12 Lecture

Chemistry: A Molecular Approach, 2nd Ed.
Nivaldo Tro
Chapter 12
Solutions
Roy Kennedy
Massachusetts Bay Community College
Wellesley Hills, MA
Copyright
2011 Pearson Education, Inc.
Thirsty Seawater
Drinking seawater can cause you to dehydrate
Seawater is a homogeneous mixture of salts with water
Seawater contains high concentrations of salts
higher than the salt content of your cells
As seawater passes through your body, it pulls water out

of your cells; due mainly to natures tendency toward
spontaneous mixing
This reduces your cells water level and usually results in
diarrhea as this extra liquid flows out with the seawater
Tro: Chemistry: A Molecular Approach, 2/e
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Seawater
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Seawater
Drinking seawater will dehydrate you and give
you diarrhea
The cell wall acts as a barrier to solute moving
so the only way for the seawater and the cell
solution to have uniform mixing is for water to
flow out of the cells of your intestine and into
your digestive tract
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Solutions
Homogeneous mixtures
composition may vary from one sample to another
appears to be one substance, though really contains
multiple materials
Most homogeneous materials we encounter are

actually solutions
e.g., air and seawater
Nature has a tendency toward spontaneous

mixing
generally, uniform mixing is more energetically
favorable
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Solutions
When table salt is mixed with water, it seems to

disappear, or become a liquid the mixture is
homogeneous
the salt is still there, as you can tell from the taste, or simply
boiling away the water
Homogeneous mixtures are called solutions

The component of the solution that changes state is
called the solute
The component that keeps its state is called the solvent
if both components start in the same state, the major
component is the solvent
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Examples of Solutions
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Common Types of Solution

Solution Phase
Gaseous solutions
Liquid solutions
Solid solutions
Solute
Phase
Solvent
Phase
Gas
Gas
Gas
Liquid
Solid
Liquid
Liquid
Liquid
Soda (CO2 in H2O)
Solid
Solid
Brass (Zn in Cu)
Example
Air (mostly N2 & O2)
Vodka (C2H5OH in H2O)
Seawater (NaCl in H2O)
Solutions that contain Hg and some other metal
are called amalgams

Solutions that contain metal solutes and a
metal solvent are called alloys
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Brass
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Solubility
When one substance (solute) dissolves in
another (solvent) it is said to be soluble
salt is soluble in water
bromine is soluble in methylene chloride
When one substance does not dissolve in

another it is said to be insoluble
oil is insoluble in water
The solubility of one substance in another

depends on two factors natures tendency
toward mixing, and the types of
intermolecular attractive forces
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Spontaneous Mixing
When solutions with different solute concentrations

come in contact, they spontaneously mix to result in a
uniform distribution of solute throughout the solution
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Mixing and the Solution Process:

Entropy
Most processes occur because the end
result has less potential energy

But formation of a solution does not
necessarily lower the potential energy of
the system
When two ideal gases are put into the
same container, they spontaneously mix
even though the difference in attractive
forces is negligible
The gases mix because the energy of

the system is lowered through the
release of entropy
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Mixing and the Solution Process

Entropy
Entropy is the measure of
energy dispersal throughout the

system
Energy has a spontaneous drive
to spread out over as large a
volume as it is allowed
By each gas expanding to fill the
container, it spreads its energy
out and lowers its entropy
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Intermolecular Forces and the

Solution Process
Energy changes in the formation of most solutions
also involve differences in attractive forces
between the particles
For the solvent and solute to mix you must
overcome
1. all of the solutesolute attractive forces
2. some of the solventsolvent attractive forces
both processes are endothermic
At least some of the energy to do this comes from

making new solutesolvent attractions
which is exothermic
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Intermolecular Attractions
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Solution Interactions
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Relative Interactions and Solution Formation
When the solute-to-solvent attractions are weaker

than the sum of the solute-to-solute and solventto-solvent attractions, the solution will only form if
the energy difference is small enough to be
overcome by the increase in entropy from mixing
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Solubility
There is usually a limit to the solubility of one
substance in another
gases are always soluble in each other
two liquids that are mutually soluble are said to be
miscible
alcohol and water are miscible
oil and water are immiscible
The maximum amount of solute that can be

dissolved in a given amount of solvent is called the
solubility
The solubility of one substance in another varies
with temperature and pressure
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Will It Dissolve?
Chemists Rule of Thumb
Like Dissolves Like
A chemical will dissolve in a solvent if it has a similar structure

to the solvent
when the solvent and solute structures are similar, the solvent
molecules will attract the solute particles at least as well as the solute
particles are attracted to each other
Polar molecules and ionic compounds will be more soluble in

polar solvents
Nonpolar molecules will be more soluble in nonpolar solvents
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Classifying Solvents
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Example 12.1a: Predict whether the following

vitamin is soluble in fat or water
Water is a polar solvent.
Fat is mostly made of
nonpolar molecules.
The four OH groups
make the molecule
highly polar and it will
also H-bond to
water.
Vitamin C is water
soluble.
Vitamin C
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Example 12.1b: Predict whether the following

vitamin is soluble in fat or water
Water is a polar solvent.
Fat is mostly made of
nonpolar molecules.
The two C=O groups are
polar, but their geometric
symmetry suggests their
pulls will cancel and the
molecule will be
nonpolar.
Vitamin K3
Vitamin K3 is fat soluble.

