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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 nature’s
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 2 Copyright © 2011 Pearson Education, Inc.
Seawater
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Seawater
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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
Tro: Chemistry: A Molecular Approach, 2/e 5 Copyright © 2011 Pearson Education, Inc.
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
Solute Solvent
Solution Phase Phase Phase Example
Gaseous solutions Gas Gas Air (mostly N2 & O2)
Gas Liquid Soda (CO2 in H2O)
Liquid solutions Liquid Liquid Vodka (C2H5OH in H2O)
Solid Liquid Seawater (NaCl in H2O)
Solid solutions Solid Solid Brass (Zn in Cu)
Tro: Chemistry: A Molecular Approach, 2/e 9 Copyright © 2011 Pearson Education, Inc.
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 – nature’s tendency
toward mixing, and the types of
intermolecular attractive forces
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Spontaneous Mixing
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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 solute–solute attractive forces
2. some of the solvent–solvent attractive forces
✔ both processes are endothermic
• At least some of the energy to do this comes from
making new solute–solvent attractions
✔ which is exothermic
Tro: Chemistry: A Molecular Approach, 2/e 14 Copyright © 2011 Pearson Education, Inc.
Intermolecular Attractions
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Solution Interactions
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Relative Interactions and Solution Formation
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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.
Vitamin C is water
Vitamin C
soluble.
Tro: Chemistry: A Molecular Approach, 2/e 21 Copyright © 2011 Pearson Education, Inc.
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.
Tro: Chemistry: A Molecular Approach, 2/e 22 Copyright © 2011 Pearson Education, Inc.
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
Tro: Chemistry: A Molecular Approach, 2/e 23 Copyright © 2011 Pearson Education, Inc.
Practice – Explain the solubility trends
seen in the table below
Tro: Chemistry: A Molecular Approach, 2/e 24 Copyright © 2011 Pearson Education, Inc.
Practice – Explain the solubility trends
seen in the table below
These alcohols all have a polar
OH part and a nonpolar CHn part.
Tro: Chemistry: A Molecular Approach, 2/e 26 Copyright © 2011 Pearson Education, Inc.
Energetics of Solution Formation: the
Enthalpy of Solution
• To make a solution you must
1. overcome all attractions between the solute
particles; therefore ΔHsolute is endothermic
2. overcome some attractions between solvent
molecules; therefore ΔHsolvent is endothermic
3. form new attractions between solute particles and
solvent molecules; therefore ΔHmix is exothermic
• The overall ΔH for making a solution depends on the
relative sizes of the ΔH for these three processes
ΔHsol’n = ΔHsolute + ΔHsolvent + ΔHmix
Tro: Chemistry: A Molecular Approach, 2/e 27 Copyright © 2011 Pearson Education, Inc.
Solution Process
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Energetics of Solution Formation
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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
ΔHsolute = −ΔHlattice energy
✔ attractive forces in water = H-bonds
✔ attractive forces between ion and water = ion–dipole
✔ ΔHhydration = heat released when 1 mole of gaseous ions
dissolves in water = ΔHsolvent + ΔHmix
Tro: Chemistry: A Molecular Approach, 2/e 30 Copyright © 2011 Pearson Education, Inc.
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
Tro: Chemistry: A Molecular Approach, 2/e 31 Copyright © 2011 Pearson Education, Inc.
Heats of Solution for
Ionic Compounds
• For an aqueous solution of an ionic compound,
the ΔHsolution is the difference between the Heat
of Hydration and the Lattice Energy
Tro: Chemistry: A Molecular Approach, 2/e 35 Copyright © 2011 Pearson Education, Inc.
Practice – What is the lattice energy of KI if
ΔHsol’n = +21.5 kJ/mol and the ΔHhydration = −583 kJ/mol?
Tro: Chemistry: A Molecular Approach, 2/e 38 Copyright © 2011 Pearson Education, Inc.
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
Tro: Chemistry: A Molecular Approach, 2/e 41 Copyright © 2011 Pearson Education, Inc.
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 ΔHsolution 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)
Tro: Chemistry: A Molecular Approach, 2/e 42 Copyright © 2011 Pearson Education, Inc.
