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13-1
Lecture PowerPoint
Chemistry
The Molecular Nature of
Matter and Change
Sixth Edition
Martin S. Silberberg
Copyright  The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
13-2
The Properties of Mixtures:
Solutions and Colloids
Chapter 13
13-3
The Properties of Mixtures: Solutions and Colloids
13.1 Types of Solutions: Intermolecular Forces and Solubility
13.2 Intermolecular Forces and Biological Macromolecules
13.3 Why Substances Dissolve: Understanding the Solution Process
13.5 Concentration Terms
13.6 Colligative Properties of Solutions
13.7 Structure and Properties of Colloids
13.4 Solubility as an Equilibrium Process
13-4
Solutions and Colloids
A solution is a homogeneous mixture and exists as a
single phase.
The particles in a solution are individual atoms, ions, or small molecules.
A colloid is a heterogeneous mixture and exists as two or
more phases, which may be visibly distinct.
The particles in a colloid are typically macromolecules or aggregations of
small molecules.
13-5
Table 13.1 Approximate Composition of a Bacterium
*Includes precursors and metabolites.
Substance
Mass %
of Cell
Number
of Types
Number of
Molecules
Water ~70 1 5x1010
Ions 1 20 ?
Sugars* 3 200 3x108
Amino acids* 0.4 100 5x107
Lipids* 2 50 3x107
Nucleotides* 0.4 200 1x107
Other small molecules 0.2 ~200 ?
Macromolecules
(proteins, nucleic acids,
polysaccharides).
23 ~5000 6x106
13-6
Solutions and Solubility
A solute dissolves in a solvent to form a solution.
Usually, the solvent is the most abundant component.
The solubility (S) of a solute is the maximum amount
that dissolves in a fixed quantity of solvent at a given
temperature.
Substances that exhibit similar types of intermolecular
force dissolve in each other.
This is often expressed by saying “like dissolves in like.”
13-7
Figure 13.1 Types of intermolecular forces in solutions.
Ion-dipole
(40-600)
H bond
(10-40)
Dipole-dipole
(5-25)
Ion-induced dipole
(3-15)
Dipole-induced dipole
(2-10)
Dispersion
(0.05-40)
13-8
Solutions and Intermolecular Forces
When a solution forms, solute-solute attractions and
solvent-solvent attractions are replaced by solute-
solvent attractions.
This can only occur if the forces within the solute and
solvent are similar to the forces that replace them.
13-9
Figure 13.2 Hydration shells around an Na+ ion.
Ion-dipole forces orient water molecules around an ion. In the innermost
shell here, six water molecules surround the cation octahedrally.
13-10
Dual Polarity and Effects on Solubility
• Alcohols are organic compounds that have dual
polarity.
– The general formula for an alcohol is CH3(CH2)nOH.
• The –OH group of an alcohol is polar.
– It interacts with water through H bonds and
– with hexane by through weak dipole-induced dipole forces.
• The hydrocarbon portion is nonpolar.
– It interacts through weak dipole-induced dipole forces with
water
– and by dispersion forces with hexane.
13-11
Table 13.2 Solubility* of a Series of Alcohols in Water and in
Hexane.
Alcohol Model
Solubility
in Water
Solubility
in Hexane
CH3OH
(methanol)
∞ 1.2
CH3CH2OH
(ethanol)
∞ ∞
CH3(CH2)2OH
(propanol)
∞ ∞
(CH3(CH2)3OH
(1-butanol)
1.1 ∞
(CH3(CH2)4OH
(1-pentanol)
0.30 ∞
(CH3(CH2)5OH
(1-hexanol)
0.058 ∞
*Expressed in mol alcohol/1000 g solvent at 20°C.
13-12
Figure 13.3 Like dissolves like: solubility of methanol in water.
Both H2O and methanol have H bonds between their molecules.
H2O Methanol
CH3OH
A solution of water and methanol.
13-13
Sample Problem 13.1 Predicting Relative Solubilities
PROBLEM: Predict which solvent will dissolve more of the given
solute.
(a) Sodium chloride in methanol (CH3OH) or in propanol
(CH3CH2CH2OH).
(b) Ethylene glycol (HOCH2CH2OH) in hexane
(CH3CH2CH2CH2CH2CH3) or in water.
(c) Diethyl ether (CH3CH2OCH2CH3) in water or in ethanol
(CH3CH2OH).
PLAN: We examine the formulas of solute and solvent to determine
the forces in and between solute and solvent. A solute is more
soluble in a solvent whose intermolecular forces are similar
to, and therefore can replace, its own.
13-14
Sample Problem 13.1
SOLUTION:
(a) Methanol. NaCl is ionic, so it dissolves in polar solvents through
ion-dipole forces. Both methanol and 1-propanol have a polar –OH
group, but the hydrocarbon portion of each alcohol interacts only
weakly with the ions and 1-propanol has a longer hydrocarbon
portion than methanol.
(b) Water. Ethylene glycol molecules have two –OH groups, so they
interact with each other through H bonding. H bonds formed with
H2O can replace these H bonds between solute molecules better
than the dipole-induced dipole forces that form with hexane.
(c) Ethanol. Diethyl ether molecules interact through diple-dipole and
dispersion forces. They can form H bonds to H2O or to ethanol.
However, ethanol can also interact with the ether effectively
through dispersion forces because it has a hydrocarbon chain.
13-15
Gas Solubility (M)* bp (K)
He
Ne
N2
CO
O2
NO
4.2 x 10-4 4.2
6.6 x 10-4 27.1
10.4 x 10-4 77.4
15.6 x 10-4 81.6
21.8 x 10-4 90.2
32.7 x 10-4 121.4
* At 273 K and 1 atm
Table 13.3 Correlation Between Boiling Point and Solubility
in Water
13-16
Figure 13.4 The arrangement of atoms in two types of alloys.
Brass, a substitutional alloy Carbon steel, an interstitial alloy
13-17
Intermolecular Forces and Biological
Macromolecules
Intermolecular forces play a key role in determining the
structure and function of biological molecules.
There are two key groups of interactions to note:
Polar and ionic groups attract water, but nonpolar
groups do not.
Distant groups on the same molecule attract each other
in the same way that groups on different molecules do.
13-18
Figure 13.5 The charged form of an amino acid under
physiological conditions.
C
H3N
R
C
O
O-
H
+
one of 20 different side chains
-carbon
13-19
Figure 13.6 A portion of a polypeptide chain.
13-20
Figure 13.7 The forces that maintain protein structure.
13-21
Figure 13.8 The cleaning ability of a soap depends on the dual
polarity of its molecules.
13-22
Figure 13.9 A membrane phospholipid.
13-23
Figure 13.10 Intermolecular forces and cell membrane
structure.
13-24
Figure 13.11 The mode of action of the antibiotic gramicidin A.
Gramicidin A and similar antibiotics form channels through the cell
membrane, allowing ions to flow through. This disrupts the normal
balance of K+/Na+ concentrations and the cell dies.
13-25
Figure 13.12 A short portion of the polynucleotide chain of DNA.
13-26
Figure 13.13 The double helix of DNA.
13-27
Energy changes in Solution Formation
Step 1: Solute particles separate from each other. This
process is endothermic.
