Physical Transformation of Pure Substances

CHAPTER 4

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Chapter 13

Some Properties of
Liquids
Viscosity
Viscosity is the resistance of a liquid to
flow.
A liquid flows by sliding molecules over
each other.
The stronger the intermolecular forces,
the higher the viscosity.
Surface Tension
Bulk molecules (those in the liquid) are
equally attracted to their neighbours.
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Chapter 11

Surface
Tension

Some Properties of
Liquids
Surface Tension
Surface molecules are only attracted inwards
towards the bulk molecules.
Therefore, surface molecules are packed more

closely than bulk molecules.

Surface

tension is the amount of energy

required to increase the surface area of a
liquid.
Cohesive forces bind molecules to each other.
Adhesive forces bind molecules to a surface.
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Chapter 11

Some Properties of
Liquids
Surface Tension
Meniscus is the shape of the liquid
surface.
If adhesive forces are greater than

cohesive forces, the liquid surface is

attracted to its container more than the
bulk molecules. Therefore, the meniscus
is U-shaped (e.g. water in glass).
If cohesive forces are greater than
adhesive forces, the meniscus is curved
downwards.
Capillary

Action: When a narrow glass

tube is placed in water, the meniscus
pulls the water up the tube.

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Chapter 11

Phase Changes
Surface

molecules are only attracted inwards

towards the bulk molecules.
Sublimation: solid gas. Hsub > 0 (endothermic).
Vaporization: liquid gas. Hvap > 0
(endothermic).
Melting or fusion: solid liquid. Hfus > 0
(endothermic).
Deposition: gas solid. Hdep < 0 (exothermic).
Condensation: gas liquid. Hcon < 0
(exothermic).
Freezing: liquid solid. Hfre < 0 (exothermic).
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Chapter 11

Phase Changes

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Chapter 11

Phase Changes
Critical Temperature and Pressure
Gases liquefied by increasing
pressure at some temperature.
Critical temperature: the minimum
temperature for liquefaction of a gas
using pressure.
Critical pressure: pressure required
for liquefaction.
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Chapter 11

Vapor Pressure
Explaining Vapor Pressure on the
Molecular Level
Some of the molecules on the surface of a
liquid have enough energy to escape the
attraction of the bulk liquid.
These molecules move into the gas phase.
As the number of molecules in the gas phase
increases, some of the gas phase molecules
strike the surface and return to the liquid.
After some time the pressure of the gas will
be constant at the vapor pressure.
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Chapter 11

Vapor Pressure
Explaining Vapor Pressure on the
Molecular Level

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Chapter 11

Vapor Pressure
Explaining Vapor Pressure on the Molecular Level
Dynamic Equilibrium: the point when as many
molecules escape the surface as strike the surface
evaporation and condensation occur at equal rate.
Vapor pressure is the pressure exerted when the liquid
and vapor are in dynamic equilibrium.
Volatility, Vapor Pressure, and Temperature
If equilibrium is never established then the liquid
evaporates.
Volatile substances evaporate rapidly.
Vapor pressure increases with increase in temperature.

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Chapter 11

Vapor Pressure
Vapor Pressure and Boiling Point
Liquids boil when the external
pressure equals the vapor pressure.
Temperature of boiling point
increases as pressure increases.

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Chapter 11

Phase Diagrams
Phase

diagram: plot of pressure vs.

temperature summarizing all
equilibria between phases.
Given a temperature and pressure,
phase diagrams tell us which phase
will exist.
Any temperature and pressure
combination not on a curve
represents a single phase.
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Chapter 11

Phase Diagrams
Features

of a phase diagram:

Triple point (A): temperature and pressure at which

all three phases are in equilibrium.

Vapor-pressure curve (A to B): generally as pressure
increases, temperature increases.
Critical point (B): critical temperature and pressure
for the gas (beyond this liquid and gas become
indistinguishable)
Melting point curve: as pressure increases, the solid
phase is favored if the solid is more dense than the
liquid.
Normal melting point: melting point at 1 atm.

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Chapter 11

Phase Diagrams

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Chapter 11

Phase Diagrams
The Phase Diagrams of H2O and
CO2

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Chapter 11

Phase Diagrams
The Phase Diagrams of H2O and
CO2
Water:
The melting point curve slopes to the left

because ice is less dense than water.

