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Chapter 11
Properties of Solutions
Section 11.1
Solution Composition
Various Types of Solutions
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Section 11.1
Phase Diagrams
Section 11.1
Phase Diagrams
The Phase Diagrams of H2O and CO2
Section 11.1
moles of solute
Molarity (M ) =
liters of solution
mass of solute
Mass (weight) percent =  100%
mass of solution
moles A
Mole fraction (  A ) =
total moles of solution
moles of solute
Molality ( m ) =
kilogram of solvent
Section 11.1
Molarity
moles of solute
Molarity (M ) =
liters of solution

Section 11.1
EXERCISE!
You have 1.00 mol of sugar in 125.0 mL of
solution. Calculate the concentration in units of
molarity.
8.00 M

Section 11.1
EXERCISE!
You have a 10.0 M sugar solution. What volume
of this solution do you need to have 2.00 mol of
sugar?
0.200 L

Section 11.1
EXERCISE!
Consider separate solutions of NaOH and KCl

made by dissolving 100.0 g of each solute in 250.0
mL of solution. Calculate the concentration of
each solution in units of molarity.
10.0 M NaOH
5.37 M KCl

Section 11.1
Mass Percent
mass of solute
Mass (weight) percent =  100%
mass of solution

Section 11.1
EXERCISE!
What is the percent-by-mass concentration of

glucose in a solution made my dissolving 5.5 g of
glucose in 78.2 g of water?
6.6%

Section 11.1
Mole Fraction
molesA
Mole fraction ( A ) =
total moles of solution

Section 11.1
EXERCISE!
A solution of phosphoric acid was made by

dissolving 8.00 g of H3PO4 in 100.0 mL of water.
Calculate the mole fraction of H3PO4. (Assume
water has a density of 1.00 g/mL.)
0.0145

Section 11.1
Molality
moles of solute
Molality (m) =
kilogram of solvent

Section 11.1
EXERCISE!
A solution of phosphoric acid was made by

dissolving 8.00 g of H3PO4 in 100.0 mL of water.
Calculate the molality of the solution. (Assume
water has a density of 1.00 g/mL.)
0.816 m

Section 11.2
The Energies of Solution Formation
Formation of a Liquid Solution

1. Separating the solute into its individual components
(expanding the solute).
2. Overcoming intermolecular forces in the solvent to
make room for the solute (expanding the solvent).
3. Allowing the solute and solvent to interact to form the
solution.

Section 11.2
Steps in the Dissolving Process

Section 11.2
Steps in the Dissolving Process

 Steps 1 and 2 require energy, since forces must be
overcome to expand the solute and solvent.
 Step 3 usually releases energy.
 Steps 1 and 2 are endothermic, and step 3 is often
exothermic.

Section 11.2
Enthalpy (Heat) of Solution

 Enthalpy change associated with the formation of the
solution is the sum of the ΔH values for the steps:
ΔHsoln = ΔH1 + ΔH2 + ΔH3
 ΔHsoln may have a positive sign (energy absorbed) or a

negative sign (energy released).

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.
Solvent (aggregated) + heat → solvent (separated) ΔHsolvent > 0
Step 3: Solute and solvent particles mix and form a

solution. This step is exothermic.
Solute (separated) + solvent (separated) → solution + heat ΔHmix < 0
13-20
Heat of Solution
DHsoln = DHsolute + DHsolvent + DHmix
The overall solution process may be either exothermic

or endothermic.
Exothermic process: DHsoln < 0 because the sum of

the endothermic processes (DHsolute + DHsolvent) is
smaller than the exothermic term (DHmix).
Endothermic process: DHsoln < 0 because the sum of

the endothermic processes (DHsolute + DHsolvent) is larger
than the exothermic term (DHmix).
13-21
Section 11.2
Enthalpy (Heat) of Solution

Section 11.2
Exothermic solution process

DHmix > DHsolute + DHsolvent
DHsoln < 0
Endothermic solution process

DHmix < DHsolute + DHsolvent
DHsoln > 0
Section 11.2
CONCEPT CHECK!
Explain why water and oil (a long chain hydrocarbon)

do not mix. In your explanation, be sure to address
how ΔH plays a role.