Solute (aggregated) + heat → solute (separated) ΔHsolute > 0
Step 2: Solvent particles separate from each other. This
process is endothermic.
Solute (separated) + solvent (separated) → solution + heat ΔHmix < 0
Step 3: Solute and solvent particles mix and form a
solution. This step is exothermic.
Solvent (aggregated) + heat → solvent (separated) ΔHsolvent > 0
13-28
Heat of Solution
DHsoln = DHsolute + DHsolvent + DHmix
Endothermic process: DHsoln < 0 because the sum of
the endothermic processes (DHsolute + DHsolvent) is larger
than the exothermic term (DHmix).
Exothermic process: DHsoln < 0 because the sum of
the endothermic processes (DHsolute + DHsolvent) is
smaller than the exothermic term (DHmix).
The overall solution process may be either exothermic
or endothermic.
13-29
Figure 13.14 Enthalpy components of the heat of solution.
Exothermic solution process
DHmix > DHsolute + DHsolvent
DHsoln < 0
Endothermic solution process
DHmix < DHsolute + DHsolvent
DHsoln > 0
13-30
Solvation and Hydration
Solvation is the process of surrounding a particle with
solvent particles. In water, solvation is called hydration.
DHsolvation = DHsolvent + DHmix
In water, DHsoln = DHsolute + DHhydr
The hydration of an ion is always exothermic because
ion-dipole forces are very strong.
M+(g) [or X-(g)] → M+(aq) [or X-(aq)] DHhydr of the ion (always < 0)
13-31
Trends in DHhydr for Ions
The higher the charge of the ion and the smaller its
radius, the closer the ion can be to the oppositely
charged pole of the H2O molecule, and the stronger the
attraction.
The heat of hydration for an ion depends on the charge
density, the ratio of charge to volume.
Charge density and DHhydr values increase across a
period.
Charge density and DHhydr values decrease down a
group.
13-32
Ion DHhydr (kJ/mol)
Ionic Radius (pm)
Group 1A(1)
Group 2A(2)
Group 7A(17)
Na+
K+
Rb+
Cs+
Mg2+
Ca2+
Sr2+
Ba2+
F-
Cl-
Br-
I-
102
138
152
167
-410
-336
-315
-282
72
100
118
133
-1903
-1591
-1424
-431
181 -313
196 -284
220 -247
135 -1317
Table 13.4 Trends in Ionic Heats of Hydration
13-33
Figure 13.15 Enthalpy diagrams for three ionic compounds
dissolving in water.
NaCl
NaOH
NH4NO3
13-34
Solutions and Entropy
Gases have the highest entropy of the three states of
matter.
The entropy (S) of a system is related to the number of
ways a system can disperse its energy and therefore to the
freedom of motion of the particles.
A solution usually has higher entropy than the pure solute
and pure solvent.
An increase in entropy is favored in both physical and
chemical processes.
13-35
Figure 13.16A Enthalpy diagram for dissolving NaCl in hexane.
For NaCl, DHmix is much smaller than DHsolute; DHsoln is so much
larger than the entropy increase due to mixing that NaCl does not
dissolve.
13-36
Figure 13.16B Enthalpy diagram for dissolving octane in hexane.
For octane, DHsoln is very small, but the entropy increase due to mixing is
large, so octane dissolves.
13-37
Solubility and Equilibrium
A saturated solution contains the maximum amount of
dissolved solute at a given temperature in the presence of
undissolved solute.
Undissolved solute is in equilibrium with dissolved solute.
Solute (undissolved)  solute (dissolved)
An unsaturated solution contains less than the
equilibrium concentration of dissolved solute. If more solute
is added, it will dissolve.
13-38
Figure 13.17 Equilibrium in a saturated solution.
solute (undissolved) solute (dissolved)
13-39
Figure 13.18 Sodium acetate crystallizing from a supersaturated
solution.
A supersaturated solution contains more
than the equilibrium concentration of solute. It
is unstable and any disturbance will cause
excess solute to crystallize immediately.
13-40
Factors that affect Solubility
Temperature affects solubility.
Most solids are more soluble at higher temperatures.
Gases become less soluble as temperature increases.
Pressure affects the solubility of gases – they become
more soluble at higher pressure.
13-41
Figure 13.19 Relation between solubility and temperature for
several ionic compounds.
13-42
Figure 13.20 Preventing thermal pollution with cooling towers.
13-43
Figure 13.21 The effect of pressure on gas solubility.
As the pressure is increased, more gas particles collide with the
liquid surface. More gas particles dissolve until equilibrium is re-
established.
13-44
Henry’s Law
Sgas = kH X Pgas
The solubility of a gas (Sgas) is directly proportional to the
partial pressure of the gas (Pgas) above the solution.
13-45
Sample Problem 13.2 Using Henry’s Law to Calculate Gas
Solubility
SOLUTION:
PROBLEM: The partial pressure of carbon dioxide gas inside a bottle
of cola is 4 atm at 25oC. What is the solubility of CO2?
The Henry’s law constant for CO2 dissolved in water is
3.3 x10-2 mol/L·atm at 25oC.
PLAN: We know P for CO2 (4 atm) and the value of kH, so we
substitute these into the Henry’s law equation.
0.1 mol/L
S = (3.3 x10-2 mol/L·atm)(4 atm) =
CO2
13-46
Concentration Term Ratio
Molarity (M)
amount (mol) of solute
volume (L) of solution
Molality (m)
amount (mol) of solute
mass (kg) of solvent
Parts by mass
mass of solute
mass of solution
Parts by volume
volume of solute
volume of solution
Mole fraction (X) amount (mol) of solute
amount (mol) of solute + amount (mol) of solvent
Table 13.5 Concentration Definitions
13-47
Sample Problem 13.3 Calculating Molality
PROBLEM: What is the molality of a solution prepared by dissolving
32.0 g of CaCl2 in 271 g of water?
PLAN: Molality is defined as moles of solute (CaCl2) divided by kg of
solvent (H2O). We convert the mass of CaCl2 to moles using
the molar mass, and then divide by the mass of H2O, being
sure to convert from grams to kilograms.
mass (g) of CaCl2
amount (mol) of CaCl2
molality (m) of CaCl2 solution
divide by M of (g/mol)
divide by kg of water
13-48
Sample Problem 13.3
SOLUTION:
molality =
= 0.288 mol CaCl2
271 g H2O
0.288 mol CaCl2
1 kg
103 g
x
= 1.06 m CaCl2
32.0 g CaCl2
1 mol CaCl2
110.98 g CaCl2
x
13-49
Sample Problem 13.4 Expressing Concentrations in Parts by
Mass, Parts by Volume, and Mole Fraction
PROBLEM: (a) Find the concentration of calcium (in ppm) in a 3.50-g
pill that contains 40.5 mg of Ca.
(b) The label on a 0.750-L bottle of Italian chianti indicates
“11.5% alcohol by volume.” How many liters of
alcohol does the wine contain?
(c) A sample of rubbing alcohol contains 142 g of
isopropyl alcohol (C3H7OH) and 58.0 g of water. What
are the mole fractions of alcohol and water?
PLAN: (a) We convert mg to g of Ca2+, find the mass ratio of Ca2+ to
pill and multiply by 106.
(b) We know the volume % of the alcohol and the total
volume, so we can find the volume of alcohol.