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Practice Decide if the following are more

soluble in hexane, C6H14, or water
nonpolar molecule
more soluble in C6H14
polar molecule
more soluble in H2O
nonpolar part dominant
more soluble in C6H14
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Practice Explain the solubility trends

seen in the table below
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Practice Explain the solubility trends

seen in the table below
These alcohols all have a polar
OH part and a nonpolar CHn part.
As we go down the table the
nonpolar part gets larger, but the
amount of OH stays the same.
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We therefore expect that the

solubility in water (polar solvent)
should decrease and the
solubility in hexane (nonpolar
solvent) should increase, and it
does. Copyright 2011 Pearson Education, Inc.
Heat of Solution
When some compounds, such as NaOH,
dissolve in water, a lot of heat is released
the container gets hot
When other compounds, such as NH4NO3,

dissolve in water, heat is absorbed from the
surroundings
the container gets cold
Why is this?
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Energetics of Solution Formation: the

Enthalpy of Solution
To make a solution you must
1. overcome all attractions between the solute
particles; therefore Hsolute is endothermic
2. overcome some attractions between solvent
molecules; therefore Hsolvent is endothermic
3. form new attractions between solute particles and
solvent molecules; therefore Hmix is exothermic
The overall H for making a solution depends on the
relative sizes of the H for these three processes
Hsoln = Hsolute + Hsolvent + Hmix
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Solution Process
1. Add energy in to overcome all solutesolute attractions

3. Form
new
attractions,
releasingattractions
energy
2. Add
energy
in solutesolvent
to overcome some
solventsolvent
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Energetics of Solution Formation

If the total energy cost for
breaking attractions between
particles in the pure solute
less than
and pure solvent is greater
the energy
released
in
than
the energy
released
in
making the new attractions
between the solute and
solvent, the overall process
exothermic
will be endothermic
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Heats of Hydration
For aqueous solutions of ionic compounds, the energy

added to overcome the attractions between water
molecules and the energy released in forming
attractions between the water molecules and ions is
combined into a term called the heat of hydration
attractive forces between ions = lattice energy
Hsolute = Hlattice energy
attractive forces in water = H-bonds

attractive forces between ion and water = iondipole
Hhydration = heat released when 1 mole of gaseous ions
dissolves in water = Hsolvent + Hmix
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Ion-Dipole Interactions
When ions dissolve in water they become hydrated
each ion is surrounded by water molecules
The formation of these ion-dipole attractions causes the

heat of hydration to
be very exothermic
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Heats of Solution for

Ionic Compounds
For an aqueous solution of an ionic compound,
the Hsolution is the difference between the Heat
of Hydration and the Lattice Energy
Hsolution = Hsolute+ Hsolvent + Hmix

Hsolution = Hlattice energy+ Hsolvent + Hmix
Hsolution = H
H+lattice
H
Henergy
hydration
lattice energy
hydration
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Heat of Hydration
Hsolution = Hhydration Hlattice energy

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Comparing Heat of Solution to

Heat of Hydration
Because the lattice energy is always exothermic, the size
and sign on the Hsoln tells us something about Hhydration
If the heat of solution is large and endothermic, then the

amount of energy it costs to separate the ions is more
than the energy released from hydrating the ions
Hhydration < Hlattice when Hsoln is (+)
If the heat of solution is large and exothermic, then the

amount of energy it costs to separate the ions is less than
the energy released from hydrating the ions
Hhydration > Hlattice when Hsoln is ()
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Practice What is the lattice energy of KI if

Hsoln = +21.5 kJ/mol and the Hhydration = 583 kJ/mol?
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Practice What is the lattice energy of KI if

Hsoln = +21.5 kJ/mol and the Hhydration = 583 kJ/mol?
Given: Hsoln = +21.5 kJ/mol, Hhydration = 583 kJ/mol
Find: Hlattice, kJ/mol
Conceptual
Plan:
Relationships:
Hsoln = Hhydration Hlattice
Solve:
Check: the unit is correct, the lattice energy being

exothermic is correct
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Solution Equilibrium
The dissolution of a solute in a solvent is an
equilibrium process
Initially, when there is no dissolved solute, the only
process possible is dissolution
Shortly after some solute is dissolved, solute particles
can start to recombine to reform solute molecules
but the rate of dissolution >> rate of deposition and
the solute continues to dissolve
Eventually, the rate of dissolution = the rate of
deposition the solution is saturated with solute and
no more solute will dissolve
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Solution Equilibrium
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Solubility Limit
A solution that has the solute and solvent in dynamic
equilibrium is said to be saturated
if you add more solute it will not dissolve
the saturation concentration depends on the temperature
and pressure of gases
A solution that has less solute than saturation is said

to be unsaturated
more solute will dissolve at this temperature
A solution that has more solute than saturation is

said to be supersaturated
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How Can You Make a Solvent Hold

More Solute Than It Is Able To?
Solutions can be made saturated at non-room conditions
then allowed to come to room conditions slowly
For some solutes, instead of coming out of solution
when the conditions change, they get stuck in-between
the solvent molecules and the solution becomes
supersaturated
Supersaturated solutions are unstable and lose all the
solute above saturation when disturbed
e.g. shaking a carbonated beverage
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Adding a Crystal of NaC2H3O2 to a

Supersaturated Solution
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Temperature Dependence of
Solubility of Solids in Water
Solubility is generally given in grams of solute that
will dissolve in 100 g of water
For most solids, the solubility of the solid increases
as the temperature increases
when Hsolution is endothermic
Solubility curves can be used to predict whether a

solution with a particular amount of solute dissolved
in water is saturated (on the line), unsaturated
(below the line), or supersaturated (above the line)
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Solubility Curves
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Temperature Dependence of Solid

