Colligative Properties of Nonelectrolyte Solutions - Boundless Chemistry

4/6/2018 Colligative Properties of Nonelectrolyte Solutions | Boundless Chemistry
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Colligative Properties of Nonelectrolyte

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Vapor Pressure of Nonelectrolyte Solutions
The vapor pressure of a solution is directly in uenced by the number of

solute molecules present in a given amount of solvent.
LEARNING OBJECTIVES
Calculate the vapor pressure of a nonelectrolyte solution using

Raoult’s law
KEY TAKEAWAYS
Key Points
The vapor pressure of a system is a measure of the

molecules ‘ tendency to escape into the gas phase.
Vapor pressure is a colligative property, meaning that

the amount it is increased or decreased is directly
related to the amount of solute present in the system.
Raoult’s law states that the partial vapor pressure of

each component of an ideal mixture of liquids is equal
to the vapor pressure of the pure component multiplied
by its mole fraction in the mixture
Key Terms
Raoult’s law:
raoult’s law: States that the partial vapor pressure of

each component of an ideal mixture of liquids is equal
to the vapor pressure of the pure component multiplied
by its mole fraction in the mixture
colligative property: A property of solutions that is

directed by the ratio of solute to solvent, regardless of
the identity of the solute.
vapor pressure: The pressure that a vapor exerts, or its

partial pressure if it is mixed with other gases.
Colligative Properties: Vapor Pressure
Vapor pressure is a measure of the tendency of a material to escape into

the environment via gas. A substance that evaporates quickly has high
vapor pressure and is referred to as a volatile substance. When a solute
is added to a solvent, the vapor pressure decreases.
Vapor pressure: Vapor pressure measures the

particle transition from the liquid phase to the gas
phase and vice versa.
Lowering Vapor Pressure
The vapor pressure of a solvent is lowered by the addition of a non-

volatile solute to form a solution. By de nition, a non-volatile substance
does not evaporate. This decrease in vapor pressure can be explained
by using the entropy di erences of the liquid and gas phases along with
the position of dissolved particles after the addition of the solute.
Entropy
When molecules transition from the liquid phase to the gas phase,
entropy of the system increases. Entropy of the gaseous state is greater
than the entropy of the liquid state because the gaseous molecules
occupy a larger volume.
If the liquid solvent becomes “diluted” with solute, the entropy of the
liquid state increases. Therefore, even though the gaseous state has a
higher entropy, the di erence in entropy between the two systems
decreases. The decrease in entropy di erence lowers the vapor
pressure.
Solute Particle Location
In a pure solvent, all of the liquid molecules on the surface can

evaporate and transition to the gaseous phase. In a solution, some spots
on the surface are occupied by solute molecules, so there is less space
occupied by solvent molecules. Overall, less solvent will transition to the
gaseous phase, resulting in a decrease in vapor pressure.
Equilibrium Vapor Pressure Given by Raoult’s Law
Raoult’s law states that the vapor pressure of an ideal solution is

dependent on the vapor pressure of the pure solvent and the mole
fraction of the component present in the solution. For an ideal solution,
equilibrium vapor pressure is given by Raoult’s law:
⋆
p = p xA
A
In this equation, p is the vapor pressure of the pure solvent and x is

⋆
A A
the mole fraction of the solvent. This law allows us to calculate the vapor
pressure of a given solution, and shows the in uence of all of the
molecules in the solution.
EXAMPLE
Calculate the vapor pressure of a solution consisting of 3

moles of a nonvolatile solute and 15 moles of water at 25 oC,
given that the vapor pressure of pure water at 25 oC is 23.8
torr.
First, calculate the mole fraction of the solvent:

moles solvent
xA =
total moles
15
xA = = 0.83
18
Second, substitute into Raoult’s law and solve:

⋆
p = p xA
A
p = 23.8 torr × 0.83
p = 19.8 torr
Freezing Point Depression
Freezing point depression is a colligative property observed in solutions,

brought on by the introduction of solute molecules to a solvent.
LEARNING OBJECTIVES
Discuss the e ects of a solute on the freezing point of a

solvent
KEY TAKEAWAYS
Key Points
The freezing point depression can be calculated using

the pure solvent freezing point and the molality of the
solution.
At the freezing point, the vapor pressure of both the

solid and liquid form of a compound must be equal.
The freezing point of a substance is the temperature at

which the solid and liquid forms are in equilibrium.
To reattain equilibrium, the freezing point of the solute

