions are unstable; crystallization can
usually be stimulated by adding a seed crystal or
scratching the side of the flask.
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.

The more similar the
intermolecular attractions,
the more likely one
substance is to be soluble
in another.
Solutions
Factors Affecting Solubility
Glucose (which has
hydrogen bonding) is
very soluble in water,
while cyclohexane (which
only has dispersion
forces) is not.
Vitamin A is soluble in
nonpolar compounds
(like fats).
Vitamin C is soluble in
water.
Solutions
Gases in Solution
In general, the
solubility of gases in
water increases with
increasing mass.
Larger molecules
have stronger
dispersion forces.
Solutions
Gases in Solution Henrys Law
The solubility of liquids and solids
does not change appreciably with
pressure.
The solubility of a gas in a liquid is
directly proportional to its pressure.
S
g
= kP
g

where
S
g
is the solubility of the gas;
k is the Henrys law constant for that
gas in that solvent;
P
g
is the partial pressure of the gas
above the liquid.

Solutions
Temperature
Generally, the
solubility of solid
solutes in liquid
solvents increases
with increasing
temperature.
Solutions
Temperature
The opposite is true
of gases:
Carbonated soft
drinks are more
bubbly if stored in
the refrigerator.
Warm lakes have
less O
2
dissolved in
them than cool lakes.
Solutions
Ways of
Expressing
Concentrations
of Solutions
Solutions
Mass Percentage
Mass % of A =
mass of A in solution
total mass of solution
100
Solutions
Parts per Million and
Parts per Billion
ppm =
mass of A in solution
total mass of solution
10
6

Parts per Million (ppm)
Parts per Billion (ppb)
ppb =
mass of A in solution
total mass of solution
10
9

Solutions
moles of A
total moles in solution
X
A
=
Mole Fraction (X)
In some applications, one needs the
mole fraction of solvent, not solute
make sure you find the quantity you
need!
Solutions
mol of solute
L of solution
M =
Molarity (M)
You will recall this concentration
measure from Chapter 4.
Because volume is temperature
dependent, molarity can change with
temperature.
Solutions
mol of solute
kg of solvent
m =
Molality (m)
Because both moles and mass do not
change with temperature, molality
(unlike molarity) is not temperature
dependent.
Solutions
Changing Molarity to Molality
If we know the
density of the
solution, we can
calculate the
molality from the
molarity, and vice
versa.
Solutions
Colligative Properties
Changes in 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
Because of solute-solvent
intermolecular attraction,
higher concentrations of
nonvolatile solutes make it
harder for solvent to escape
to the vapor phase.
Therefore, the vapor
pressure of a solution is
lower than that of the pure
solvent.
Solutions
Raoults Law
P
A
= X
A
P
A

where
X
A
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 mole
fraction of the solvent.
Solutions
Boiling Point Elevation and
Freezing Point Depression
Nonvolatile 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:
AT
b
= K
b
m

where K
b
is the molal
boiling point elevation
constant, a property of
the solvent.
AT
b
is added to the normal
boiling point of the solvent.
Solutions
Freezing Point Depression
The change in freezing
point can be found
similarly:
AT
f
= K
f
m

Here K
f
is the molal
freezing point
depression constant of
the solvent.
AT
f
is subtracted from the normal
freezing point of the solvent.

Solutions
Boiling Point Elevation and
Freezing Point Depression
Note that in both
equations, AT does
not depend on what
the solute is, but
only on how many
particles are
dissolved.
AT
b
= K
b
m


AT
f
= K
f
m
Solutions
Colligative Properties of
Electrolytes
Since colligative properties depend on the number of
particles dissolved, solutions of electrolytes (which
dissociate in solution) should show greater changes
than those of nonelectrolytes.