Solubility in Water (g/100 g H2O)
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Purification by Recrystallization
One of the common operations
performed by a chemist is removing
impurities from a solid compound
One method of purification involves
dissolving a solid in a hot solvent
until the solution is saturated
As the solution slowly cools, the
solid crystallizes out, leaving
impurities behind
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Recrystallization of KNO3
KNO3 can be purified by
dissolving a little less

then 106 g in 100 g of
water at 60 C then
allowing it to cool slowly
When it cools to 0 C
only 13.9 g will remain
in solution, the rest will
precipitate out
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Practice Decide if each of the following solutions is

saturated, unsaturated, or supersaturated
50 g KNO3 in 100 g H2O @ 34 C
saturated
50 g KNO3 in 100 g H2O @ 50 C
unsaturated
50 g KNO3 in 50 g H2O @ 50 C
supersaturated
100 g NH4Cl in 200 g H2O @ 70 C
unsaturated
100 g NH4Cl in 150 g H2O @ 50 C
supersaturated
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Temperature Dependence of Solubility of

Gases in Water
Gases generally have lower solubility in water
than ionic or polar covalent solids because
most are nonpolar molecules
gases with high solubility usually are actually
reacting with water
For all gases, the solubility of the gas

decreases as the temperature increases
the Hsolution is exothermic because you do not need
to overcome solutesolute attractions
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Temperature Dependence of Gas Solubility

in Water (g/100 g H2O)
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Pressure Dependence of Solubility of

Gases in Water
The larger the partial pressure of a gas in
contact with a liquid, the more soluble the gas
is in the liquid
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Henrys Law
The solubility of a gas
(Sgas) is directly
proportional to its
partial pressure, (Pgas)
Sgas = kHPgas
kH is called the Henrys

Law Constant
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Relationship between Partial Pressure

and Solubility of a Gas
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persrst
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Example 12.2: What pressure of CO 2 is required

to keep the [CO2] = 0.12 M in soda at 25 C?
Given: S = [CO2] = 0.12 M,
Find: P of CO2, atm
[CO2]
Conceptual
Plan:
Relationships: S = k P, k = 3.4 x 102 M/atm

H
H
Solve:
Check: the unit is correct, the pressure higher than 1 atm

meets our expectation from general experience
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Practice How many grams of NH3 will dissolve in

0.10 L of solution when its partial pressure is 7.6 torr?
(kH = 58 M/atm)
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Practice How many grams of NH3 will dissolve in

0.10 L of solution when its partial pressure is 7.6 torr?
Given: P of NH3 = 7.6 torr; 0.10 L
Find: mass of NH3, g
Conceptual
Plan:
Relationships:
S=kHP, kH= 58 M/atm, 1 atm = 760torr, 1 mol =17.04 g
Solve:
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Concentrations
Solutions have variable composition
To describe a solution, you need to describe the
components and their relative amounts

The terms dilute and concentrated can be used
as qualitative descriptions of the amount of solute
in solution
Concentration = amount of solute in a given
amount of solution
occasionally amount of solvent
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Solution Concentration
Molarity
Moles of solute per 1 liter of solution
Used because it describes how many
molecules of solute in each liter of solution

If a sugar solution concentration is 2.0 M, 1
liter of solution contains 2.0 moles of sugar, 2
liters = 4.0 moles sugar, 0.5 liters = 1.0 mole
sugar
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Molarity and Dissociation

The molarity of the ionic compound allows you
to determine the molarity of the dissolved ions

CaCl2(aq) = Ca2+(aq) + 2 Cl(aq)
A 1.0 M CaCl2(aq) solution contains 1.0 moles
of CaCl2 in each liter of solution
1 L = 1.0 moles CaCl2, 2 L = 2.0 moles CaCl2
Because each CaCl2 dissociates to give one

Ca2+, a 1.0 M CaCl2 solution is 1.0 M Ca2+
1 L = 1.0 moles Ca2+, 2 L = 2.0 moles Ca2+
Because each CaCl2 dissociates to give 2 Cl, a

1.0 M CaCl2 solution is 2.0 M Cl
1 L = 2.0 moles Cl, 2 L = 4.0 moles Cl

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Solution Concentration
Molality, m
Moles of solute per 1 kilogram of solvent
defined in terms of amount of solvent, not solution
like the others
Does not vary with temperature

because based on masses, not volumes
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Parts Solute in Parts Solution

Parts can be measured by mass or volume
Parts are generally measured in same units
by mass in grams, kilogram, lbs, etc.
by volume in mL, L, gallons, etc.
mass and volume combined in grams and mL
Percentage = parts of solute in every 100 parts solution

if a solution is 0.9% by mass, then there are 0.9 grams of solute in every 100 grams
of solution
or 0.9 kg solute in every 100 kg solution
Parts per million = parts of solute in every 1 million parts solution

if a solution is 36 ppm by volume, then there are 36 mL of solute in 1 million mL of
solution
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Percent Concentration
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Parts Per Million Concentration
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PPM
grams of solute per 1,000,000 g of solution
mg of solute per 1 kg of solution
1 liter of water = 1 kg of water
for aqueous solutions we often approximate the kg of the
solution as the kg or L of water
for dilute solutions, the difference in density between the
solution and pure water is usually negligible
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Parts Per Billion Concentration
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Using Concentrations as
Conversion Factors
Concentrations show the relationship between the
amount of solute and the amount of solvent
12%(m/m) sugar(aq) means 12 g sugar 100 g solution
or 12 kg sugar 100 kg solution; or 12 lbs. 100 lbs. solution
5.5%(m/v) Ag in Hg means 5.5 g Ag 100 mL solution