(c) We convert g of solute and solvent to moles in order to
calculate the mole fractions.
13-50
Sample Problem 13.4
SOLUTION:
(a)
3.5 g
103 mg
1 g
40.5 mg Ca2+ x
x 106 = 1.16x104 ppm Ca2+
(b)
11.5 L alcohol
100. L chianti
0.750 L chianti x = 0.0862 L alcohol
moles isopropyl alcohol = 142 g x 1 mole
60.09 g
= 2.36 mol C3H7OH
(c)
moles water = 58.0 g x 1 mole
18.02 g
= 3.22 mol H2O
13-51
Sample Problem 13.4
= 0.423
2.36 mol C2H8O2
2.36 mol C3H7OH + 3.22 mol H2O
XC3H7OH =
= 0.577
3.22 mol H2O
2.36 mol C3H7OH + 3.22 mol H2O
XH2O =
13-52
Interconverting Concentration Terms
• To convert a term based on amount (mol) to one based
on mass, you need the molar mass.
• To convert a term based on mass to one based on
volume, you need the solution density.
• Molality involves quantity of solvent, whereas the other
concentration terms involve quantity of solution.
13-53
Sample Problem 13.5 Interconverting Concentration Terms
PROBLEM: Hydrogen peroxide is a powerful oxidizing agent used in
concentrated solution in rocket fuels and in dilute solution
as a hair bleach. An aqueous solution H2O2 is 30.0% by
mass and has a density of 1.11 g/mL. Calculate its
(a) Molality (b) Mole fraction of H2O2 (c) Molarity
PLAN: (a) To find the mass of solvent we assume the % is per 100 g
of solution. Take the difference in the mass of the solute
and solution for the mass of peroxide.
(b) Convert g of solute and solvent to moles before finding X.
(c) Use the density to find the volume of the solution.
13-54
Sample Problem 13.5
SOLUTION:
(a) From mass % to molality:
g of H2O = 100. g solution - 30.0 g H2O2 = 70.0 g H2O
= 12.6 m H2O2
30.0 g H2O2 x = 0.882 mol H2O2
1 mol H2O2
34.02 g H2O2
molality =
70.0 g x 1 kg
103 g
0.882 mol H2O2
13-55
Sample Problem 13.5
(b) From mass % to mole fraction:
70.0 g H2O x
1 mol H2O
18.02 g H2O
= 3.88 mol H2O
= 0.185
3.88 mol H2O + 0.882 mol H2O2
0.882 mol H2O2
XH2O2
=
(c) From mass % and density to molarity:
volume (mL) of solution = 100.0 g x
1 mL
1.11 g
= 90.1 mL
molarity =
mol H2O2
L soln
=
90.1 mL x 1 L soln
103 mL
0.882 mol H2O2
= 9.79 M H2O2
13-56
Colligative Properties of Solutions
Colligative properties are properties that depend on the
number of solute particles, not their chemical identity.
An electrolyte separates into ions when it dissolves in
water.
Strong electrolytes dissociate completely while weak electrolytes
dissociate very little.
A nonelectrolyte does not dissociate to form ions.
Each mole of dissolved compound yields 1 mole of particles in
solution.
The number of particles in solution can be predicted from
the formula and type of the solute.
13-57
Figure 13.22 Conductivity of three types of electrolyte solutions.
strong electrolyte weak electrolyte nonelectrolyte
13-58
Vapor Pressure Lowering
The vapor pressure of a solution containing a nonvolatile
nonelectrolyte is always lower than the vapor pressure of
the pure solvent.
The vapor pressure lowering is proportional to the mole
fraction of the solute present.
Psolvent = Xsolvent x P°solvent
Raoult’s law states that the vapor pressure of the solvent
above the solution is proportional to the mole fraction of
the solvent present:
DPsolvent = Xsolute x P°solvent
13-59
Figure 13.23 Effect of solute on the vapor pressure of solution.
Equilibrium is reached with a
given number of particles in
the vapor.
Equilibrium is reached with
fewer particles in the vapor.
13-60
Sample Problem 13.6 Using Raoult’s Law to Find ΔP
PROBLEM: Find the vapor pressure lowering, DP, when 10.0 mL of
glycerol (C3H8O3) is added to 500. mL of water at 50.°C.
At this temperature, the vapor pressure of pure water is
92.5 torr and its density is 0.988 g/mL. The density of
glycerol is 1.26 g/mL.
PLAN: We are given the vapor pressure of pure H2O, so to calculate
DP we just need the mole fraction of glycerol, Xglycerol.
multiply by density
volume (mL) of glycerol
mass (g) of glycerol
mole fraction (X) of glycerol
multiply by M
amount (mol) of glycerol
vapor pressure lowering
multiply by P°glycerol
13-61
Sample Problem 13.6
SOLUTION:
= 0.137 mol C3H8O3
DP = 0.00498 x 92.5 torr
= 27.4 mol H2O
500.0 mL H2O x
0.988 g H2O
1 mL H2O
1 mol H2O
18.02 g H2O
x
10.0 mL C3H8O3 x 1.26 g C3H8O3
1 mL C3H8O3
1 mol C3H8O3
92.09 g C3H8O3
x
= 0.461 torr
0.137 mol C3H8O3
0.137 mol C3H8O3 + 27.4 mol H2O
Xglycerol = = 0.00498
13-62
Boiling Point Elevation
A solution always boils at a higher temperature than the
pure solvent.
This colligative property is a result of vapor pressure lowering.
DTb = Kbm
The boiling point elevation is proportional to the molality
of the solution.
Kb is the molal boiling point elevation constant for the solvent.
13-63
Figure 13.24 Boiling and freezing points of solvent and solution.
13-64
Freezing Point Depression
A solution always freezes at a lower temperature than the
pure solvent.
DTf = Kfm
The freezing point depression is proportional to the molality
of the solution.
Kf is the molal freezing point depression constant for the solvent.
13-65
*At 1 atm.
Solvent
Boiling
Point (oC)* Kb
(°C/m)
Kf
(°C/m)
Melting
Point
(°C)
Acetic acid
Benzene
Carbon disulfide
Carbon tetrachloride
Chloroform
Diethyl ether
Ethanol
Water
117.9
80.1
46.2
76.5
61.7
34.5
78.5
100.0
3.07 16.6 3.90
2.53 5.5 4.90
2.34 -111.5 3.83
5.03 -23 30.
3.63 -63.5 4.70
2.02 -116.2 1.79
1.22 -117.3 1.99
0.512 0.0 1.86
Table 13.6 Molal Boiling Point Elevation and Freezing Point
Depression Constants of Several Solvents
13-66
Sample Problem 13.7 Determining Boiling and Freezing Points
of a Solution
PROBLEM: You add 1.00 kg of ethylene glycol (C2H6O2) antifreeze to
4450 g of water in your car’s radiator. What are the
boiling and freezing points of the solution?