Triple point occurs at 0.0098C and 4.58
mmHg.
Normal melting (freezing) point is 0C.
Normal boiling point is 100C.
HallCritical
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2003
Chapter 11
point
is 374C and 218 atm.

Phase Diagrams
The Phase Diagrams of H2O and
CO2
Carbon Dioxide:
Triple point occurs at -56.4C and 5.11

atm.
Normal sublimation point is -78.5C. (At
1 atm CO2 sublimes it does not melt.)
Critical point occurs at 31.1C and 73

atm.
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Chapter 11

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Chapter 13

Properties of Solutions

CHAPTER 4

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Chapter 13

The Solution Process

A

solution is a homogeneous mixture

of solute (present in smallest
amount) and solvent (present in
largest amount).
Solutes and solvent are components
of the solution.
In the process of making solutions
with condensed phases,
intermolecular forces become
rearranged.

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Chapter 13

The Solution Process

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Chapter 13

The Solution Process

Energy Changes and
Solution Formation
There are three
energy steps in
forming a solution:
separation of solute

molecules (H1),
separation of solvent
molecules (H2),
formation of solutesolvent interactions
(H3).
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Chapter 13

The Solution Process

Energy Changes and Solution
Formation
We define the enthalpy change in
the solution process as
Hsoln = H1 + H2 + H3.
Hsoln can either be positive or
negative depending on the
intermolecular forces.
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Chapter 13

The Solution Process

Energy Changes and Solution
Formation
Breaking attractive intermolecular
forces is always endothermic.
Forming attractive intermolecular
forces is always exothermic.

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Chapter 13

The Solution Process

Energy Changes and Solution
Formation
To determine whether Hsoln is
positive or negative, we consider the
strengths of all solute-solute and
solute-solvent interactions:
H1 and H2 are both positive.
H3 is always negative.
It is possible to have either H3 > (H1 +
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Chapter 13

The Solution Process

Energy Changes and Solution Formation
Examples:
NaOH added to water has Hsoln = -44.48 kJ/mol.
NH4NO3 added to water has Hsoln = + 26.4 kJ/mol.

Rule:

polar solvents dissolve polar solutes.

Non-polar solvents dissolve non-polar solutes
If Hsoln is too endothermic a solution will not form.
NaCl in gasoline: the ion-dipole forces are weak

because gasoline is non-polar. Therefore, the iondipole forces do not compensate for the
separation of ions.
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Chapter 13

The Solution Process

Energy

Changes and Solution

Formation
Water in octane: water has strong H-

bonds. There are no attractive forces

between water and octane to
compensate for the H-bonds.

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Chapter 13

The Solution Process

Solution Formation, Spontaneity, and
Disorder
A spontaneous process occurs without
outside intervention.
When energy of the system decreases (e.g.
dropping a book and allowing it to fall to a
lower potential energy), the process is
spontaneous.
Some spontaneous processes do not involve
the system moving to a lower energy state
(e.g. an endothermic reaction).
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Chapter 13

The Solution Process

Solution Formation, Spontaneity, and
Disorder
If the process leads to a greater state of
disorder, then the process is spontaneous.
Example: a mixture of CCl 4 and C6H14 is less
ordered than the two separate liquids.
Therefore, they spontaneously mix even
though Hsoln is very close to zero.
There are solutions that form by physical
processes and those by chemical processes.
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Chapter 13

The Solution Process

Solution Formation, Spontaneity, and Disorder

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Chapter 13

The Solution Process

Solution Formation and Chemical Reactions
Example: a mixture of CCl4 and C6H14 is less
ordered
Consider:
Ni(s) + 2HCl(aq) NiCl2(aq) + H2(g).
Note

the chemical form of the substance being

dissolved has changed (Ni NiCl2).
When all the water is removed from the
solution, no Ni is found only NiCl26H2O.
Therefore, Ni dissolution in HCl is a chemical
process.
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Chapter 13

The Solution Process

Solution Formation and Chemical
Reactions
Example:
NaCl(s) + H2O (l) Na+(aq) + Cl(aq).
When

the water is removed from the

solution, NaCl is found. Therefore,
NaCl dissolution is a physical
process.