and solvent mixture is lowered relative to the original
pure solvent.
Key Terms
freezing point depression: Adding a solute to a solvent

decreases the temperature at which the liquid solvent
becomes a solid.
vapor pressure: The pressure that a vapor exerts, or the

partial pressure if it is mixed with other gases.
van ‘t Ho factor: A measure of the e ect of a solute

on colligative properties.
freezing point: The temperature at which a liquid

freezes, and the solid and liquid phases are in
equilibrium; normally the same as the melting point.
Freezing point depression is the phenomena that describes why adding

a solute to a solvent results in the lowering of the freezing point of the
solvent. When a substance starts to freeze, the molecules slow down
due to the decreases in temperature, and the intermolecular forces start
to take over. The molecules will then arrange themselves in a pattern,
and thus turn into a solid. For example, as water is cooled to the freezing
point, its molecules become slower and hydrogen bonds begin to “stick”
more, eventually creating a solid. If salt is added to the water, the Na+
and Cl– ions attract to the water molecules and interfere with the
formation of the large network solid known as ice. In order to achieve a
solid, the solution must be cooled to an even lower temperature.
The freezing point depression can also be explained in terms of vapor

pressure. Adding solute to a solvent will essentially dilute the solvent
molecules, and according to Raoult’s law, this leads to a decrease in
vapor pressure. Considering the fact that the vapor pressure of the solid
and liquid forms must be the same at freezing point, because otherwise
the system would not be at equilibrium, the lowering of the vapor
pressure leads to the lowering of the temperature at which the vapor
pressures of the liquid and frozen forms of the solution will be equal.
E ect of solutes on physical properties: A triple phase

diagram which shows the pressure and temperature of
the normal boiling and freezing points of a solvent
(green lines) and the boiling and freezing points of a
solution (purple lines). Notice that at 1 atm of pressure,
the freezing point has been lowered (represented by
numbers 2 and 4).
The freezing point depression can be calculated by the formula:
ΔTf = i × Kf × molality
In this equation, ΔT is the freezing point depression, Kf is the freezing

f
point depression constant, and i is the van ‘t Ho factor. The freezing

point depression constant changes depending on the solvent, and the
van ‘t Ho factor accounts for the number of particles that a dissolving

solute creates in solution.
EXAMPLE
What is the freezing point of an aqueous solution when

enough NaCl has been added to create a 0.25 m solution? The
Kf value for water is 1.858 oC/m.
To solve this, you must remember that NaCl breaks into two
ions, Na+ and Cl–, when it dissolves in water. In simplest terms,
this means it has an “i” factor of 2.
ΔTf = i × Kf × molality
oC
ΔTf = 2 × 1.86 × 0.25 m

m
oC
ΔTf = 0.93
This might seem like the end of the problem, but it is not. The
value of 0.93 oC is the change in the freezing point. The new
freezing point of water, which is normally 0 oC, is equal to: 0 –
0.93 = -0.93 oC.
Boiling Point Elevation
The boiling point of a solvent is elevated in the presence of solutes.
LEARNING OBJECTIVES
Discuss the e ects of a solute on the boiling point of a solvent
KEY TAKEAWAYS
Key Points
One of the colligative properties of a solution is boiling

point elevation.
The amount that the boiling point increases in the

presence of solute can be calculated by using the
boiling point elevation constant and the molality of the
solution.
The addition of solute dilutes the solvent molecules and

makes it harder for them to escape into the gaseous
phase.
Key Terms
boiling point: The temperature at which a liquid boils,

with the vapor pressure equal to the given external
pressure.
boiling point elevation: The temperature at which a

substance’s vapor pressure equals the external
pressure increases when another compound is added.
colligative property: A property of solutions that is

directed by the ratio of solute to solvent, regardless of
the identity of the solute.
Colligative Properties and Boiling Point Elevation
There is one category of properties that can only be applied to solutions;

these are known as colligative properties. Properties can be considered
colligative only if they are dependent on the amount of solute present in
the solution, disregarding the identity of the solute itself.
The boiling point of a solvent will increase when a solute is dissolved in

it. This is referred to as boiling point elevation. The elevation of the
boiling point is directly dependent on the amount of solute present in
the solution, but it is not based on the identity of the solute, so it is
considered a colligative property.
The Relationship Between Boiling Point Elevation and Vapor

Pressure
Boiling point elevation can be explained in terms of vapor pressure.