22%(v/v) alcohol(aq) means 22 mL EtOH 100 mL solution
The concentration can then be used to convert the

amount of solute into the amount of solution, or
vice- versa
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Example 12.3: What volume of 10.5% by

mass soda contains 78.5 g of sugar?
Given: 78.5 g sugar
Find: volume, mL
Conceptual g solute
Plan:
g soln
mL soln
Relationships: 100 g soln = 10.5 g sugar, 1 mL soln = 1.04 g

Solve:
Check: the unit is correct, the magnitude seems reasonable

as the mass of sugar 10% the volume of solution
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Preparing a Solution
Need to know amount of solution and
concentration of solution
Calculate the mass of solute needed
start with amount of solution
use concentration as a conversion factor
5% by mass 5 g solute 100 g solution
Dissolve the grams of solute in enough solvent to

total the total amount of solution.
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Practice How would you prepare 250.0 mL of

19.5% by mass CaCl2? (d = 1.18 g/mL)
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Practice How would you prepare 250.0 mL of

19.5% by mass CaCl2? (d = 1.18 g/mL)
Given: 250.0 mL solution
Find: mass CaCl2, g
Conceptual mL soln
Plan:
g soln
g solute
Relationships: 100 g soln = 19.5 g CaCl2, 1 mL soln = 1.18 g

Solve:
Answer: Dissolve 57.5 g of CaCl2 in enough water to total

250.0 mL
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Solution Concentrations
Mole Fraction, XA
The mole fraction is the fraction of the moles of one component in
the total moles of all the components of the solution
Total of all the mole fractions in a solution = 1
Unitless
The mole percentage is the percentage of the moles of one
component in the total moles of all the components of the solution
= mole fraction x 100%
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Example 12.4a: What is the molarity of a solution

prepared by mixing 17.2 g of C2H6O2 with 0.500 kg of
H2O to make 515 mL of solution?
Given: 17.2
g Cmol
kg H2kg
O, H
515
soln
0.2771
C2,H0.500
0.515
L
2H6O
6O2, 0.500
2O, mL
Find: M
Conceptual g C2H6O2
Plan:
mol C2H6O2
mL soln
L soln
Relationships: M = mol/L, 1 mol C2H6O2 = 62.07 g, 1 mL = 0.001 L

Solve:
Check: the unit is correct, the magnitude is
reasonable
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Practice Calculate the molarity of a solution made by

dissolving 34.0 g of NH3 in 2.00 x 103 mL of solution
(MMNH3 = 17.04 g/mol)
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Practice Calculate the molarity of a solution made by

dissolving 34.0 g of NH3 in 2.00 x 103 mL of solution
Given: 2.00
34.0 mol
g NH
NH
mL
L soln
soln
3, 2000
3, 2.00
Find: M
M
Conceptual
Plan:
g NH3
mol NH3
mL soln
L soln
Relationships: M = mol/L, 1 mol NH3 = 17.04 g, 1 mL = 0.001 L

Solve:
reasonable
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Example 12.4b: What is the molality of a solution

prepared by mixing 17.2 g of C2H6O2 with 0.500 kg
of H2O to make 515 mL of solution?
Given: 17.2 g C2H6O2, 0.500 kg H2O, 515 mL soln
Find: m
mol C2H6O2
Conceptual g C2H6O2
Plan:
kg H2O
Relationships: m = mol/kg, 1 mol C2H6O2 = 62.07 g

Solve:
reasonable
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Practice Calculate the molality of a solution made by

dissolving 34.0 g of NH3 in 2.00 x 103 mL of water
(MMNH3 = 17.04 g/mol, dH2O = 1.00 g/mL)
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Given: 34.0
2.00 gmol
kgHH
NHNH
mL
3, 2.00
2O
3, 2000
2O
Find: m
Conceptual
Plan:
g NH3
mL H2O
mol NH3
g H2 O
kg H2O
Relationships: m=mol/kg, 1 molNH3=17.04 g, 1kg=1000 g, 1.00g=1 mL

Solve:
reasonable
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dissolving 34.0 g of NH3 in 2.00 x 103 g of solution
(MMNH3 = 17.04 g/mol)
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dissolving 34.0 g of NH3 in 2.00 x 103 g of solution
Given:
Find:
2.00
34.0 mol
g NHNH
g kg
solution
H 2O
3, 2000
3, 1.97
m
Conceptual
g NH3
Plan:
g soln
mol NH3
g H2 O
kg H2O
Relationships: m=mol/kg, 1 molNH3=17.04 g, 1kg=1000 g

Solve:
reasonable
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Example 12.4c: What is the percent by mass of a

solution prepared by mixing 17.2 g of C2H6O2 with
0.500 kg of H2O to make 515 mL of solution?
Find: %(m/m)
Conceptual
Plan:
g C2H6O2
g solvent
g soln
Relationships: 1 kg = 1000 g
Solve:
reasonable
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Practice Calculate the percent by mass of a solution made by

(MMNH3 = 17.04 g/mol, dH2O = 1.00 g/mL)
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Practice Calculate the percent by mass of a solution made by