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Chapter 13

Saturated Solutions and

Solubility
Dissolve:

solute + solvent

solution.
Crystallization: solution solute +
solvent.
Saturation: crystallization and
dissolution are in equilibrium.
Solubility: amount of solute required
to form a saturated solution.
Supersaturated: a solution formed
when more solute is dissolved than

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Chapter 13

Prentice Hall 2003

Chapter 13

Factors Affecting
Solubility
Solute-Solvent Interaction
Polar liquids tend to dissolve in polar solvents.
Miscible liquids: mix in any proportions.
Immiscible liquids: do not mix.
Intermolecular forces are important: water
and ethanol are miscible because the broken
hydrogen bonds in both pure liquids are reestablished in the mixture.
The number of carbon atoms in a chain affect
solubility: the more C atoms the less soluble
in water.
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Chapter 13

Factors Affecting
Solubility
Solute-Solvent Interaction
The number of -OH groups within a
molecule increases solubility in
water.
Generalization: like dissolves like.
The more polar bonds in the
molecule, the better it dissolves in a
polar solvent.
The less polar the molecule the less
it dissolves in a polar solvent and the

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Chapter 13

Factors Affecting
Solubility
Solute-Solvent Interaction

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Chapter 13

Factors Affecting
Solubility
Solute-Solvent Interaction

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Chapter 13

Factors Affecting
Solubility
Solute-Solvent Interaction
Network solids do not dissolve
because the strong intermolecular
forces in the solid are not reestablished in any solution.
Pressure Effects
Solubility of a gas in a liquid is a
function of the pressure of the gas.
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Chapter 13

Factors Affecting
Solubility
Pressure Effects

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Chapter 13

Factors Affecting
Solubility
Pressure Effects
The higher the pressure, the more molecules of gas are
close to the solvent and the greater the chance of a
gas molecule striking the surface and entering the
solution.
Therefore, the higher the pressure, the greater the solubility.
The lower the pressure, the fewer molecules of gas are close

to the solvent and the lower the solubility.

If

Sg is the solubility of a gas, k is a constant, and Pg is

the partial pressure of a gas, then Henrys Law gives:

S g kPg
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Chapter 13

Factors Affecting
Solubility
Pressure Effects
Carbonated beverages are bottled
with a partial pressure of CO2 > 1
atm.
As the bottle is opened, the partial
pressure of CO2 decreases and the
solubility of CO2 decreases.
Therefore, bubbles of CO2 escape
from solution.
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Chapter 13

Prentice Hall 2003

Chapter 13

Factors Affecting
Solubility
Temperature Effects
Experience tells us that sugar
dissolves better in warm water than
cold.
As temperature increases, solubility
of solids generally increases.
Sometimes, solubility decreases as
temperature increases (e.g.
Ce2(SO4)3).
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Chapter 13

Factors Affecting
Solubility
Temperature Effects
Experience tells us that carbonated
beverages go flat as they get warm.
Therefore, gases get less soluble as
temperature increases.
Thermal pollution: if lakes get too
warm, CO2 and O2 become less
soluble and are not available for
plants or animals.
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Chapter 13

Ways of Expressing
Concentration
Mass Percentage, ppm, and ppb
All methods involve quantifying
amount of solute per amount of
solvent (or solution).
Generally amounts or measures are
masses, moles or liters.
Qualitatively solutions are dilute or
concentrated.
mass of component in solution
Definitions:
mass % of component
100
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Chapter 13

total mass of solution

Prentice Hall 2003

Chapter 13

Ways of Expressing
Concentration
Mass Percentage, ppm, and ppb
mass of component in solution
ppm of component
10 6
total mass of solution

Parts

per million (ppm) can be

expressed as 1 mg of solute per
kilogram of solution.
If the density of the solution is 1g/mL,

then 1 ppm = 1 mg solute per liter of

solution.
Parts

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per billion (ppb) are 1 g of

Chapter 13

Ways of Expressing
Concentration
Mass Percentage, ppm, and ppb
mass of component in solution
ppb of component
109
total mass of solution
Mole Fraction, Molarity, and Molality

Recall

mass can be converted to

moles using the molar mass.

moles of component in solution

Mole fraction of component
total moles of solution

moles solute
Molarity
liters of solution
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Chapter 13

Ways of Expressing
Concentration
Mole Fraction, Molarity, and
Molality
We define
moles solute
Molality, m
kg of solvent

Converting

between molarity (M) and

molality (m) requires density.

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Chapter 13

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Chapter 13

Prentice Hall 2003

Chapter 13

Colligative Properties
Colligative

properties depend on quantity

of solute molecules. (E.g. freezing point
depression and melting point elevation.)