Solubility Curves
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Temperature Dependence of Solid
Solubility in Water (g/100 g H2O)
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Purification by Recrystallization
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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 ºC
saturated
50 g KNO3 in 50 g H2O @ 50 ºC
supersaturated
Tro: Chemistry: A Molecular Approach, 2/e 48 Copyright © 2011 Pearson Education, Inc.
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
Tro: Chemistry: A Molecular Approach, 2/e 52 Copyright © 2011 Pearson Education, Inc.
Henry’s Law
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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 CO2 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
Conceptual [CO2] P
Plan:
Relationships: S = k P, k = 3.4 x 10−2 M/atm
H H
Solve:
Tro: Chemistry: A Molecular Approach, 2/e 57 Copyright © 2011 Pearson Education, Inc.
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)
Tro: Chemistry: A Molecular Approach, 2/e 58 Copyright © 2011 Pearson Education, Inc.
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:
Tro: Chemistry: A Molecular Approach, 2/e 59 Copyright © 2011 Pearson Education, Inc.
Concentrations
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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
Tro: Chemistry: A Molecular Approach, 2/e 61 Copyright © 2011 Pearson Education, Inc.
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−
Tro: Chemistry: A Molecular Approach, 2/e 62 Copyright © 2011 Pearson Education, Inc.
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
Tro: Chemistry: A Molecular Approach, 2/e 63 Copyright © 2011 Pearson Education, Inc.
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 mL64 of solutionCopyright © 2011 Pearson Education, Inc.
Tro: Chemistry: A Molecular Approach, 2/e
Percent Concentration
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Parts Per Million Concentration
Tro: Chemistry: A Molecular Approach, 2/e 66 Copyright © 2011 Pearson Education, Inc.
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
Tro: Chemistry: A Molecular Approach, 2/e 67 Copyright © 2011 Pearson Education, Inc.
Parts Per Billion Concentration
Tro: Chemistry: A Molecular Approach, 2/e 68 Copyright © 2011 Pearson Education, Inc.
Using Concentrations as
Conversion Factors
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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 mL
g sol’n
Plan: solute sol’n
Tro: Chemistry: A Molecular Approach, 2/e 70 Copyright © 2011 Pearson Education, Inc.
Preparing a Solution
Tro: Chemistry: A Molecular Approach, 2/e 71 Copyright © 2011 Pearson Education, Inc.
Practice – How would you prepare 250.0 mL of
19.5% by mass CaCl2? (d = 1.18 g/mL)
Tro: Chemistry: A Molecular Approach, 2/e 72 Copyright © 2011 Pearson Education, Inc.
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 CaCl , g
2
Conceptual mL g
g sol’n
Plan: sol’n solute
Tro: Chemistry: A Molecular Approach, 2/e 73 Copyright © 2011 Pearson Education, Inc.
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%
Tro: Chemistry: A Molecular Approach, 2/e 74 Copyright © 2011 Pearson Education, Inc.
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: 0.2771
17.2 g Cmol
HCOH , 0.500 kg H2kg
O , 0.500
2 6 22 6 2
O,H515O, mL sol’n
0.515 L
2
Find: M
Conceptual g mol
Plan: C 2H 6O 2 C 2H 6O 2
mL M
L sol’n
sol’n
Relationships: M = mol/L, 1 mol C H O = 62.07 g, 1 mL = 0.001 L
2 6 2
Solve:
Tro: Chemistry: A Molecular Approach, 2/e 76 Copyright © 2011 Pearson Education, Inc.
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 NHNH, 2000
3 3
, 2.00mL
L sol’n
sol’n
Find: M
M
Conceptual g NH3 mol NH3
Plan:
mL M
L sol’n
sol’n
Relationships: M = mol/L, 1 mol NH = 17.04 g, 1 mL = 0.001 L
3
Solve:
Tro: Chemistry: A Molecular Approach, 2/e 79 Copyright © 2011 Pearson Education, Inc.