Section 11.2
The Energy Terms for Various Types of Solutes and Solvents

ΔH1 ΔH2 ΔH3 ΔHsoln Outcome
Polar solute, polar solvent Large Large Large, negative Small Solution forms
Nonpolar solute, polar solvent Small Large Small Large, positive No solution
forms
Nonpolar solute, nonpolar Small Small Small Small Solution forms

solvent
Polar solute, nonpolar solvent Large Small Small Large, positive No solution
forms

Section 11.2
Types of intermolecular forces in solutions.
Ion-dipole Ion-induced dipole
(40-600) (3-15)
H bond Dipole-induced dipole

(10-40) (2-10)
Dispersion
Dipole-dipole (0.05-40)
(5-25)
Section 11.2
Solids Dissolving in Liquids
The same rules apply.
 Compare the intermolecular forces.
 I2 is quite soluble in CCl4, but not very soluble in water. Explain why?
Section 11.2
In General
 One factor that favors a process is an increase in
probability of the state when the solute and solvent are
mixed.
 Processes that require large amounts of energy tend not
to occur.
 Overall, remember that “like dissolves like”.

Section 11.2
Equilibrium in a saturated solution.
solute (undissolved) solute (dissolved)

Section 11.2
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.
Section 11.3
Factors Affecting Solubility
 Structure Effects:
 Polarity
 Pressure Effects:
 Henry’s law
 Temperature Effects:
 Affecting aqueous solutions

Section 11.3
Structure Effects
 Hydrophobic (water fearing)
 Non-polar substances
 Hydrophilic (water loving)
 Polar substances

Section 11.3
Relation between solubility and temperature for
several ionic compounds.
Section 11.3
Preventing thermal pollution with cooling towers.
Section 11.3
Pressure Effects
 Little effect on solubility of solids or liquids
 Henry’s law: C = kP
C = concentration of dissolved gas
k = constant
P = partial pressure of gas solute
above the solution
 Amount of gas dissolved in a solution is directly proportional to
the pressure of the gas above the solution.

Section 11.3
A Gaseous Solute

Section 11.3
Temperature Effects (for Aqueous Solutions)

 Although the solubility of most solids in water increases
with temperature, the solubilities of some substances
decrease with increasing temperature.
 Predicting temperature dependence of solubility is very
difficult.
 Solubility of a gas in solvent typically decreases with
increasing temperature.

Section 11.3
The Solubilities
of Several Solids
as a Function of
Temperature

Section 11.3
The Solubilities of
Several Gases in Water

Section 11.4
The Vapor Pressures of Solutions

Section 11.4

Section 11.4
Equilibrium is reached Equilibrium is reached

with a given number with fewer particles in
of particles in the the vapor.
vapor.
Section 11.4

Section 11.4
Liquid/Vapor Equilibrium
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Section 11.4
Vapor Pressure Lowering: Addition of a Solute

Section 11.4
Vapor Pressures of Solutions

 Nonvolatile solute lowers the vapor pressure of a
solvent.
 Raoult’s Law: Psoln = solv Psolv
Psoln = observed vapor pressure of solution
solv = mole fraction of solvent
Psolv = vapor pressure of pure solvent

Section 11.4
A Solution Obeying Raoult’s Law

Section 11.4
Nonideal Solutions
 Liquid-liquid solutions where both components are
volatile.
 Modified Raoult’s Law:
PTotal = APA + BPB
 Nonideal solutions behave ideally as the mole fractions

approach 0 and 1.

Section 11.4
Vapor Pressure for a Solution of Two Volatile Liquids

Section 11.4
Liquid-vapor equilibrium for benzene-toluene mixtures at

25°C
Section 11.4
Deviations from Raoult’s law

occur for nonideal solutions.
Consider a binary system made of
A and B molecules.
Positive deviation occurs when
the attraction forces between A-A
and B-B pairs are stronger than
between A-B. As a result, both A
and B will have more tendency to
escape to the vapor phase.
Examples:
 CCl4 – C2H5OH system.
 n-C6H14 – C2H5OH system

Section 11.4
For a binary system made of A

and B molecules.
Negative deviation occurs when
the attraction force between A-B
pairs is stronger than between A-
A and B-B pairs. As a result, both
A and B will have less tendency
to escape to the vapor phase.
Examples:
 CCl4 – CH3CHO system.
 H2O – CH3CHO system

Section 11.4
Another important
observation is that
at the limits of infinite
dilution, the vapor
pressure of the solvent
obeys Raoult’s law.
Section 11.4
CS2 and dimethoxymethane: Positive trichloromethane/acetone: Negative
deviation from ideal (Raoult’s Law) behavior. deviation from ideal (Raoult’s Law) behavior.
Methanol, ethanol, propanol

mixed with water. Which one
is which? (All show positive
deviations from ideal behavior)
Section 11.4
Raoult and Henry PA  x A PA* as x A  1

Raoult’s law
(Raoult’s Law)
Henry’s law
PA  x A k H , A as x A  0
Henry’s behavior: Henry’s law constant: k H , A  PA*
 The Henry’s law constant reflects the intermolecular interactions between the two components.
 Solutions following both Raoult’s and Henry’s Laws are called ideal-dilute solutions.
Section 11.4
Summary of the Behavior of Various Types of Solutions