PLAN: We need to find the molality of the solution and then calculate
the boiling point elevation and freezing point depression.
divide by M
mass (g) of solute
amount (mol) of solute
molality (m)
divide by kg of solvent
DTb DTf
Tb(solution)
Tf(solution)
DTb = Kbm
Tb + DTb
DTf = Kfm Tf - DTf
13-67
Sample Problem 13.7
SOLUTION:
1.00x103 g C2H6O2 x 1 mol C2H6O2
62.07 g C2H6O2
= 16.1 mol C2H6O2
16.1 mol C2H6O2
4.450 kg H2O
= 3.62 m C2H6O2
molality =
DTb = 3.62 m x 0.512°C/m = 1.85°C
Tb(solution) = 100.00 + 1.85 = 101.85°C
DTf = 3.62 m x 1.86°C/m = 6.73°C
Tb(solution) = 0.00 - 6.73 = -6.73°C
13-68
Osmotic Pressure
Osmosis is the movement of solvent particles from a
region of higher to a region of lower concentration through
a semipermeable membrane.
Π = MRT
Solvent will always flow from a more dilute solution to a
more concentrated one.
Osmotic pressure is the pressure that must be applied to
prevent the net flow of solvent.
M = molarity
R = 0.0821 atm·L/mol·K
T = Kelvin temperature
13-69
Figure 13.25 The development of osmotic pressure.
13-70
Sample Problem 13.8 Determining Molar Mass from Osmotic
Pressure
PROBLEM: Biochemists have discovered more than 400 mutant
varieties of hemoglobin, the blood protein that carries O2.
A physician dissolves 21.5 mg of one variety in water to
make 1.50 mL of solution at 5.0°C. She measures an
osmotic pressure of 3.61 torr. What is the molar mass of
the protein?
PLAN: We convert Π to atm and T to degrees K and calculate
molarity from osmotic pressure. We can then determine the
molar mass using the number of moles and the known mass.
Π = MRT
Π (atm)
M (mol/L)
M (g/mol)
amount (mol) of solute
divide mass (g) by moles
convert to mol
13-71
Sample Problem 13.8
SOLUTION:
1 atm
760 torr
M =
Π
RT
=
3.61 torr x
(0.0821 L·atm/mol·K)(278.15 K)
= 2.08 x10-4 M
= 6.89x104 g/mol
2.08 x10-4 mol
1 L 103 mL
1 L = 3.12x10-7 mol
x
21.5 mg x 1 g
103 mg
= 0.0215 g
M =
0.0215 g
3.12x10-7 mol
13-72
Volatile Nonelectrolyte Solutions
For a volatile nonelectrolyte, the vapor of the solution
contains both solute and solvent.
The presence of each volatile component lowers the
vapor pressure of the other, since each one lowers the
mole fraction of the other.
For such a solution, the vapor will have a higher mole
fraction of the more volatile component.
The vapor has a different composition than the solution.
13-73
Strong Electrolyte Solutions
A strong electrolyte dissociates completely to form ions.
Each mole of solute gives more than 1 mol of dissolved
particles.
The van’t Hoff factor takes into account the dissociation
of a strong electrolyte to predict the effect on the solution.
The formula of the compound indicates the expected
number of particles in solution.
Each mol of NaCl is expected to give 2 moles of dissolved ions,
i =
measured value for electrolyte solution
expected value for nonelectrolyte solution
13-74
Colligative Properties of Electrolyte Solutions
For vapor pressure lowering: DP = i(Csolute x Po
solvent)
For boiling point elevation: DTb = i(bm)
For freezing point depression: DTf = i(fm)
For osmotic pressure: Π = i(MRT)
13-75
Figure 13.26
Nonideal behavior of
strong electrolyte
solutions.
Ions in solution may remain clustered
near ions of opposite charge, creating
an ionic atmosphere. The ions do not
act independently, and the effective
concentration of dissolved particles is
less than expected.
13-76
Figure 13.27 An ionic atmosphere model for nonideal behavior of
electrolyte solutions.
Ions may remain clustered together in solution, forming an ionic
atmosphere. This effect is greater for a more concentrated solution.
13-77
Sample Problem 13.9 Depicting Strong Electrolyte Solutions
A 0.952-g sample of magnesium chloride dissolves in
100. g of water in a flask.
PROBLEM:
(a) Which scene depicts the solution best?
(b) What is the amount (mol) represented by each green sphere?
(c) Assuming the solution is ideal, what is its freezing point (at 1 atm)?
13-78
Sample Problem 13.9
PLAN: (a) We find the numbers of cations and anions per formula unit
from the name and compare it with the three scenes.
(b) We convert the given mass to amount (mol), and use the
answer from part (a) to find the moles of chloride ions. We
can then determine the number of moles per sphere.
(c) We find the molality (m) from the data provided and use it to
calculate DTf for the solution.
(a) The formula for magnesium chloride is MgCl2. Only scene A has 1
Mg2+ for every 2 Cl- ions.
SOLUTION:
13-79
Sample Problem 13.9
(b) The solution contains 0.952 g of MgCl2 in 100. g of water.
0.952 g MgCl2 x 1 mol MgCl2
95.21 g MgCl2
= 0.0100 mol MgCl2
Every 1 mol of MgCl2 forms 1 mol Mg2+ and 2 mol Cl- so
there should be 0.0200 mol Cl- ions. There are 8 green spheres :
0.0200 mol Cl- ions
8 green spheres
= 2.50x10-3 mol/sphere
13-80
Sample Problem 13.9
(c) Assuming an ideal solution, i = 3 for MgCl2 since there are 3 ions
per formula unit.
molality =
0.0100 mol MgCl2
100. g x
1 kg
1000 g
= 0.100 m MgCl2
DTf = i(Kfm) = 3(1.86°C/m x 0.100 m) = 0.558°C
Tf = 0.000°C – 0.558°C = -0.558°C
13-81
Figure 13.28 Fractional distillation in petroleum refining.
13-82
Figure 13.29a Osmotic pressure and cell shape.
A red blood cell in an isotonic solution has its normal shape.
13-83
Figure 13.29b Osmotic pressure and cell shape.
A hypotonic solution has a lower concentration of particles than
the cell. A cell in a hypotonic solution absorbs water and swells
until it bursts.
13-84
Figure 13.29c Osmotic pressure and cell shape.
A hypertonic solution has a higher concentration of dissolved particles
than the cell. If a cell is placed in a hypertonic solution, water moves
out of the cell, causing it to shrink.
13-85
Table 13.7 Types of Colloids
Dispersed
Substance
Dispersing
Medium
Colloid Type Example(s)
Aerosol
Aerosol
Foam
Solid foam
Emulsion
Solid emulsion
Sol
Solid sol
Liquid Gas Fog
Solid Gas Smoke
Gas Liquid Whipped cream
Gas Solid Marshmallow
Liquid Liquid Milk
Liquid Solid Butter
Solid Liquid Paint; cell fluid
Solid Solid Opal
13-86
Figure 13.30 Light scattering and the Tyndall effect.
The narrow, barely visible light
beam that passes through a
solution (left), is scattered and
broadened by passing through
a colloid (right).
Sunlight is scattered by dust in
air.
13-87
Figure 13.31 The Nile delta (reddish-brown area).
At the mouths of rivers, colloidal clay particles coalesce into muddy deltas.
13-88
Figure B13.1
Figure B13.1 The typical steps in municipal water treatment.
Chemical Connections
13-89
Figure B13.2 Ion exchange to remove hard-water cations.
Chemical Connections
13-90
Figure B13.3 Reverse osmosis to remove ions.