Practice – Calculate the molality of a solution made by
dissolving 34.0 g of NH3 in 2.00 x 103 mL of water
2.00 gmol
Given: 34.0 NHNH , 2.00
, 2000
3 3
mLkgHHOO
22
Find: m
Conceptual g NH3 mol NH3
Plan:
mL g kg m
H 2O H 2O H 2O
Relationships: m=mol/kg, 1 molNH =17.04 g, 1kg=1000 g, 1.00g=1 mL
3
Solve:
Tro: Chemistry: A Molecular Approach, 2/e 81 Copyright © 2011 Pearson Education, Inc.
Practice – Calculate the molality of a solution made by
dissolving 34.0 g of NH3 in 2.00 x 103 g of solution
Given: 2.00
34.0 mol
g NHNH, 2000
3 3
, 1.97g kg
solution
H 2O
Find: m
Conceptual g NH3 mol NH3
Plan:
g kg m
g sol’n
H 2O H 2O
Relationships: m=mol/kg, 1 molNH =17.04 g, 1kg=1000 g
3
Solve:
Tro: Chemistry: A Molecular Approach, 2/e 84 Copyright © 2011 Pearson Education, Inc.
Practice – Calculate the percent by mass of a solution made by
dissolving 34.0 g of NH3 in 2.00 x 103 mL of water
Tro: Chemistry: A Molecular Approach, 2/e 86 Copyright © 2011 Pearson Education, Inc.
Practice – Calculate the parts per million of a solution made by
dissolving 0.340 g of NH3 in 2.00 x 103 mL of water
Tro: Chemistry: A Molecular Approach, 2/e 89 Copyright © 2011 Pearson Education, Inc.
Practice – Calculate the mole fraction of a solution made by
dissolving 34.0 g of NH3 in 2.00 x 103 mL of water
34.0 mol
Given: 2.00 g NHNH, 2000
3 3
mLmol
, 111.1 H2OH2O, 113.1 tot mol
Find: χχ
Conceptual g NH3 mol NH3
Plan:
mL g mol χ
H 2O H 2O H 2O
Relationships: χ=mol/mol, 1 mol NH3=17.04 g, 1mol H2O =18.02 g, 1.00 g =1 mL
Solve:
Tro: Chemistry: A Molecular Approach, 2/e 92 Copyright © 2011 Pearson Education, Inc.
Tro: Chemistry: A Molecular Approach, 2/e 93 Copyright © 2011 Pearson Education, Inc.
Example 12.5: What is the molarity of 6.55% by
mass glucose (C6H12O6) solution?
Given: 6.55 g C6mol
H12O
6.55%(m/m)
0.03636 C662,H100
OO,g0.09709
12
sol’n L
6 26
Find: M
Conceptual g mol
Plan: C6H12O6 C6H12O6
g M
mL L sol’n
sol’n
Relationships: M =mol/L, 1mol C H O =180.16g, 1mL=0.001L, 1mL=1.03g
6 12 6
Solve:
Tro: Chemistry: A Molecular Approach, 2/e 95 Copyright © 2011 Pearson Education, Inc.
Practice – Calculate the molality of a 16.2 M
H2SO4 solution
Given: 16.2 mol
M H2HSOSO , 1.00 L sol’n
2 4 4 0.210 kg H2O
Find: m
g mol
Conceptual
H2SO4 H2SO4
Plan:
g
g kg m
L mL H2O H2O
sol’n
Relationships: m=mol/kg, 1molH SO =98.08g, 1kg=1000g, 1.80g=1mL
2 4
Solve:
Tro: Chemistry: A Molecular Approach, 2/e 96 Copyright © 2011 Pearson Education, Inc.
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
Tro: Chemistry: A Molecular Approach, 2/e 97 Copyright © 2011 Pearson Education, Inc.
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, equilibrium
Addition of is
a nonvolatile
re-established,
solute The but
pure
reduces with
ratea of
solvent
the
smaller number
establishes
vaporization, a liquid ⇔ vapor
of vapor
decreasing the
moleculesamount
– therefore the vapor
equilibrium
of vapor
pressure will be lower
Tro: Chemistry: A Molecular Approach, 2/e 98 Copyright © 2011 Pearson Education, Inc.