Deviation
Interactive Forces Between
ΔT for Solution from
Solute (A) and Solvent (B) ΔHsoln Example
Formation Raoult’s
Particles
Law
None (ideal Benzene-

A  A, B  B  A  B Zero Zero
solution) toluene
Negative Acetone-
A  A, B  B < A  B Positive Negative
(exothermic) water
Positive Ethanol-
A  A, B  B > A  B Negative Positive
(endothermic) hexane

Section 11.4
Henry’s Law
The solubility of a gas (Sgas) is directly proportional to the
partial pressure of the gas (Pgas) above the solution.
Sgas = kH X Pgas
Section 11.4
 The mass of a gas (m2)

dissolved by a given
volume of solvent at
constant T is
proportional to the
pressure of the gas (P2)
above and in equilibrium
with the solution.
m2 = k2 P2
where k2 is the Henry’s
law constant.
Section 11.4
Henry’s Law
 For a mixture of gases
dissolved in a solution.
Henry’s law can be
applied for each gas
independently.
 The more commonly
used forms of Henry’s
law are:
P2 = k’ x2
P2 = k” c2
Section 11.4
Henry’s Law
 The vapor pressure of a
solute, P2 , in a solution in
which the solute has a mole
fraction of x2 is given by:
P2 = x2 P2*
where P2* is the vapor pressure
of the solute in a pure liquefied
state.
 It is also found that at the
limits of infinite dilution, the
vapor pressure of the solute
obeys Henry’s law.
Section 11.4
Chart Title
Ideal and Dilute Solutions
Chemical Potential
Partial Molar Quantities
Raoult's Law (Ideal) Gibbs-Duhem Equation Henry's Law (Dilute)
Thermodynamics of Ideal Solutions
Phase Diagrams
Colligative Properties
Freezing Point Depression Boiling Point Elevation Osmotic Pressure

Section 11.4
We need to know how the Gibbs energy of a liquid varies with composition
order to discuss properties of liquid mixtures (like solutions).
Vapor Pressure = PA* Pure Liquid Solution Partial Pressure = PA
 
For vapor phase: For vapor phase:
    RT ln
*
A

A
PA*

 A   A  RT ln PA
P
P
At equilibrium… At equilibrium…
 *A ( g )   *A (l )  A ( g )   A (l )
=A =A =B
 
For liquid phase: For solution:
    RT ln
*  PA*
 A    RT ln

A
PA
P
A A P
Combine these expressions…
Section 11.4
Ideal Solutions
• Two types of molecules are randomly distributed

• Typically, molecules are similar in size and shape
• Intermolecular forces in pure liquids & mixture are similar
• Examples: benzene & toluene, hexane and heptane
(more precise thermodynamic definition coming)
In ideal solutions, the partial vapor pressure of component

A is simply given by Raoult’s Law:
PA  x P *
A A
vapor pressure of pure A

mole fraction of A in solution
Section 11.4
PA
 A   A  RT ln *
*
 A   *A  RT ln x A
PA
PA  x A PA
*
This serves to define an ideal
solution if true for all values of xA
The total vapor pressure of an ideal solution:
40 °C
Ptotal  PA  PB
Ptotal  x A PA*  xB PB*
Ptotal  PA*  xB ( PB*  PA* )
Section 11.4
CONCEPT CHECK!
For each of the following solutions, would you expect it

to be relatively ideal (with respect to Raoult’s Law),
show a positive deviation, or show a negative deviation?
a) Hexane (C6H14) and chloroform (CHCl3)
b) Ethyl alcohol (C2H5OH) and water
c) Hexane (C6H14) and octane (C8H18)

Section 11.5
Boiling-Point Elevation and Freezing-Point
Depression
Colligative Properties
 Depend only on the number, not on the identity, of the
solute particles in an ideal solution:
 Boiling-point elevation
 Freezing-point depression
 Osmotic pressure

Section 11.5
Depression
Boiling-Point Elevation
 Nonvolatile solute elevates the boiling point of the
solvent.
 ΔT = Kbmsolute
ΔT = boiling-point elevation
Kb = molal boiling-point elevation constant
msolute = molality of solute

Section 11.5
Depression
Boiling Point Elevation: Liquid/Vapor Equilibrium

Section 11.5
Depression
Boiling Point Elevation: Addition of a Solute

Section 11.5
Depression
Boiling Point Elevation: Solution/Vapor Equilibrium

Section 11.5
Depression
Freezing-Point Depression
 When a solute is dissolved in a solvent, the freezing
point of the solution is lower than that of the pure
solvent.
 ΔT = Kfmsolute
ΔT = freezing-point depression
Kf = molal freezing-point depression constant
msolute = molality of solute