Given:
Find:
Conceptual
Plan:
34.0 g NH3, 2000 g

mL
H2H
O,
2O2034 g soln
%(m/m)
g NH3
mL H2O
g soln
g H2 O
Relationships: % = g/g x 100%, 1.00 g=1 mL

Solve:
reasonable
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Practice Calculate the parts per million of a solution made by

(MMNH3 = 17.04 g/mol, dH2O = 1.00 g/mL)
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Practice Calculate the parts per million of a solution made by

Given:
Find:
Conceptual
Plan:
0.340 g NH3, 2000 g

mL
H2H
O,
2O2000 g soln
ppm
g NH3
mL H2O
g soln
g H2 O
ppm
Relationships: ppm = g/g x 106, 1.00 g=1 mL

Solve:
reasonable
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Example 12.4d: What is the mole fraction of a

Find:
Conceptual g C2H6O2
Plan:
mol C2H6O2
g H2 O
mol H2O
Relationships: = molA/moltot, 1 mol C2H6O2=62.07 g, 1 mol H2O=18.02 g

Solve:
reasonable
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Practice Calculate the mole fraction of a solution made

by dissolving 34.0 g of NH3 in 2.00 x 103 mL of water
(MMNH3 = 17.04 g/mol, dH2O = 1.00 g/mL)
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Practice Calculate the mole fraction of a solution made by

Given: 2.00
34.0 mol
g NHNH
mLmol
H2OH2O, 113.1 tot mol
3, 2000
3, 111.1
Find:
Conceptual
Plan:
Relationships:
g NH3
mL H2O
mol NH3
g H2 O
mol H2O
=mol/mol, 1 mol NH3=17.04 g, 1mol H2O =18.02 g, 1.00 g =1 mL
Solve:
reasonable
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Example 12.4d: What is the mole percent of a

Find:
Conceptual g C2H6O2
Plan:
mol C2H6O2
g H2 O
mol H2O
Relationships: = molA/moltot, 1 mol C2H6O2 = 62.07g, 1 mol H2O=18.02 g

Solve:
reasonable
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Converting Concentration Units

1. Write the given concentration as a ratio
2. Separate the numerator and denominator
separate into the solute part and solution part
3. Convert the solute part into the required unit

4. Convert the solution part into the required unit
5. Use the definitions to calculate the new
concentration units
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Example 12.5: What is the molarity of 6.55% by

mass glucose (C6H12O6) solution?
6.55
g C6mol
H12OC626,H100
soln L
6.55%(m/m)
0.03636
OO2,6g0.09709
12
6
M
Conceptual g C6H12O6
mol C6H12O6
Given:
Find:
Plan:
g soln
mL
L soln
Relationships: M =mol/L, 1mol C6H12O6=180.16g, 1mL=0.001L, 1mL=1.03g

Solve:
reasonable
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Practice Calculate the molality of 16.2 M H2SO4(aq)

(MMH2SO4 = 98.08 g/mol, dsoln = 1.80 g/mL)
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Practice Calculate the molality of a 16.2 M

H2SO4 solution
Given: 16.2 mol
soln
M H2HSO
0.210Lkg
H 2O
2SO
4 4, 1.00
Find: m
Conceptual
Plan:
g H2SO4
L
mL
g soln
mol H2SO4
g H 2O
kg H2O
Relationships: m=mol/kg, 1molH2SO4=98.08g, 1kg=1000g, 1.80g=1mL

Solve:
Check: the unit is correct, the magnitude is reasonable

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Colligative Properties
Colligative properties are properties whose value
depends only on the number of solute particles, and not
on what they are
value of the property depends on the concentration of the
solution
The difference in the value of the property between the

solution and the pure substance is generally related to
the different attractive forces and solute particles
occupying solvent molecules positions
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Vapor Pressure of Solutions

The vapor pressure of a solvent above a
solution is lower than the vapor pressure of
the pure solvent
the solute particles replace some of the solvent
molecules at the surface
Eventually,
is reAdditionequilibrium
of a nonvolatile
established,
butpure
withthe
a smaller
solvent
solute The
reduces
rate of
number
of vapordecreasing
establishes
amolecules
liquid vapor
vaporization,
the
therefore the
vapor
equilibrium
amount
ofpressure
vapor will
be lower
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Thirsty Solutions Revisited

A concentrated solution will draw solvent
molecules toward it due to the natural drive for

materials in nature to mix
Similarly, a concentrated solution will draw pure
solvent vapor into it due to this tendency to mix
The result is reduction in vapor pressure
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Thirsty Solutions
Beakers
with equal
When
equilibrium
is
liquid levelsthe
of liquid
pure
established,
solvent
and
a
level
in the
solution
solution
are placed
beaker
is higher
than in
a bell
jar. Solvent
the
solution
level in
molecules
evaporate
the
pure solvent
from each
and fill
beaker
theone
thirsty
the bellgrabs
jar, and
solution
establishing
an
holds
solvent vapor
equilibrium
with the
more
effectively
liquids in the
beakers.
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Raoults Law
The vapor pressure of a volatile solvent above
a solution is equal to its normal vapor pressure,
P, multiplied by its mole fraction in the solution
Psolvent in solution = solventP
because the mole fraction is always less than 1, the
vapor pressure of the solvent in solution will always
be less than the vapor pressure of the pure solvent
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Example 12.6: Calculate the vapor pressure of

water in a solution prepared by mixing 99.5 g of
C12H22O11 with 300.0 mL of H2O
Given:
Find:
99.5 g C12H22O11, 300.0 mL H2O