Thirsty Solutions Revisited
Tro: Chemistry: A Molecular Approach, 2/e 99 Copyright © 2011 Pearson Education, Inc.
Thirsty Solutions
Beakers
When with equal
equilibrium is
liquid levelsthe
established, of liquid
pure
solvent
level in theand a solution
solution
are placed
beaker in athan
is higher bell
jar.
the Solvent
solution level in
molecules
the pure solventevaporate
from each
beaker – theone and fill
thirsty
the bellgrabs
solution jar, and
establishing
holds an
solvent vapor
equilibrium
more with the
effectively
liquids in the beakers.
Tro: Chemistry: A Molecular Approach, 2/e 100 Copyright © 2011 Pearson Education, Inc.
Raoult’s Law
Tro: Chemistry: A Molecular Approach, 2/e 101 Copyright © 2011 Pearson Education, Inc.
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: 99.5 g C12H22O11, 300.0 mL H2O
Find: PH2O
g mol
Conceptual
C12H22O11 C12H22O11
Plan:
mL g mol χH2O PH2O
H2O H2O H2O
Relationships: P°H2O = 23.8 torr, 1mol C12H22O11 = 342.30g, 1mol H2O = 18.02g
Solve:
Tro: Chemistry: A Molecular Approach, 2/e 102 Copyright © 2011 Pearson Education, Inc.
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)
Tro: Chemistry: A Molecular Approach, 2/e 103 Copyright © 2011 Pearson Education, Inc.
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: 25.0 g C6H12O6, 215 g H2O
Find: PH2O
g mol
Conceptual
C6H12O6 C6H12O6
Plan: ΧH2
g mol PH2O
H2O H2O O
Relationships: P°H2O = 92.5torr, 1mol C6H12O6 = 180.2g, 1mol H2O = 18.02g
Solve:
because glucose is nonvolatile, the total vapor pressure = vapor pressure H2O
Tro: Chemistry: A Molecular Approach, 2/e 104 Copyright © 2011 Pearson Education, Inc.
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
ΔP = Pºsolvent − Psolution = χsolute • Pºsolvent
Tro: Chemistry: A Molecular Approach, 2/e 105 Copyright © 2011 Pearson Education, Inc.
Raoult’s 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 solvent’s
Psolute = χsolute•P°solute and Psolvent = χsolvent•P°solvent
Tro: Chemistry: A Molecular Approach, 2/e 106 Copyright © 2011 Pearson Education, Inc.
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: 3.95 g CS2, Pº
0.05187molCS ,P ==285torr,
PºCS2
2 CS2 CS2 515 torr,0.04184molC
=515torr, 2.43 g C3H633H
0.04184molC O, PºPC3H6O
H66O,
O, Pº
C3H6O ==332torr
332 torr
=148torr
C3H6O
Find: P
PCS2,,PPC3H6O, P, total
P
CS2 C3H6O total
Solve:
Tro: Chemistry: A Molecular Approach, 2/e 107 Copyright © 2011 Pearson Education, Inc.
Practice – Calculate the total vapor pressure of an ideal
solution made by mixing 0.500 mol of ether (C4H10O)
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)
Tro: Chemistry: A Molecular Approach, 2/e 108 Copyright © 2011 Pearson Education, Inc.
Practice – Calculate the total vapor pressure of an ideal
solution made by mixing 0.500 mol of ether (C4H10O)
with 0.250 mol of ethanol (C2H6O) at 20°C
Given: 0.500 mol C4H10O, Pº
PC4H10O
ether
=440
=293torr,
torr,0.250
0.250mol
molCCHHO,O,PºPethanol
2 26 6 C2H6O
==14.9
44.6 torr
torr
Find: PPtotal
total
Solve:
Tro: Chemistry: A Molecular Approach, 2/e 109 Copyright © 2011 Pearson Education, Inc.
Ideal vs. Nonideal Solution
Tro: Chemistry: A Molecular Approach, 2/e 110 Copyright © 2011 Pearson Education, Inc.