Vapor pressure is de ned as the pressure exerted by a vapor in
thermodynamic equilibrium with its condensed phases at a given
temperature. In layman’s terms, it is simply a measure of the tendency of
the solution molecules to escape by entering the gas phase. A liquid
boils when its vapor pressure is equal to the air pressure.
image
Boiling point: The boiling point of a pure liquid. When the vapor pressure of
the liquid matches the atmospheric pressure, the liquid will boil.
Boiling Point Elevation
A solvent’s vapor pressure will lower when a solute is added. This

happens because of the displacement of solvent molecules by the
solute. This means that some of the of solvent molecules at the surface
of the liquid are replaced by the solute; it can occur in both electrolytic
and non-electrolytic solutions. The lower number of solvent molecules at
the surface means that fewer will evaporate, and thus the vapor
pressure is lowered. For the vapor pressure to equal the atmospheric
pressure, a higher temperature is required, and a higher boiling point is
observed.
Calculating Boiling Point Elevation
The extent of the boiling point elevation can be calculated. It is directly

proportional to the molal concentration of the solution. The amount the
boiling point is elevated is determined using the equation:
ΔTb = i × Kb × m
In this equation, ΔT is the boiling point elevation, K is the boiling

b b
point elevation constant, and m is the molality of the solution. The “i”
factor of the equation also factors in any dissociation that the solute may
undergo; since boiling point elevation is a colligative property, the

number of ions present in an electrolyte a ects the elevation.
EXAMPLE
Calculate the boiling point of an aqueous solution where

enough NaCl is added to make a 0.37 molal solution. The Kb
oC
for water is 0.512 m

.
ΔTb = i × Kb × m
oC
ΔTb = 2 × 0.512 × 0.37 m

m
oC
ΔTb = 0.38
Water normally boils at 100 oC, so the new boiling point of the
solution would be 100.38 oC.
Osmotic Pressure
Osmotic pressure is the pressure needed to nullify the e ects of

osmosis and is directly in uenced by the amount of solute in the system.
LEARNING OBJECTIVES
Discuss the e ects of a solute on the osmotic pressure of a

solution
KEY TAKEAWAYS
Key Points
Osmosis is de ned as the ow of water/ solvent

molecules through a semipermeable membrane from a
region of low to high solute concentration, until

equilibrium is established.
To counter osmotic ow, some pressure must be

applied to the solution in order to prevent pure solvent
from going through the semipermeable membrane
separating the two liquids; this is known as the osmotic
pressure.
The osmotic pressure is the pressure required to

counter, not sustain, osmosis.
The osmotic pressure can be approximated by using

the following formula: Π = iMRT.
Key Terms
osmotic pressure: The hydrostatic pressure exerted by

a solution across a semipermeable membrane from a
pure solvent; the pressure needed to counteract
osmosis.
semipermeable membrane: One that will allow certain

molecules or ions to pass through it by di usion.
osmosis: The net movement of solvent molecules from

a region of high solvent potential to a region of lower
solvent potential through a partially permeable
membrane.
ideal solution: A solution with thermodynamic

properties analogous to those of a mixture of ideal
gases.
A solution is de ned as a homogeneous mixture of both a solute and

solvent. Solutions generally have di erent properties than the solvent
and solute molecules that compose them. Some special properties of
solutions are dependent solely on the amount of dissolved solute
molecules, regardless of what that solute is; these properties are known
as colligative properties.
Osmosis is de ned as the net ow or movement of solvent molecules
through a semipermeable membrane through which solute molecules

cannot pass. If a solution consisting of both solute and solvent
molecules is placed on one side of a membrane and pure solvent is
placed on the other side, there is a net ow of solvent into the solution
side of the membrane.
Imagine osmosis taking place in an upright U-tube. The height of the

solution will continue to increase due to a net ow of solvent until the
added pressure of the height will cause the ow of solution to stop. The
height di erence between the two sides can be be converted into
pressure to nd the osmotic pressure exerted on the solution by the
pure solvent.
image
U-Tube showing osmotic pressure: On the left side of the U-tube is an
aqueous solution, and on the right side is pure water. The pure water is
trying to dilute the solution by travelling through the semipermeable
membrane. Eventually the added weight of the extra water on the left
causes enough pressure to stop osmosis.
Osmotic pressure is the pressure that needs to be applied to a solution

to prevent the inward ow of water across a semipermeable membrane.
Osmotic pressure can also be explained as the pressure necessary to
nullify osmosis. One way to stop osmosis is to increase the hydrostatic
pressure on the solution side of the membrane; this ultimately squeezes
the solvent molecules closer together, increasing their “escaping
tendency.” The escaping tendency of the solution can be raised until it
eventually equals that of the molecules in the pure solvent; at this point,
osmosis will cease. The osmotic pressure is the pressure required to
achieve osmotic equilibrium.
Osmotic pressure: Osmotic pressure is the pressure required to stop

osmosis.
The osmotic pressure (II) of an ideal solution can be approximated by the