PH2O
Conceptual g C12H22O11
Plan:
mL H2O
g H 2O
mol C12H22O11
H2O
mol H2O
PH2O
Relationships: PH2O = 23.8 torr, 1mol C12H22O11 = 342.30g, 1mol H2O = 18.02g
Solve:
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Practice - Calculate the total vapor pressure of a

solution made by dissolving 25.0 g of glucose
(C6H12O6) in 215 g of water at 50 C.
(MMC6H12O6=180.2 g/mol, MMH2O = 18.02 g/mol
Vapor Pressure of H2O @ 50 C = 92.5 torr)
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Practice - Calculate the total vapor pressure of a

solution made by dissolving 25.0 g of glucose
(C6H12O6) in 215 g of water at 50 C
Given:
Find:
Conceptual
Plan:
25.0 g C6H12O6, 215 g H2O

PH2O
g C6H12O6
mol C6H12O6
g H 2O
H2O
mol H2O
PH2O
Relationships: PH2O = 92.5torr, 1mol C6H12O6 = 180.2g, 1mol H2O = 18.02g
Solve:
because glucose is nonvolatile, the total vapor pressure = vapor pressure H2O
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Vapor Pressure Lowering

The vapor pressure of a solvent in a solution is always
lower than the vapor pressure of the pure solvent
The vapor pressure of the solution is directly
proportional to the amount of the solvent in the
solution
The difference between the vapor pressure of the pure
solvent and the vapor pressure of the solvent in
solution is called the vapor pressure lowering
P = Psolvent Psolution = solute Psolvent
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Raoults Law for Volatile Solute

When both the solvent and the solute can evaporate,
both molecules will be found in the vapor phase
The total vapor pressure above the solution will be the
sum of the vapor pressures of the solute and solvent
for an ideal solution
Ptotal = Psolute + Psolvent
The solvent decreases the solute vapor pressure in the

same way the solute decreased the solvents
Psolute = solutePsolute and Psolvent = solventPsolvent
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Example 12.7: Calculate the component and total

vapor pressure of a solution prepared by mixing
3.95 g of CS2 with 2.43 g of C3H6O
Given:
Find:
Conceptual
Plan:
0.05187molCS
P
=148torr
PCS2
=515torr,
0.04184molC
P
3.95 g CS2, P2,CS2
==285torr,
515 torr,0.04184molC
2.43 g C3H63H
O,
PPC3H6O
==332torr
332 torr
6O,
C3H6O
CS2
3H
6O,
C3H6O
P
PCS2,,PPC3H6O, P
, total
P
CS2
C3H6O
total
g CS2
mol CS2
g C 3H6O
mol C3H6O
Relationships: 1mol CS2 = 76.15 g, 1mol C3H6O = 58.0 g
Solve:
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Practice Calculate the total vapor pressure of an ideal

solution made by mixing 0.500 mol of ether (C 4H10O)
with 0.250 mol of ethanol (C2H6O) at 20 C.
(vapor pressure of ether @ 20 C = 440 torr
vapor pressure of ethanol @ 20 C = 44.6 torr)
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Practice Calculate the total vapor pressure of an ideal

solution made by mixing 0.500 mol of ether (C 4H10O)
with 0.250 mol of ethanol (C2H6O) at 20C
Given:
Find:
Conceptual
Plan:
0.500 mol C4H10O, P

PC4H10O
=293torr,
torr,0.250
0.250mol
molCC
PPethanol
= 44.6torr
torr
ether=440
2H
2H
6O,
6O,
C2H6O=14.9
PPtotal
total
mol C4H10O
mol C2H6O
Relationships:
Solve:
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Ideal vs. Nonideal Solution

In ideal solutions, the made solutesolvent
interactions are equal to the sum of the broken
solutesolute and solventsolvent interactions
ideal solutions follow Raoults Law
Effectively, the solute is diluting the solvent

If the solutesolvent interactions are stronger
or weaker than the broken interactions the
solution is nonideal
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Vapor Pressure of a
Nonideal Solution
When the solutesolvent interactions are stronger than
the solutesolute solventsolvent, the total vapor
pressure of the solution will be less than predicted by
Raoults Law
because the vapor pressures of the solute and solvent are
lower than ideal
When the solutesolvent interactions are weaker than

the solutesolute solventsolvent, the total vapor
pressure of the solution will be more than predicted by
Raoults Law
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Deviations from Raoults Law
112
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Example 12.7, contd: The experimentally measured total

vapor pressure of the solution is 645 torr. Is the solution
ideal? If not, what can you say about the relative
strength of carbon disulfideacetone interactions?
Given:
Find:
Ptotal(expt) = 645 torr, Ptotal(ideal) = 443 torr

is the solution ideal?, interaction strength if not ideal
Solve:
Ptotal(expt) = 645 torr > Ptotal(ideal) = 443 torr
The solution is not ideal and shows positive deviations from
Raoults law. Therefore, carbon disulfideacetone
interactions must be weaker than acetoneacetone and
carbon disulfidecarbon disulfide interactions.
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Other Colligative Properties Related to

Vapor Pressure Lowering
Vapor pressure lowering occurs at all
temperatures
This results in the temperature required to boil
the solution being higher than the boiling point
of the pure solvent
This also results in the temperature required to
freeze the solution being lower than the
freezing point of the pure solvent
114
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115
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Freezing Salt Water