Vapor Pressure of a
Nonideal Solution
• When the solute–solvent interactions are stronger
than the solute–solute + solvent–solvent, the total
vapor pressure of the solution will be less than
predicted by Raoult’s Law
✔ because the vapor pressures of the solute and solvent
are lower than ideal
• When the solute–solvent interactions are weaker
than the solute–solute + solvent–solvent, the total
vapor pressure of the solution will be more than
predicted by Raoult’s Law
Tro: Chemistry: A Molecular Approach, 2/e 111 Copyright © 2011 Pearson Education, Inc.
Deviations from Raoult’s Law
Tro: Chemistry: A Molecular Approach, 2/e 112 Copyright © 2011 Pearson Education, Inc.
Example 12.7, cont’d: 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 disulfide–acetone interactions?
Given: Ptotal(expt) = 645 torr, Ptotal(ideal) = 443 torr
Solve:
Ptotal(expt) = 645 torr > Ptotal(ideal) = 443 torr
Tro: Chemistry: A Molecular Approach, 2/e 113 Copyright © 2011 Pearson Education, Inc.
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
Tro: Chemistry: A Molecular Approach, 2/e 114 Copyright © 2011 Pearson Education, Inc.
Tro: Chemistry: A Molecular Approach, 2/e 115 Copyright © 2011 Pearson Education, Inc.
Freezing Salt Water
• Pure water freezes at 0 ºC. 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
moreA Molecular
Tro: Chemistry: can attach themselves
Approach, 2/e 116 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) = ΔTf = m•Kf
• 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
Tro: Chemistry: A Molecular Approach, 2/e 117 Copyright © 2011 Pearson Education, Inc.
Kf
Tro: Chemistry: A Molecular Approach, 2/e 118 Copyright © 2011 Pearson Education, Inc.
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 ΔTf
Plan:
Tro: Chemistry: A Molecular Approach, 2/e 120 Copyright © 2011 Pearson Education, Inc.
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, FPsol’n = −1.94°C
Find: T , °C
f
Conceptual FPsol’
ΔTf m mol MM
Plan: ΔTnf m ∙ kgH2O= mol MM=g/mol
=FPH2O−FPsol’n
Relationships: ΔTf=mKf, m =mol/kg, MM=g/mol, Kf=1.86 °C/m, FPH2O=0.00 °C
Solve:
Tro: Chemistry: A Molecular Approach, 2/e 121 Copyright © 2011 Pearson Education, Inc.
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) = ΔTb = m•Kb
• 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
Tro: Chemistry: A Molecular Approach, 2/e 122 Copyright © 2011 Pearson Education, Inc.
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 ΔTb m
Plan:
kg mol
g C 2H 6O 2
H 2O C 2H 6O 2
Relationships: ΔTb = m •Kb, Kb H2O = 0.512 °C/m, BPH2O = 100.0 °C
MMC2H6O2 = 62.07 g/mol, 1 kg = 1000 g
Solve:
Tro: Chemistry: A Molecular Approach, 2/e 123 Copyright © 2011 Pearson Education, Inc.
Practice – Calculate the boiling point of a
solution made by dissolving 1.00 g of
glycerin, C3H8O3, in 54.0 g of water
Tro: Chemistry: A Molecular Approach, 2/e 124 Copyright © 2011 Pearson Education, Inc.
Practice – Calculate the boiling point of a solution made by
dissolving 1.00 g of glycerin, C3H8O3, in 54.0 g of water
Tro: Chemistry: A Molecular Approach, 2/e 125 Copyright © 2011 Pearson Education, Inc.
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
semi-permeable membrane
• A semi-permeable membrane allows
solvent to flow through it, but not solute
Tro: Chemistry: A Molecular Approach, 2/e 126 Copyright © 2011 Pearson Education, Inc.
Osmotic Pressure
• The amount of pressure needed to keep
osmotic flow from taking place is called the
osmotic pressure
• The osmotic pressure, Π, is directly
proportional to the molarity of the solute
particles
✔ R = 0.08206 (atm∙L)/(mol∙K)
Π = MRT
Tro: Chemistry: A Molecular Approach, 2/e 127 Copyright © 2011 Pearson Education, Inc.