Chemical Connections

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ch13_lecture_6e_final3.ppt

  • 1. 13-1 Lecture PowerPoint Chemistry The Molecular Nature of Matter and Change Sixth Edition Martin S. Silberberg Copyright  The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
  • 2. 13-2 The Properties of Mixtures: Solutions and Colloids Chapter 13
  • 3. 13-3 The Properties of Mixtures: Solutions and Colloids 13.1 Types of Solutions: Intermolecular Forces and Solubility 13.2 Intermolecular Forces and Biological Macromolecules 13.3 Why Substances Dissolve: Understanding the Solution Process 13.5 Concentration Terms 13.6 Colligative Properties of Solutions 13.7 Structure and Properties of Colloids 13.4 Solubility as an Equilibrium Process
  • 4. 13-4 Solutions and Colloids A solution is a homogeneous mixture and exists as a single phase. The particles in a solution are individual atoms, ions, or small molecules. A colloid is a heterogeneous mixture and exists as two or more phases, which may be visibly distinct. The particles in a colloid are typically macromolecules or aggregations of small molecules.
  • 5. 13-5 Table 13.1 Approximate Composition of a Bacterium *Includes precursors and metabolites. Substance Mass % of Cell Number of Types Number of Molecules Water ~70 1 5x1010 Ions 1 20 ? Sugars* 3 200 3x108 Amino acids* 0.4 100 5x107 Lipids* 2 50 3x107 Nucleotides* 0.4 200 1x107 Other small molecules 0.2 ~200 ? Macromolecules (proteins, nucleic acids, polysaccharides). 23 ~5000 6x106
  • 6. 13-6 Solutions and Solubility A solute dissolves in a solvent to form a solution. Usually, the solvent is the most abundant component. The solubility (S) of a solute is the maximum amount that dissolves in a fixed quantity of solvent at a given temperature. Substances that exhibit similar types of intermolecular force dissolve in each other. This is often expressed by saying “like dissolves in like.”
  • 7. 13-7 Figure 13.1 Types of intermolecular forces in solutions. Ion-dipole (40-600) H bond (10-40) Dipole-dipole (5-25) Ion-induced dipole (3-15) Dipole-induced dipole (2-10) Dispersion (0.05-40)
  • 8. 13-8 Solutions and Intermolecular Forces When a solution forms, solute-solute attractions and solvent-solvent attractions are replaced by solute- solvent attractions. This can only occur if the forces within the solute and solvent are similar to the forces that replace them.
  • 9. 13-9 Figure 13.2 Hydration shells around an Na+ ion. Ion-dipole forces orient water molecules around an ion. In the innermost shell here, six water molecules surround the cation octahedrally.
  • 10. 13-10 Dual Polarity and Effects on Solubility • Alcohols are organic compounds that have dual polarity. – The general formula for an alcohol is CH3(CH2)nOH. • The –OH group of an alcohol is polar. – It interacts with water through H bonds and – with hexane by through weak dipole-induced dipole forces. • The hydrocarbon portion is nonpolar. – It interacts through weak dipole-induced dipole forces with water – and by dispersion forces with hexane.
  • 11. 13-11 Table 13.2 Solubility* of a Series of Alcohols in Water and in Hexane. Alcohol Model Solubility in Water Solubility in Hexane CH3OH (methanol) ∞ 1.2 CH3CH2OH (ethanol) ∞ ∞ CH3(CH2)2OH (propanol) ∞ ∞ (CH3(CH2)3OH (1-butanol) 1.1 ∞ (CH3(CH2)4OH (1-pentanol) 0.30 ∞ (CH3(CH2)5OH (1-hexanol) 0.058 ∞ *Expressed in mol alcohol/1000 g solvent at 20°C.
  • 12. 13-12 Figure 13.3 Like dissolves like: solubility of methanol in water. Both H2O and methanol have H bonds between their molecules. H2O Methanol CH3OH A solution of water and methanol.
  • 13. 13-13 Sample Problem 13.1 Predicting Relative Solubilities PROBLEM: Predict which solvent will dissolve more of the given solute. (a) Sodium chloride in methanol (CH3OH) or in propanol (CH3CH2CH2OH). (b) Ethylene glycol (HOCH2CH2OH) in hexane (CH3CH2CH2CH2CH2CH3) or in water. (c) Diethyl ether (CH3CH2OCH2CH3) in water or in ethanol (CH3CH2OH). PLAN: We examine the formulas of solute and solvent to determine the forces in and between solute and solvent. A solute is more soluble in a solvent whose intermolecular forces are similar to, and therefore can replace, its own.
  • 14. 13-14 Sample Problem 13.1 SOLUTION: (a) Methanol. NaCl is ionic, so it dissolves in polar solvents through ion-dipole forces. Both methanol and 1-propanol have a polar –OH group, but the hydrocarbon portion of each alcohol interacts only weakly with the ions and 1-propanol has a longer hydrocarbon portion than methanol. (b) Water. Ethylene glycol molecules have two –OH groups, so they interact with each other through H bonding. H bonds formed with H2O can replace these H bonds between solute molecules better than the dipole-induced dipole forces that form with hexane. (c) Ethanol. Diethyl ether molecules interact through diple-dipole and dispersion forces. They can form H bonds to H2O or to ethanol. However, ethanol can also interact with the ether effectively through dispersion forces because it has a hydrocarbon chain.
  • 15. 13-15 Gas Solubility (M)* bp (K) He Ne N2 CO O2 NO 4.2 x 10-4 4.2 6.6 x 10-4 27.1 10.4 x 10-4 77.4 15.6 x 10-4 81.6 21.8 x 10-4 90.2 32.7 x 10-4 121.4 * At 273 K and 1 atm Table 13.3 Correlation Between Boiling Point and Solubility in Water
  • 16. 13-16 Figure 13.4 The arrangement of atoms in two types of alloys. Brass, a substitutional alloy Carbon steel, an interstitial alloy
  • 17. 13-17 Intermolecular Forces and Biological Macromolecules Intermolecular forces play a key role in determining the structure and function of biological molecules. There are two key groups of interactions to note: Polar and ionic groups attract water, but nonpolar groups do not. Distant groups on the same molecule attract each other in the same way that groups on different molecules do.
  • 18. 13-18 Figure 13.5 The charged form of an amino acid under physiological conditions. C H3N R C O O- H + one of 20 different side chains -carbon
  • 19. 13-19 Figure 13.6 A portion of a polypeptide chain.
  • 20. 13-20 Figure 13.7 The forces that maintain protein structure.
  • 21. 13-21 Figure 13.8 The cleaning ability of a soap depends on the dual polarity of its molecules.
  • 22. 13-22 Figure 13.9 A membrane phospholipid.
  • 23. 13-23 Figure 13.10 Intermolecular forces and cell membrane structure.
  • 24. 13-24 Figure 13.11 The mode of action of the antibiotic gramicidin A. Gramicidin A and similar antibiotics form channels through the cell membrane, allowing ions to flow through. This disrupts the normal balance of K+/Na+ concentrations and the cell dies.
  • 25. 13-25 Figure 13.12 A short portion of the polynucleotide chain of DNA.
  • 26. 13-26 Figure 13.13 The double helix of DNA.