Morse equation:
Π = iMRT
Here, i is the van ‘t Ho factor, M is the molarity of the solution, R is the

gas constant, and T is the absolute temperature in Kelvin. We can see
from this equation that the amount of solute present in the solution will
directly a ect the osmotic pressure of the system.
EXAMPLE
What is the osmotic pressure of a 1.35 M solution of NaCl at 25

oC?
First, ll in all of the necessary information, and then solve:
i = 2 (NaCl breaks into two particles)
M = 1.35 moles
R = 0.0821 L×atm
K×mol
L×atm
K×mol
T = 25 oC + 273 = 298 K
Π = 2 × 1.35 × 0.0821 × 298
Π = 66.1 atm
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4/6/2018 Colligative Properties of Nonelectrolyte Solutions | Boundless Chemistry

Colligative Properties of Nonelectrolyte

Vapor Pressure of Nonelectrolyte Solutions

The vapor pressure of a solution is directly in uenced by the number of

Calculate the vapor pressure of a nonelectrolyte solution using

The vapor pressure of a system is a measure of the

Vapor pressure is a colligative property, meaning that

Raoult’s law states that the partial vapor pressure of

raoult’s law: States that the partial vapor pressure of

colligative property: A property of solutions that is

vapor pressure: The pressure that a vapor exerts, or its

Colligative Properties: Vapor Pressure

Vapor pressure is a measure of the tendency of a material to escape into

Vapor pressure: Vapor pressure measures the

Lowering Vapor Pressure

The vapor pressure of a solvent is lowered by the addition of a non-

Solute Particle Location

In a pure solvent, all of the liquid molecules on the surface can

Equilibrium Vapor Pressure Given by Raoult’s Law

Raoult’s law states that the vapor pressure of an ideal solution is

In this equation, p is the vapor pressure of the pure solvent and x is

Calculate the vapor pressure of a solution consisting of 3

First, calculate the mole fraction of the solvent:

Second, substitute into Raoult’s law and solve:

Freezing Point Depression

Freezing point depression is a colligative property observed in solutions,

Discuss the e ects of a solute on the freezing point of a

The freezing point depression can be calculated using

At the freezing point, the vapor pressure of both the

The freezing point of a substance is the temperature at

To reattain equilibrium, the freezing point of the solute

freezing point depression: Adding a solute to a solvent

vapor pressure: The pressure that a vapor exerts, or the

van ‘t Ho factor: A measure of the e ect of a solute

freezing point: The temperature at which a liquid

Freezing point depression is the phenomena that describes why adding

The freezing point depression can also be explained in terms of vapor

E ect of solutes on physical properties: A triple phase

The freezing point depression can be calculated by the formula:

In this equation, ΔT is the freezing point depression, Kf is the freezing

point depression constant, and i is the van ‘t Ho factor. The freezing

van ‘t Ho factor accounts for the number of particles that a dissolving

What is the freezing point of an aqueous solution when

ΔTf = 2 × 1.86 × 0.25 m

Boiling Point Elevation

The boiling point of a solvent is elevated in the presence of solutes.

Discuss the e ects of a solute on the boiling point of a solvent

One of the colligative properties of a solution is boiling

The amount that the boiling point increases in the

The addition of solute dilutes the solvent molecules and

boiling point: The temperature at which a liquid boils,

boiling point elevation: The temperature at which a

colligative property: A property of solutions that is

Colligative Properties and Boiling Point Elevation

There is one category of properties that can only be applied to solutions;

The boiling point of a solvent will increase when a solute is dissolved in

The Relationship Between Boiling Point Elevation and Vapor

Boiling point elevation can be explained in terms of vapor pressure.

Boiling Point Elevation

A solvent’s vapor pressure will lower when a solute is added. This

Calculating Boiling Point Elevation

The extent of the boiling point elevation can be calculated. It is directly

In this equation, ΔT is the boiling point elevation, K is the boiling