Tro: Chemistry: A Molecular Approach, 2/e 128 Copyright © 2011 Pearson Education, Inc.
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, Π = 2.45 torr, T = 25 °C
Find: molar mass, g/mol
Conceptual Π,T M
Plan:
mol
mL L
protein
Relationships: P=MRT, T(K)=T(°C)+273.15, R= 0.08206atm∙L/mol∙K
M = mol/L, 1 mL = 0.001 L, MM=g/mol, 1atm =760 torr
Solve:
Tro: Chemistry: A Molecular Approach, 2/e 129 Copyright © 2011 Pearson Education, Inc.
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 10−3 atm at 25 °C. Calculate the
molar mass of lysozyme.
Tro: Chemistry: A Molecular Approach, 2/e 130 Copyright © 2011 Pearson Education, Inc.
Practice – What is the molar mass of lysozyme if
0.0750 g per 100.0 mL gives an osmotic pressure of
1.32x 10−3 atm at 25 °C?
Given: 0.0750 g/100 mL, Π = 1.32 x 10−3 atm, T = 25 °C
Find: molar mass, g/mol
Conceptual Π,T M
Plan:
mol
mL L
protein
Relationships: P=MRT, T(K)=T(°C)+273.15, R= 0.08206atm∙L/mol∙K
M = mol/L, 1 mL = 0.001 L, MM=g/mol, 1atm =760 torr
Solve:
Tro: Chemistry: A Molecular Approach, 2/e 131 Copyright © 2011 Pearson Education, Inc.
van’t Hoff Factors
• Ionic compounds produce multiple solute
particles for each formula unit
• The theoretical van’t Hoff factor, i, is the ratio
of moles of solute particles to moles of formula
units dissolved
• The measured van’t Hoff factors are generally
less than the theoretical due to ion pairing in
solution
✔ therefore the measured van’t Hoff factor often
causes the ΔT to be lower than you might expect
Tro: Chemistry: A Molecular Approach, 2/e 132 Copyright © 2011 Pearson Education, Inc.
Tro: Chemistry: A Molecular Approach, 2/e 133 Copyright © 2011 Pearson Education, Inc.
Example 12.11: What is the measured van’t Hoff factor
if 0.050 m CaCl2(aq) has freezing point of −0.27 ºC ?
Tro: Chemistry: A Molecular Approach, 2/e 134 Copyright © 2011 Pearson Education, Inc.
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 ºC
Given: 0.102 mol Ca(NO3)2(aq), 0.927 mol H2O, T = 55 °C, P°
Find: H2O = 118.1 torr (at 55 °C)
Psolution
Conceptual χ, PH2O Psolution
Plan:
Relationships: Psolution = i∙χΗ2Ο∙PºH2O
Solve:
Tro: Chemistry: A Molecular Approach, 2/e 135 Copyright © 2011 Pearson Education, Inc.
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
Tro: Chemistry: A Molecular Approach, 2/e 136 Copyright © 2011 Pearson Education, Inc.
Practice – Calculate the theoretical boiling point of a solution
made by dissolving 10.0 g of NaCl in 54.0 g of H2O
Tro: Chemistry: A Molecular Approach, 2/e 137 Copyright © 2011 Pearson Education, Inc.
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Tro: Chemistry: A Molecular Approach, 2/e 138 Copyright © 2011 Pearson Education, Inc.
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
Tro: Chemistry: A Molecular Approach, 2/e 139 Copyright © 2011 Pearson Education, Inc.
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 pass through retained
through
Tro: Chemistry: A Molecular Approach, 2/e 141 Copyright © 2011 Pearson Education, Inc.
Types of Colloidal Suspensions
Tro: Chemistry: A Molecular Approach, 2/e 142 Copyright © 2011 Pearson Education, Inc.
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
Tro: Chemistry: A Molecular Approach, 2/e 143 Copyright © 2011 Pearson Education, Inc.
Soap
Tro: Chemistry: A Molecular Approach, 2/e 144 Copyright © 2011 Pearson Education, Inc.
Soap
Tro: Chemistry: A Molecular Approach, 2/e 145 Copyright © 2011 Pearson Education, Inc.