  • 27. 13-27 Energy changes in Solution Formation Step 1: Solute particles separate from each other. This process is endothermic. Solute (aggregated) + heat → solute (separated) ΔHsolute > 0 Step 2: Solvent particles separate from each other. This process is endothermic. Solute (separated) + solvent (separated) → solution + heat ΔHmix < 0 Step 3: Solute and solvent particles mix and form a solution. This step is exothermic. Solvent (aggregated) + heat → solvent (separated) ΔHsolvent > 0
  • 28. 13-28 Heat of Solution DHsoln = DHsolute + DHsolvent + DHmix Endothermic process: DHsoln < 0 because the sum of the endothermic processes (DHsolute + DHsolvent) is larger than the exothermic term (DHmix). Exothermic process: DHsoln < 0 because the sum of the endothermic processes (DHsolute + DHsolvent) is smaller than the exothermic term (DHmix). The overall solution process may be either exothermic or endothermic.
  • 29. 13-29 Figure 13.14 Enthalpy components of the heat of solution. Exothermic solution process DHmix > DHsolute + DHsolvent DHsoln < 0 Endothermic solution process DHmix < DHsolute + DHsolvent DHsoln > 0
  • 30. 13-30 Solvation and Hydration Solvation is the process of surrounding a particle with solvent particles. In water, solvation is called hydration. DHsolvation = DHsolvent + DHmix In water, DHsoln = DHsolute + DHhydr The hydration of an ion is always exothermic because ion-dipole forces are very strong. M+(g) [or X-(g)] → M+(aq) [or X-(aq)] DHhydr of the ion (always < 0)
  • 31. 13-31 Trends in DHhydr for Ions The higher the charge of the ion and the smaller its radius, the closer the ion can be to the oppositely charged pole of the H2O molecule, and the stronger the attraction. The heat of hydration for an ion depends on the charge density, the ratio of charge to volume. Charge density and DHhydr values increase across a period. Charge density and DHhydr values decrease down a group.
  • 32. 13-32 Ion DHhydr (kJ/mol) Ionic Radius (pm) Group 1A(1) Group 2A(2) Group 7A(17) Na+ K+ Rb+ Cs+ Mg2+ Ca2+ Sr2+ Ba2+ F- Cl- Br- I- 102 138 152 167 -410 -336 -315 -282 72 100 118 133 -1903 -1591 -1424 -431 181 -313 196 -284 220 -247 135 -1317 Table 13.4 Trends in Ionic Heats of Hydration
  • 33. 13-33 Figure 13.15 Enthalpy diagrams for three ionic compounds dissolving in water. NaCl NaOH NH4NO3
  • 34. 13-34 Solutions and Entropy Gases have the highest entropy of the three states of matter. The entropy (S) of a system is related to the number of ways a system can disperse its energy and therefore to the freedom of motion of the particles. A solution usually has higher entropy than the pure solute and pure solvent. An increase in entropy is favored in both physical and chemical processes.
  • 35. 13-35 Figure 13.16A Enthalpy diagram for dissolving NaCl in hexane. For NaCl, DHmix is much smaller than DHsolute; DHsoln is so much larger than the entropy increase due to mixing that NaCl does not dissolve.
  • 36. 13-36 Figure 13.16B Enthalpy diagram for dissolving octane in hexane. For octane, DHsoln is very small, but the entropy increase due to mixing is large, so octane dissolves.
  • 37. 13-37 Solubility and Equilibrium A saturated solution contains the maximum amount of dissolved solute at a given temperature in the presence of undissolved solute. Undissolved solute is in equilibrium with dissolved solute. Solute (undissolved)  solute (dissolved) An unsaturated solution contains less than the equilibrium concentration of dissolved solute. If more solute is added, it will dissolve.
  • 38. 13-38 Figure 13.17 Equilibrium in a saturated solution. solute (undissolved) solute (dissolved)
  • 39. 13-39 Figure 13.18 Sodium acetate crystallizing from a supersaturated solution. A supersaturated solution contains more than the equilibrium concentration of solute. It is unstable and any disturbance will cause excess solute to crystallize immediately.
  • 40. 13-40 Factors that affect Solubility Temperature affects solubility. Most solids are more soluble at higher temperatures. Gases become less soluble as temperature increases. Pressure affects the solubility of gases – they become more soluble at higher pressure.
  • 41. 13-41 Figure 13.19 Relation between solubility and temperature for several ionic compounds.
  • 42. 13-42 Figure 13.20 Preventing thermal pollution with cooling towers.
  • 43. 13-43 Figure 13.21 The effect of pressure on gas solubility. As the pressure is increased, more gas particles collide with the liquid surface. More gas particles dissolve until equilibrium is re- established.
  • 44. 13-44 Henry’s Law Sgas = kH X Pgas The solubility of a gas (Sgas) is directly proportional to the partial pressure of the gas (Pgas) above the solution.
  • 45. 13-45 Sample Problem 13.2 Using Henry’s Law to Calculate Gas Solubility SOLUTION: PROBLEM: The partial pressure of carbon dioxide gas inside a bottle of cola is 4 atm at 25oC. What is the solubility of CO2? The Henry’s law constant for CO2 dissolved in water is 3.3 x10-2 mol/L·atm at 25oC. PLAN: We know P for CO2 (4 atm) and the value of kH, so we substitute these into the Henry’s law equation. 0.1 mol/L S = (3.3 x10-2 mol/L·atm)(4 atm) = CO2
  • 46. 13-46 Concentration Term Ratio Molarity (M) amount (mol) of solute volume (L) of solution Molality (m) amount (mol) of solute mass (kg) of solvent Parts by mass mass of solute mass of solution Parts by volume volume of solute volume of solution Mole fraction (X) amount (mol) of solute amount (mol) of solute + amount (mol) of solvent Table 13.5 Concentration Definitions
  • 47. 13-47 Sample Problem 13.3 Calculating Molality PROBLEM: What is the molality of a solution prepared by dissolving 32.0 g of CaCl2 in 271 g of water? PLAN: Molality is defined as moles of solute (CaCl2) divided by kg of solvent (H2O). We convert the mass of CaCl2 to moles using the molar mass, and then divide by the mass of H2O, being sure to convert from grams to kilograms. mass (g) of CaCl2 amount (mol) of CaCl2 molality (m) of CaCl2 solution divide by M of (g/mol) divide by kg of water
  • 48. 13-48 Sample Problem 13.3 SOLUTION: molality = = 0.288 mol CaCl2 271 g H2O 0.288 mol CaCl2 1 kg 103 g x = 1.06 m CaCl2 32.0 g CaCl2 1 mol CaCl2 110.98 g CaCl2 x
  • 49. 13-49 Sample Problem 13.4 Expressing Concentrations in Parts by Mass, Parts by Volume, and Mole Fraction PROBLEM: (a) Find the concentration of calcium (in ppm) in a 3.50-g pill that contains 40.5 mg of Ca. (b) The label on a 0.750-L bottle of Italian chianti indicates “11.5% alcohol by volume.” How many liters of alcohol does the wine contain? (c) A sample of rubbing alcohol contains 142 g of isopropyl alcohol (C3H7OH) and 58.0 g of water. What are the mole fractions of alcohol and water? PLAN: (a) We convert mg to g of Ca2+, find the mass ratio of Ca2+ to pill and multiply by 106. (b) We know the volume % of the alcohol and the total volume, so we can find the volume of alcohol. (c) We convert g of solute and solvent to moles in order to calculate the mole fractions.