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.
Solutions
vant Hoff Factor
One mole of NaCl in
water does not
really give rise to
two moles of ions.
Some Na
+
and Cl

reassociate for a
short time, so the
true concentration of
particles is
somewhat less than
two times the
concentration of
NaCl.
Solutions
vant Hoff Factor
Reassociation is
more likely at higher
concentration.
Therefore, the
number of particles
present is
concentration
dependent.
Solutions
The vant Hoff Factor
We modify the
previous equations
by multiplying by the
vant Hoff factor, i

AT
f
= K
f
m i
Solutions
Ex. Electrolyte (i = ?)
IMPORTANT the colligative properties
of freezing point and boiling point are
proportional to the number of particles
present in the solution.
van Hoft factor, i
NaCl i = 2 moles Ie. 1m =
2m
CaCl
2
i = 3 moles Ie. 1m = 3m
Al
2
(SO
4
)
3
i = 5 moles Ie. 1m =
5m
Solutions
Osmosis
Some substances form semipermeable membranes, allowing
some smaller particles to pass through, but blocking other
larger particles.
In biological systems, most semipermeable membranes allow
water to pass through, but solutes are not free to do so.
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).
Solutions
Osmotic Pressure
The pressure required to stop osmosis,
known as osmotic pressure, t, is
n
V
t = ( )RT = MRT
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
same), the solutions are isotonic.
Solutions
Osmosis in 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.

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
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
Ideal Solutions
Two types of molecules are randomly distributed
Typically, molecules are similar in size and shape
Intermolecular forces in pure liquids & mixture are similar
Examples: benzene & toluene, hexane and heptane
(more precise thermodynamic definition coming)
In ideal solutions, the partial vapor pressure of component
A is simply given by Raoults Law:
*
A A A
P x P =
vapor pressure of pure A
mole fraction of A in solution
Solutions
Total VP of an ideal solution
B A total
P P P + =
*
*
ln
A
A
A A
P
P
RT + =
*
A A A
P x P =
A A A
x RT ln
*
+ =
This serves to define an ideal
solution if true for all values of x
A

The total vapor pressure of an ideal solution:
* *
B B A A total
P x P x P + =
40 C
) (
* * *
A B B A total
P P x P P + =
Solutions
Deviations from Raoults Law
Methanol, ethanol, propanol
mixed with water. Which one
is which? (All show positive
deviations from ideal behavior)
CS
2
and dimethoxymethane: Positive
deviation from ideal (Raoults Law) behavior.
trichloromethane/acetone: Negative
deviation from ideal (Raoults Law) behavior.
Solutions
Raoult and Henry
1 as
*

A A A A
x P x P
0 as
,

A A H A A
x k x P
Raoults law
Henrys law constant:
*
,

A A H
P k =
The Henrys law constant reflects the intermolecular interactions between
the two components.

Solutions following both Raoults and Henrys Laws are called ideal-dilute
solutions.
Henrys behavior:
Henrys law
(Raoults Law)
Solutions
The Vapor Pressure of
Solutions
Nonvolatile Solute/Solvent
0
solvent solvent solution
P x P =
Raoults Law
Solutions
Solutions
Solutions
Raoults Law with Multiple
Volatile compounds
Ideal solution: A solution, obeys Raoults
law, formed with no accompanying energy
change, when the intermolecular attractive
forces between the molecules of the solvent
are the same as those between the molecules
in the separate components.
Solutions
Rauolts Law
e solution vapor abov
d B in the re of A an ial pressu : the part and P P
B and pure of pure A r pressure : the vapo and P P
of A and B f raction : the mole and x x
P x P x P P P
B A
B A
B A
B B A A B A total
0 0
0 0
+ = + =
Solutions
1.What is the total vapor pressure in a mixture of
50.0 g CH
3
OH (P = 93.3 torr) and 25.0 g H
2
O
(P = 17.5 torr)?

2.In a mixture of 86.0 g C
6
H
6
(P = 93.96 torr)
and 90.0 g C
2
H
4
Cl
2
(P = 224.9 torr), what is
the total vapor pressure?
Solutions
Nonideal Solution
Solutions that do not obey Raoults Law are
called nonideal solutions.
Solute-solvent interactions are significantly
different from solute-solute and solvent-solvent
interactions, the solution is likely to be a
nonideal solution.
Intermolecular forces between components in a
dissolved solution can cause deviations from the
calculated vapor pressure.
Solutions
Negative Deviation from
Raoults Law
Both components have a lower escaping
tendency in the solution than in the pure
liquids.
C
O
H
3
C
O
H
H
H
3
C
o