Pure water freezes at 0 C. At this temperature, ice and liquid
water are in dynamic equilibrium.
Adding salt disrupts the equilibrium. The salt particles
dissolve in the water, but do not attach easily to the solid ice.
When an aqueous solution containing a dissolved solid solute
freezes slowly, the ice that forms does not normally contain
much of the solute.
To return the system to equilibrium, the temperature must be
lowered sufficiently to make the water molecules slow down
enough so that more can attach themselves to the ice.
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Freezing Point Depression

The freezing point of a solution is lower than the freezing point
of the pure solvent
therefore the melting point of the solid solution is lower
The difference between the freezing point of the solution and

freezing point of the pure solvent is directly proportional to the
molal concentration of solute particles
FPsolvent FPsolution) = Tf = mKf
The proportionality constant is called the Freezing Point

Depression Constant, Kf
the value of Kf depends on the solvent
the units of Kf are C/m
117
Copyright
Kf
118
Copyright
Example 12.8: What is the freezing point of a 1.7 m

aqueous ethylene glycol solution, C2H6O2?
Given: 1.7 m C2H6O2(aq)
Find: T , C
f
Conceptual
m
Plan:
Tf
Relationships: Tf = m Kf, Kf for H2O = 1.86 C/m, FPH2O = 0.00 C

Solve:
Check: the unit is correct, the freezing point lower
than the normal freezing point makes sense

119
Copyright
Practice Calculate the molar mass of a

compound if a solution of 12.0 g dissolved in
80.0 g of water freezes at 1.94 C
(Kf water = 1.86 C/m)
120
Copyright
Practice Calculate the molar mass of a compound if

a solution of 12.0 g dissolved in 80.0 g of water freezes
at 1.94 C
Given: masssolute = 12.0 g, massH2O= 80.0 g, FPsoln = 1.94C
Find: T , C
f
Conceptual
Plan:
Relationships:
FPsoln
Tf
Tf =FPH2OFPsoln
mol
MM
m kgH2O= mol MM=g/mol
Tf=mKf, m =mol/kg, MM=g/mol, Kf=1.86 C/m, FPH2O=0.00 C
Solve:
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Boiling Point Elevation

The boiling point of a solution is higher than the boiling point
of the pure solvent
for a nonvolatile solute
The difference between the boiling point of the solution and

boiling point of the pure solvent is directly proportional to the
molal concentration of solute particles
BPsolution BPsolvent) = Tb = mKb
The proportionality constant is called the Boiling Point
Elevation Constant, Kb
the value of Kb depends on the solvent
the units of Kb are C/m
122
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Example 12.9: How many grams of ethylene glycol,

C2H6O2, must be added to 1.0 kg H2O to give a
solution that boils at 105 C?
Given: 1.0 kg H2O, Tb = 105 C
Find: mass C H O , g
2 6 2
Conceptual
Tb
Plan:
kg H2O
mol C2H6O2
g C2H6O2
Relationships: Tb = m Kb, Kb H2O = 0.512 C/m, BPH2O = 100.0 C

MMC2H6O2 = 62.07 g/mol, 1 kg = 1000 g
Solve:
123
Copyright
Practice Calculate the boiling point of a

solution made by dissolving 1.00 g of
glycerin, C3H8O3, in 54.0 g of water
124
Copyright
Practice Calculate the boiling point of a solution made by

dissolving 1.00 g of glycerin, C3H8O3, in 54.0 g of water
Given: 1.00 g C3H8O3, 54.0 g H2O
Find: T
b, soln, C
Conceptual g C3H8O3, kg H2O
Plan:
Relationships:
Tb
m = mol/kg,Tb = mKb, Kb for H2O = 0.512 C/m,

BPH2O = 100.0 C, 1 mol C3H8O3 = 92.09 g
Solve:
125
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Osmosis
Osmosis is the flow of solvent from a
solution of low concentration into a solution
of high concentration
The solutions may be separated by a semipermeable membrane
A semi-permeable membrane allows

solvent to flow through it, but not solute
126
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Osmotic Pressure
The amount of pressure needed to keep osmotic
flow from taking place is called the osmotic
pressure
The osmotic pressure, , is directly proportional
to the molarity of the solute particles
R = 0.08206 (atmL)/(molK)
= MRT
127
Copyright
128
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Example 12.10: What is the molar mass of a protein

if 5.87 mg per 10 mL gives an osmotic pressure of
2.45 torr at 25 C?
Given: 5.87 mg/10 mL, = 2.45 torr, T = 25 C
Find: molar mass, g/mol
Conceptual
,T
M
Plan:
mL
mol protein
Relationships: P=MRT, T(K)=T(C)+273.15, R= 0.08206atmL/molK

M = mol/L, 1 mL = 0.001 L, MM=g/mol, 1atm =760 torr
Solve:
129
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Practice Lysozyme is an enzyme used to cleave

cell walls. A solution made by dissolving 0.0750 g
of lysozyme in 100.0 mL results in an osmotic
pressure of 1.32 x 103 atm at 25 C. Calculate the
molar mass of lysozyme.
130
Copyright
Practice What is the molar mass of lysozyme if

0.0750 g per 100.0 mL gives an osmotic pressure of
1.32x 103 atm at 25 C?
Given: 0.0750 g/100 mL, = 1.32 x 103 atm, T = 25 C
Find: molar mass, g/mol
Conceptual
,T
M
Plan:
mL
mol protein
Relationships: P=MRT, T(K)=T(C)+273.15, R= 0.08206atmL/molK

M = mol/L, 1 mL = 0.001 L, MM=g/mol, 1atm =760 torr
Solve:
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vant Hoff Factors