Section 11.5
Depression
Freezing Point Depression: Solid/Liquid Equilibrium

Section 11.5
Depression
Freezing Point Depression: Addition of a Solute

Section 11.5
Depression
Freezing Point Depression: Solid/Solution Equilibrium

Section 11.5
Depression
Changes in Boiling Point and Freezing Point of Water

Section 11.5
Depression
EXERCISE!
A solution was prepared by dissolving 25.00 g of

glucose in 200.0 g water. The molar mass of
glucose is 180.16 g/mol. What is the boiling point
of the resulting solution (in °C)? Glucose is a
molecular solid that is present as individual
molecules in solution.
100.35 °C

Section 11.5
Depression
EXERCISE!
You take 20.0 g of a sucrose (C12H22O11) and NaCl

mixture and dissolve it in 1.0 L of water. The freezing
point of this solution is found to be -0.426°C.
Assuming ideal behavior, calculate the mass percent
composition of the original mixture, and the mole
fraction of sucrose in the original mixture.
72.8% sucrose and 27.2% sodium chloride;

mole fraction of the sucrose is 0.313
Section 11.5
Depression
EXERCISE!
A plant cell has a natural concentration of

0.25 m. You immerse it in an aqueous solution with a
freezing point of –0.246°C. Will the
cell explode, shrivel, or do nothing?

Section 11.6
Osmotic Pressure
 Osmosis – flow of solvent into the solution through a

semipermeable membrane.
  = MRT
 = osmotic pressure (atm)
M = molarity of the solution
R = gas law constant
T = temperature (Kelvin)

Section 11.6
Osmotic Pressure

Section 11.6
Osmotic Pressure
Osmosis

Section 11.6
Osmotic Pressure

Section 11.6
Osmotic Pressure
EXERCISE!
When 33.4 mg of a compound is dissolved in

10.0 mL of water at 25°C, the solution has an
osmotic pressure of 558 torr. Calculate the
molar mass of this compound.
111 g/mol

Section 11.7
Colligative Properties of Electrolyte Solutions
van’t Hoff Factor, i

 The relationship between the moles of solute dissolved
and the moles of particles in solution is usually
expressed as:
moles of particles in solution
i =
moles of solute dissolved

Section 11.7
Ion Pairing
 At a given instant a small percentage of the sodium and
chloride ions are paired and thus count as a single
particle.

Section 11.7
Examples
 The expected value for i can be determined for a salt by
noting the number of ions per formula unit (assuming
complete dissociation and that ion pairing does not
occur).
 NaCl i=2
 KNO3 i=2
 Na3PO4 i=4

Section 11.7
Ion Pairing
 Ion pairing is most important in concentrated solutions.
 As the solution becomes more dilute, the ions are
farther apart and less ion pairing occurs.
 Ion pairing occurs to some extent in all electrolyte
solutions.
 Ion pairing is most important for highly charged ions.

Section 11.7
Modified Equations
DT = imK
 = iMRT

Section 11.8
Colloids
 A suspension of tiny particles in some medium.

 Tyndall effect – scattering of light by particles.
 Suspended particles are single large molecules or
aggregates of molecules or ions ranging in size from 1 to
1000 nm.

Section 11.8
Colloids
Types of Colloids

Section 11.8
Colloids
Coagulation
 Destruction of a colloid.
 Usually accomplished either by heating or by adding an
electrolyte.

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Chapter 11

Various Types of Solutions

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Consider separate solutions of NaOH and KCl

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What is the percent-by-mass concentration of

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A solution of phosphoric acid was made by

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A solution of phosphoric acid was made by

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Formation of a Liquid Solution

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Steps in the Dissolving Process

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Steps in the Dissolving Process

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Enthalpy (Heat) of Solution

 ΔHsoln may have a positive sign (energy absorbed) or a

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Step 1: Solute particles separate from each other. This

Step 2: Solvent particles separate from each other. This

Step 3: Solute and solvent particles mix and form a

DHsoln = DHsolute + DHsolvent + DHmix

The overall solution process may be either exothermic

Exothermic process: DHsoln < 0 because the sum of

Endothermic process: DHsoln < 0 because the sum of

Enthalpy (Heat) of Solution

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Exothermic solution process

Endothermic solution process

Explain why water and oil (a long chain hydrocarbon)

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The Energy Terms for Various Types of Solutes and Solvents

Nonpolar solute, nonpolar Small Small Small Small Solution forms

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H bond Dipole-induced dipole

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solute (undissolved) solute (dissolved)

A supersaturated solution contains more

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Temperature Effects (for Aqueous Solutions)

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Equilibrium is reached Equilibrium is reached

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Vapor Pressure Lowering: Addition of a Solute

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Vapor Pressures of Solutions

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