Lowering Vapor Pressure

Non-volatile solvents reduce the ability of
the surface solvent molecules to escape
the liquid.
Therefore, vapor pressure is lowered.
The amount of vapor pressure lowering
depends on the amount of solute.
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Chapter 13

Colligative Properties
Lowering Vapor Pressure

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Chapter 13

Colligative Properties
Lowering Vapor Pressure
Raoults Law: PA is the vapor
pressure with solute, PA is the vapor
pressure without solvent, and A is
PA A P A
the mole fraction of A, then
Recall

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PA A Ptotal

Daltons Law:

Chapter 13

Prentice Hall 2003

Chapter 13

Colligative Properties
Lowering Vapor Pressure
Ideal solution: one that obeys Raoults law.
Raoults law breaks down when the solventsolvent and solute-solute intermolecular forces
are greater than solute-solvent intermolecular
forces.
Boiling-Point Elevation
Goal: interpret the phase diagram for a solution.
Non-volatile solute lowers the vapor pressure.
Therefore the triple point - critical point curve is
lowered
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Chapter 13

Colligative Properties
Boiling-Point Elevation
At 1 atm (normal boiling point of
pure liquid) there is a lower vapor
pressure of the solution. Therefore,
a higher temperature is required to
reach a vapor pressure of 1 atm for
the solution (Tb).
Molal boiling-point-elevation
Tb Kb m
constant, Kb, expresses how much
T changes with molality, m:

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Chapter 13

Colligative Properties
Freezing Point Depression
At 1 atm (normal boiling point of
pure liquid) there is no depression by
definition
When a solution freezes, almost pure
solvent is formed first.
Therefore, the sublimation curve for the

pure solvent is the same as for the

solution.
Therefore, the triple point occurs at a
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Chapter 13

Colligative Properties
Freezing Point Depression
The melting-point (freezing-point)
curve is a vertical line from the triple
point.
The solution freezes at a lower
temperature (Tf) than the pure
solvent.
Decrease in freezing point (Tf) is
T f K f m
directly proportional to molality (Kf is
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Chapter 13

Prentice Hall 2003

Chapter 13

Prentice Hall 2003

Chapter 13

Colligative Properties
Freezing Point Depression

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Chapter 13

Colligative Properties
Osmosis
Semipermeable membrane: permits passage of
some components of a solution. Example: cell
membranes and cellophane.
Osmosis: the movement of a solvent from low
solute concentration to high solute concentration.
There is movement in both directions across a
semipermeable membrane.
As solvent moves across the membrane, the fluid
levels in the arms becomes uneven.
Eventually the pressure difference between the
arms stops osmosis.
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Chapter 13

Colligative Properties
Osmosis

Prentice Hall 2003

Chapter 13

Colligative Properties
Osmosis
Osmotic pressure, , is the pressure
required to stop osmosis:
V nRT

RT
V
MRT
Isotonic

solutions: two solutions with

the same separated by a
semipermeable membrane.

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Chapter 13

Prentice Hall 2003

Chapter 13

Colligative Properties
Osmosis
Hypotonic solutions: a solution of
lower than a hypertonic solution.
Osmosis is spontaneous.
Red blood cells are surrounded by
semipermeable membranes.

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Chapter 13

Colligative Properties
Osmosis
Crenation:
red blood cells placed in hypertonic

solution (relative to intracellular

solution);
there is a lower solute concentration in
the cell than the surrounding tissue;
osmosis occurs and water passes
through the membrane out of the cell.
The cell shrivels up.
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Chapter 13

Colligative Properties
Osmosis

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Chapter 13

Colligative Properties
Osmosis
Hemolysis:
red blood cells placed in a hypotonic

solution;
there is a higher solute concentration in
the cell;
osmosis occurs and water moves into
the cell.
The cell bursts.
To

prevent crenation or hemolysis, IV

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Chapter 13

Colligative Properties
Osmosis
Cucumber placed in NaCl solution loses water
to shrivel up and become a pickle.
Limp carrot placed in water becomes firm
because water enters via osmosis.
Salty food causes retention of water and
swelling of tissues (edema).
Water moves into plants through osmosis.
Salt added to meat or sugar to fruit prevents
bacterial infection (a bacterium placed on the
salt will lose water through osmosis and die).
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Chapter 13

Colligative Properties
Osmosis
Active transport is the movement of
nutrients and waste material through
a biological system.
Active transport is not spontaneous.

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Chapter 13