  • 50. 13-50 Sample Problem 13.4 SOLUTION: (a) 3.5 g 103 mg 1 g 40.5 mg Ca2+ x x 106 = 1.16x104 ppm Ca2+ (b) 11.5 L alcohol 100. L chianti 0.750 L chianti x = 0.0862 L alcohol moles isopropyl alcohol = 142 g x 1 mole 60.09 g = 2.36 mol C3H7OH (c) moles water = 58.0 g x 1 mole 18.02 g = 3.22 mol H2O
  • 51. 13-51 Sample Problem 13.4 = 0.423 2.36 mol C2H8O2 2.36 mol C3H7OH + 3.22 mol H2O XC3H7OH = = 0.577 3.22 mol H2O 2.36 mol C3H7OH + 3.22 mol H2O XH2O =
  • 52. 13-52 Interconverting Concentration Terms • To convert a term based on amount (mol) to one based on mass, you need the molar mass. • To convert a term based on mass to one based on volume, you need the solution density. • Molality involves quantity of solvent, whereas the other concentration terms involve quantity of solution.
  • 53. 13-53 Sample Problem 13.5 Interconverting Concentration Terms PROBLEM: Hydrogen peroxide is a powerful oxidizing agent used in concentrated solution in rocket fuels and in dilute solution as a hair bleach. An aqueous solution H2O2 is 30.0% by mass and has a density of 1.11 g/mL. Calculate its (a) Molality (b) Mole fraction of H2O2 (c) Molarity PLAN: (a) To find the mass of solvent we assume the % is per 100 g of solution. Take the difference in the mass of the solute and solution for the mass of peroxide. (b) Convert g of solute and solvent to moles before finding X. (c) Use the density to find the volume of the solution.
  • 54. 13-54 Sample Problem 13.5 SOLUTION: (a) From mass % to molality: g of H2O = 100. g solution - 30.0 g H2O2 = 70.0 g H2O = 12.6 m H2O2 30.0 g H2O2 x = 0.882 mol H2O2 1 mol H2O2 34.02 g H2O2 molality = 70.0 g x 1 kg 103 g 0.882 mol H2O2
  • 55. 13-55 Sample Problem 13.5 (b) From mass % to mole fraction: 70.0 g H2O x 1 mol H2O 18.02 g H2O = 3.88 mol H2O = 0.185 3.88 mol H2O + 0.882 mol H2O2 0.882 mol H2O2 XH2O2 = (c) From mass % and density to molarity: volume (mL) of solution = 100.0 g x 1 mL 1.11 g = 90.1 mL molarity = mol H2O2 L soln = 90.1 mL x 1 L soln 103 mL 0.882 mol H2O2 = 9.79 M H2O2
  • 56. 13-56 Colligative Properties of Solutions Colligative properties are properties that depend on the number of solute particles, not their chemical identity. An electrolyte separates into ions when it dissolves in water. Strong electrolytes dissociate completely while weak electrolytes dissociate very little. A nonelectrolyte does not dissociate to form ions. Each mole of dissolved compound yields 1 mole of particles in solution. The number of particles in solution can be predicted from the formula and type of the solute.
  • 57. 13-57 Figure 13.22 Conductivity of three types of electrolyte solutions. strong electrolyte weak electrolyte nonelectrolyte
  • 58. 13-58 Vapor Pressure Lowering The vapor pressure of a solution containing a nonvolatile nonelectrolyte is always lower than the vapor pressure of the pure solvent. The vapor pressure lowering is proportional to the mole fraction of the solute present. Psolvent = Xsolvent x P°solvent Raoult’s law states that the vapor pressure of the solvent above the solution is proportional to the mole fraction of the solvent present: DPsolvent = Xsolute x P°solvent
  • 59. 13-59 Figure 13.23 Effect of solute on the vapor pressure of solution. Equilibrium is reached with a given number of particles in the vapor. Equilibrium is reached with fewer particles in the vapor.
  • 60. 13-60 Sample Problem 13.6 Using Raoult’s Law to Find ΔP PROBLEM: Find the vapor pressure lowering, DP, when 10.0 mL of glycerol (C3H8O3) is added to 500. mL of water at 50.°C. At this temperature, the vapor pressure of pure water is 92.5 torr and its density is 0.988 g/mL. The density of glycerol is 1.26 g/mL. PLAN: We are given the vapor pressure of pure H2O, so to calculate DP we just need the mole fraction of glycerol, Xglycerol. multiply by density volume (mL) of glycerol mass (g) of glycerol mole fraction (X) of glycerol multiply by M amount (mol) of glycerol vapor pressure lowering multiply by P°glycerol
  • 61. 13-61 Sample Problem 13.6 SOLUTION: = 0.137 mol C3H8O3 DP = 0.00498 x 92.5 torr = 27.4 mol H2O 500.0 mL H2O x 0.988 g H2O 1 mL H2O 1 mol H2O 18.02 g H2O x 10.0 mL C3H8O3 x 1.26 g C3H8O3 1 mL C3H8O3 1 mol C3H8O3 92.09 g C3H8O3 x = 0.461 torr 0.137 mol C3H8O3 0.137 mol C3H8O3 + 27.4 mol H2O Xglycerol = = 0.00498
  • 62. 13-62 Boiling Point Elevation A solution always boils at a higher temperature than the pure solvent. This colligative property is a result of vapor pressure lowering. DTb = Kbm The boiling point elevation is proportional to the molality of the solution. Kb is the molal boiling point elevation constant for the solvent.
  • 63. 13-63 Figure 13.24 Boiling and freezing points of solvent and solution.
  • 64. 13-64 Freezing Point Depression A solution always freezes at a lower temperature than the pure solvent. DTf = Kfm The freezing point depression is proportional to the molality of the solution. Kf is the molal freezing point depression constant for the solvent.
  • 65. 13-65 *At 1 atm. Solvent Boiling Point (oC)* Kb (°C/m) Kf (°C/m) Melting Point (°C) Acetic acid Benzene Carbon disulfide Carbon tetrachloride Chloroform Diethyl ether Ethanol Water 117.9 80.1 46.2 76.5 61.7 34.5 78.5 100.0 3.07 16.6 3.90 2.53 5.5 4.90 2.34 -111.5 3.83 5.03 -23 30. 3.63 -63.5 4.70 2.02 -116.2 1.79 1.22 -117.3 1.99 0.512 0.0 1.86 Table 13.6 Molal Boiling Point Elevation and Freezing Point Depression Constants of Several Solvents
  • 66. 13-66 Sample Problem 13.7 Determining Boiling and Freezing Points of a Solution PROBLEM: You add 1.00 kg of ethylene glycol (C2H6O2) antifreeze to 4450 g of water in your car’s radiator. What are the boiling and freezing points of the solution? PLAN: We need to find the molality of the solution and then calculate the boiling point elevation and freezing point depression. divide by M mass (g) of solute amount (mol) of solute molality (m) divide by kg of solvent DTb DTf Tb(solution) Tf(solution) DTb = Kbm Tb + DTb DTf = Kfm Tf - DTf
  • 67. 13-67 Sample Problem 13.7 SOLUTION: 1.00x103 g C2H6O2 x 1 mol C2H6O2 62.07 g C2H6O2 = 16.1 mol C2H6O2 16.1 mol C2H6O2 4.450 kg H2O = 3.62 m C2H6O2 molality = DTb = 3.62 m x 0.512°C/m = 1.85°C Tb(solution) = 100.00 + 1.85 = 101.85°C DTf = 3.62 m x 1.86°C/m = 6.73°C Tb(solution) = 0.00 - 6.73 = -6.73°C
  • 68. 13-68 Osmotic Pressure Osmosis is the movement of solvent particles from a region of higher to a region of lower concentration through a semipermeable membrane. Π = MRT Solvent will always flow from a more dilute solution to a more concentrated one. Osmotic pressure is the pressure that must be applied to prevent the net flow of solvent. M = molarity R = 0.0821 atm·L/mol·K T = Kelvin temperature
  • 69. 13-69 Figure 13.25 The development of osmotic pressure.