Ionic compounds produce multiple solute particles
for each formula unit
The theoretical vant Hoff factor, i, is the ratio of
moles of solute particles to moles of formula units
dissolved
The measured vant Hoff factors are generally less
than the theoretical due to ion pairing in solution
therefore the measured vant Hoff factor often causes
the T to be lower than you might expect
132
Copyright
133
Copyright
Example 12.11: What is the measured vant Hoff factor

if 0.050 m CaCl2(aq) has freezing point of 0.27 C ?
Given: 0.050 m CaCl2(aq), Tf = 0.27C
Find:
i
Conceptual
m, Tf
i
Plan:
Relationships: Tf = imKf, Kf for H2O = 1.86 C/m, FPH2O = 0.00 C
Solve:
134
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Example 12.12: A solution contains 0.102 mol

Ca(NO3)2 and 0.927 mol H2O. Calculate the vapor
pressure of the solution at 55 C
Given: 0.102 mol Ca(NO3)2(aq), 0.927 mol H2O, T = 55 C,
PH2O = 118.1 torr (at 55 C)
Find: Psolution
Conceptual
, PH2O
Plan:
Relationships: Psolution = iPH2O
Psolution
Solve:
135
Copyright
Practice Calculate the theoretical boiling

point of a solution made by dissolving 10.0 g
of NaCl (MM 58.44) in 54.0 g of water
136
Copyright
Practice Calculate the theoretical boiling point of a solution

made by dissolving 10.0 g of NaCl in 54.0 g of H2O
Given: 10.0 g NaCl, 54.0 g H2O
Find: T
b, soln, C
Conceptual g NaCl, kg H2O
Plan:
Relationships:
Tb
m = mol/kg,Tb = imKb Kb for H2O = 0.512 C/m,

BPH2O = 100.0C, 1 mol C3H8O3 = 92.09 g
Solve:
137
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AAn
hyperosmotic
hyposmotic
isosmoticsolution
solution
solution
has
has
has
athe
lower
a higher
same
osmotic
osmotic
pressure
pressure
than
as the
the solution
solution inside
inside the
the cell
cell as
as aa result
result there
there is
is no
a
net
netflow
flowofofwater
waterinto
out
into
of
the
or
the
cell,
out
cell,
of
causing
causing
the cellit to
it to
swell
shrivel
138
Copyright
Mixtures
Solutions = homogeneous
Suspensions = heterogeneous, separate on
standing
Colloids = heterogeneous, do not separate on
standing
particles can coagulate
cannot pass through semi-permeable membrane
hydrophilic
stabilized by attraction for solvent (water)
hydrophobic
stabilized by charged surface repulsions
Show the Tyndall Effect and Brownian motion

139
Copyright
Mixtures
Solution
Colloid
Suspenion
Particle size
< 1 nm
1-1000 nm
> 1000 nm
Gravity effect
none
none
settle out
Centrifuge effect
none
settle out
settle out
Ordinary filters
pass
through
pass through
retained
Ultrafilters
pass
through
retained
retained
Colligative properties
large
small
none
Visibility of particle w/ lite

microscope
invisible
barely visible
visible
Visibility of particle w/ elec.

mcrscp.
invisible
visible
visible
Light scattering
none
Tyndall Effect
scatter all light
Brownian movement
none visible
visible
none
Electrical charge
maybe
many
negligible
140
Copyright
Brownian Motion
141
Copyright
Types of Colloidal Suspensions
142
Copyright
Soaps
Triglycerides can be broken down into fatty acid salts
and glycerol by treatment with a strong hydroxide

solution
Fatty acid salts have a very polar head because it is
ionic and a very nonpolar tail because it is all C and
H
hydrophilic head and hydrophobic tail
This unique structure allows the fatty acid salts, called

soaps, to help oily substances be attracted to water
micelle formation
emulsification
143
Copyright
Soap
144
Copyright
Soap
145
Copyright

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Chemistry: A Molecular Approach, 2nd Ed.

2011 Pearson Education, Inc.

As seawater passes through your body, it pulls water out

Tro: Chemistry: A Molecular Approach, 2/e

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Tro: Chemistry: A Molecular Approach, 2/e

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Tro: Chemistry: A Molecular Approach, 2/e

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Most homogeneous materials we encounter are

Nature has a tendency toward spontaneous

Tro: Chemistry: A Molecular Approach, 2/e

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When table salt is mixed with water, it seems to

Homogeneous mixtures are called solutions

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Tro: Chemistry: A Molecular Approach, 2/e

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Common Types of Solution

Soda (CO2 in H2O)

Brass (Zn in Cu)

Solutions that contain Hg and some other metal

are called amalgams

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Tro: Chemistry: A Molecular Approach, 2/e

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When one substance does not dissolve in

The solubility of one substance in another

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When solutions with different solute concentrations

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Mixing and the Solution Process:

Most processes occur because the end

result has less potential energy

The gases mix because the energy of

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Mixing and the Solution Process

energy dispersal throughout the

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Intermolecular Forces and the

At least some of the energy to do this comes from

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Tro: Chemistry: A Molecular Approach, 2/e

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Tro: Chemistry: A Molecular Approach, 2/e

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Relative Interactions and Solution Formation

When the solute-to-solvent attractions are weaker

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The maximum amount of solute that can be

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A chemical will dissolve in a solvent if it has a similar structure

Polar molecules and ionic compounds will be more soluble in

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Tro: Chemistry: A Molecular Approach, 2/e

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Example 12.1a: Predict whether the following

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