o
+
Solutions
Positive Deviation from
Raoults Law
If two liquids mix endothermically, this
indicates that the solute-solvent interactions are
weaker than the interactions among the
molecules in the pure liquids.
More energy is required to expand the liquid
than is released when the liquids are mixed. The
molecules in the solution have a higher
tendency to escape than expected.
CH
3
CH
2
OH
CH
3
CH
2
CH
2
CH
2
CH
2
CH
3
Solutions
ideal system positive deviation negative deviation
Solutions
Solutions
54
Ideal Solutions
A Solution is any homogeneous phase that contains more
than one component. These components cant be physically
differentiated.
A Solvent is the component with the larger proportion or
quantity in the solution. A Solute is the component with the
smaller proportion or quantity in the solution.
The idea of I deal Solutions is used to simplify the study of
the phase equilibrium for solution. The solution is considered
to be ideal when:
its components are assumed to have similar structures
and sizes, and when
it represents complete uniformity of molecular forces
(basically attraction forces).
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55
Ideal Solutions
When considering a binary system, we are
often interested to study the behavior of that
system in terms of the variables P, T and n.
Solutions
56
Raoults Law
Recall that the vapor pressure is
a measure of the tendency of
the substance to escape from
the liquid.
For an ideal solution composed
of two components (binary
systems) , Raoults law relates
between the vapor pressure of
each component in its pure state
(P*) to the partial vapor
pressure of that component
when it is in the ideal solution
(P).
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57
Raoults Law
To know what partial vapor
pressure a component in a
solution has is important. This
is because it gives you
information about the cohesive
forces in the system.
Solutions
58
Raoults Law
If the solution has partial
vapor pressures that follow:
*
2 2 2
*
1 1 1
P x P
P x P
=
=
then the system is said to obey
Raoults law and to be ideal,
taken into consideration T is
fixed for the solvent and
solution.
Examples include:
Benzene toluene.
C
2
H
5
Cl C
2
H
5
Br.
CHCl
3
HClC=CCl
2
.
Solutions
59
Application of Raoults Law
Problem 5.21:
Benzene and toluene form nearly ideal solutions. If at 300
K, P*(toluene) = 3.572 kPa and P*(benzene) = 9.657 kPa,
compute the vapor pressure of a solution containing 0.60
mole fraction of toluene. What is the mole fraction of
toluene in the vapor over this liquid?
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60
Deviations from Raoults Law
Deviations from Raoults law
occur for nonideal solutions.
Consider a binary system made of
A and B molecules.
Positive deviation occurs when
the attraction forces between A-A
and B-B pairs are stronger than
between A-B. As a result, both A
and B will have more tendency to
escape to the vapor phase.
Examples:
CCl
4
C
2
H
5
OH system.
n-C
6
H
14
C
2
H
5
OH system
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61
Deviations from Raoults Law
For a binary system made of A
and B molecules.
Negative deviation occurs when
the attraction force between A-B
pairs is stronger than between A-
A and B-B pairs. As a result, both
A and B will have less tendency
to escape to the vapor phase.
Examples:
CCl
4
CH
3
CHO system.
H
2
O CH
3
CHO system
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62
Deviations from Raoults Law
Another important
observation is that
at the limits of infinite
dilution, the vapor
pressure of the solvent
obeys Raoults law.
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63
Henrys Law
The mass of a gas (m
2
)
dissolved by a given
volume of solvent at
constant T is
proportional to the
pressure of the gas (P
2
)
above and in equilibrium
with the solution.
m
2
= k
2
P
2
where k
2
is the Henrys
law constant.
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64
Henrys Law
For a mixture of gases
dissolved in a solution.
Henrys law can be
applied for each gas
independently.
The more commonly
used forms of Henrys
law are:
P
2
= k x
2
P
2
= k c
2

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65
Henrys Law
The vapor pressure of a
solute, P
2
, in a solution in
which the solute has a mole
fraction of x
2
is given by:
P
2
= x
2
P
2
*
where P
2
* is the vapor pressure
of the solute in a pure liquefied
state.
It is also found that at the
limits of infinite dilution, the
vapor pressure of the solute
obeys Henrys law.
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66
Application of Henrys Law