  • 70. 13-70 Sample Problem 13.8 Determining Molar Mass from Osmotic Pressure PROBLEM: Biochemists have discovered more than 400 mutant varieties of hemoglobin, the blood protein that carries O2. A physician dissolves 21.5 mg of one variety in water to make 1.50 mL of solution at 5.0°C. She measures an osmotic pressure of 3.61 torr. What is the molar mass of the protein? PLAN: We convert Π to atm and T to degrees K and calculate molarity from osmotic pressure. We can then determine the molar mass using the number of moles and the known mass. Π = MRT Π (atm) M (mol/L) M (g/mol) amount (mol) of solute divide mass (g) by moles convert to mol
  • 71. 13-71 Sample Problem 13.8 SOLUTION: 1 atm 760 torr M = Π RT = 3.61 torr x (0.0821 L·atm/mol·K)(278.15 K) = 2.08 x10-4 M = 6.89x104 g/mol 2.08 x10-4 mol 1 L 103 mL 1 L = 3.12x10-7 mol x 21.5 mg x 1 g 103 mg = 0.0215 g M = 0.0215 g 3.12x10-7 mol
  • 72. 13-72 Volatile Nonelectrolyte Solutions For a volatile nonelectrolyte, the vapor of the solution contains both solute and solvent. The presence of each volatile component lowers the vapor pressure of the other, since each one lowers the mole fraction of the other. For such a solution, the vapor will have a higher mole fraction of the more volatile component. The vapor has a different composition than the solution.
  • 73. 13-73 Strong Electrolyte Solutions A strong electrolyte dissociates completely to form ions. Each mole of solute gives more than 1 mol of dissolved particles. The van’t Hoff factor takes into account the dissociation of a strong electrolyte to predict the effect on the solution. The formula of the compound indicates the expected number of particles in solution. Each mol of NaCl is expected to give 2 moles of dissolved ions, i = measured value for electrolyte solution expected value for nonelectrolyte solution
  • 74. 13-74 Colligative Properties of Electrolyte Solutions For vapor pressure lowering: DP = i(Csolute x Po solvent) For boiling point elevation: DTb = i(bm) For freezing point depression: DTf = i(fm) For osmotic pressure: Π = i(MRT)
  • 75. 13-75 Figure 13.26 Nonideal behavior of strong electrolyte solutions. Ions in solution may remain clustered near ions of opposite charge, creating an ionic atmosphere. The ions do not act independently, and the effective concentration of dissolved particles is less than expected.
  • 76. 13-76 Figure 13.27 An ionic atmosphere model for nonideal behavior of electrolyte solutions. Ions may remain clustered together in solution, forming an ionic atmosphere. This effect is greater for a more concentrated solution.
  • 77. 13-77 Sample Problem 13.9 Depicting Strong Electrolyte Solutions A 0.952-g sample of magnesium chloride dissolves in 100. g of water in a flask. PROBLEM: (a) Which scene depicts the solution best? (b) What is the amount (mol) represented by each green sphere? (c) Assuming the solution is ideal, what is its freezing point (at 1 atm)?
  • 78. 13-78 Sample Problem 13.9 PLAN: (a) We find the numbers of cations and anions per formula unit from the name and compare it with the three scenes. (b) We convert the given mass to amount (mol), and use the answer from part (a) to find the moles of chloride ions. We can then determine the number of moles per sphere. (c) We find the molality (m) from the data provided and use it to calculate DTf for the solution. (a) The formula for magnesium chloride is MgCl2. Only scene A has 1 Mg2+ for every 2 Cl- ions. SOLUTION:
  • 79. 13-79 Sample Problem 13.9 (b) The solution contains 0.952 g of MgCl2 in 100. g of water. 0.952 g MgCl2 x 1 mol MgCl2 95.21 g MgCl2 = 0.0100 mol MgCl2 Every 1 mol of MgCl2 forms 1 mol Mg2+ and 2 mol Cl- so there should be 0.0200 mol Cl- ions. There are 8 green spheres : 0.0200 mol Cl- ions 8 green spheres = 2.50x10-3 mol/sphere
  • 80. 13-80 Sample Problem 13.9 (c) Assuming an ideal solution, i = 3 for MgCl2 since there are 3 ions per formula unit. molality = 0.0100 mol MgCl2 100. g x 1 kg 1000 g = 0.100 m MgCl2 DTf = i(Kfm) = 3(1.86°C/m x 0.100 m) = 0.558°C Tf = 0.000°C – 0.558°C = -0.558°C
  • 81. 13-81 Figure 13.28 Fractional distillation in petroleum refining.
  • 82. 13-82 Figure 13.29a Osmotic pressure and cell shape. A red blood cell in an isotonic solution has its normal shape.
  • 83. 13-83 Figure 13.29b Osmotic pressure and cell shape. A hypotonic solution has a lower concentration of particles than the cell. A cell in a hypotonic solution absorbs water and swells until it bursts.
  • 84. 13-84 Figure 13.29c Osmotic pressure and cell shape. A hypertonic solution has a higher concentration of dissolved particles than the cell. If a cell is placed in a hypertonic solution, water moves out of the cell, causing it to shrink.
  • 85. 13-85 Table 13.7 Types of Colloids Dispersed Substance Dispersing Medium Colloid Type Example(s) Aerosol Aerosol Foam Solid foam Emulsion Solid emulsion Sol Solid sol Liquid Gas Fog Solid Gas Smoke Gas Liquid Whipped cream Gas Solid Marshmallow Liquid Liquid Milk Liquid Solid Butter Solid Liquid Paint; cell fluid Solid Solid Opal
  • 86. 13-86 Figure 13.30 Light scattering and the Tyndall effect. The narrow, barely visible light beam that passes through a solution (left), is scattered and broadened by passing through a colloid (right). Sunlight is scattered by dust in air.
  • 87. 13-87 Figure 13.31 The Nile delta (reddish-brown area). At the mouths of rivers, colloidal clay particles coalesce into muddy deltas.
  • 88. 13-88 Figure B13.1 Figure B13.1 The typical steps in municipal water treatment. Chemical Connections
  • 89. 13-89 Figure B13.2 Ion exchange to remove hard-water cations. Chemical Connections
  • 90. 13-90 Figure B13.3 Reverse osmosis to remove ions. Chemical Connections