1.
2 Solutions
Denniston
Topping
Caret
5th Edition
2.1 Properties of Solutions
• Solution - Solutions are homogeneous mixtures
of two or more pure substances.
• Solute - the substance in the mixture present in
lesser quantity
• Solvent - the substance present in the largest
quantity
• Aqueous solution - solution where the solvent is
water
• Solutions can be liquids as well as solids and
gases
2.1 Properties of Solutions Examples of Solutions
• Air - oxygen and several trace gases are
dissolved in the gaseous solvent, nitrogen
• Alloys - brass and other homogeneous
metal mixtures in the solid state
• Focus on liquid solutions as many
important chemical reactions take place in
liquid solutions
Examples of Solutions
• In a solution, the solute is dispersed uniformly throughout the
solvent.
2.1 Properties of Solutions General Properties of Liquid
Solutions
• Clear, transparent, no visible particles
• May have color
• Electrolytes are formed from solutes that are soluble
ionic compounds
• Nonelectrolytes do not dissociate
NaCl( s ) H
2O
Na (aq ) Cl- (aq )
• Volumes of solute and solvent are not additive
– 1 L ethanol + 1 L water does not give 2 L of solution
2.1 Properties of Solutions Degree of Solubility
• Solubility - how much of a particular solute can
dissolve in a certain solvent at a specified
temperature
2.1 Properties of Solutions Saturation
• Saturated solution - a solution that contains all the
solute that can be dissolved at a particular
temperature
• Supersaturated solution - contains more solute
than can be dissolved at the current temperature
• How is this done?
• Heat solvent, saturate it with solute then cool slowly
• Sometimes the excess will precipitate out
• If it doesn’t precipitate, the solution will be
supersaturated
2.1 Properties of Solutions Solubility and Equilibrium
• If excess solute is added to a solvent, some
dissolves
• At first, rate of dissolution is large
• Later, reverse reaction – precipitation – occurs
more quickly
• When equilibrium is reached the rates of
dissolution and precipitation are equal, there is
some dissolved and some undissolved solute
• A saturated solution is an example of a dynamic
equilibrium
Degree of saturation
• Saturated solution
Solvent holds as much
solute as is possible at
that temperature.
Undissolved solid
remains in flask.
Dissolved solute is in
dynamic equilibrium
with solid solute
particles.
Degree of saturation
• Unsaturated Solution
Less than the maximum
amount of solute for that
temperature is dissolved
in the solvent.
No solid remains in flask.
Degree of saturation
• Supersaturated
Solvent holds more solute than is normally possible at
that temperature.
These solutions are unstable; crystallization can often
be stimulated by adding a “seed crystal” or scratching
the side of the flask.
Degree of saturation
Unsaturated, Saturated or Supersaturated?
How much solute can be dissolved in a solution?
More on this in Chap 17
(solubility products, p 739)
2.1 Properties of Solutions Solubility of Gases: Henry’s Law
• Henry’s law – the number of moles of a gas
dissolved in a liquid at a given temperature is
proportional to the partial pressure of the gas
above the liquid
• Gas solubility in a liquid is directly proportional to
the pressure of the gas in the atmosphere in
contact with the liquid
• Gases are most soluble at low temperatures
• Solubility decreases significantly at higher
temperatures
– Carbonated beverages – CO2 solubility less when warm
Gases in Solution
QuickTime™ and a
TIFF (LZW) decompressor
are needed to see this picture.
Gases in Solution
• The solubility of
Increa liquids and solids
does not change
sing appreciably with
pressure.
pressu • But, the solubility of a
re gas in a liquid is
directly proportional
above to its pressure.
solutio
Henry’s Law
Sg = kPg
where
• Sg is the solubility of the
gas;
• k is the Henry’s law
constant for that gas in
that solvent;
• Pg is the partial pressure
of the gas above the
liquid.
Factors Affecting Solubility
• Chemists use the axiom
“like dissolves like”:
Polar substances tend to
dissolve in polar solvents.
Nonpolar substances tend to
dissolve in nonpolar
solvents.
2.1 Properties of Solutions Factors Affecting Solubility
• Factors which affect solubility:
1 Polarity of solute and solvent
• The more different they are, the lower the solubility
2 Temperature
• Increase in temperature usually increases solubility
3 Pressure
• Usually has no effect
• If solubility is of gas in liquid, directly proportional
to applied pressure
Factors Affecting Solubility
The stronger the
intermolecular
attractions between
solute and solvent, the
more likely the solute
will dissolve.
xample: ethanol in water
thanol = CH3CH2OH
Intermolecular forces = H-bonds;
dipole-dipole; dispersion
Factors Affecting Solubility
Glucose (which has
hydrogen bonding) is
very soluble in water.
Cyclohexane (which
only has dispersion
forces) is not water-
soluble.
Factors Affecting Solubility
• Vitamin A is soluble in nonpolar compounds (like
fats).
• Vitamin C is soluble in water.
Which vitamin
is water-
soluble and
which is fat-
soluble?
Gases in Solution
QuickTime™ and a
TIFF (LZW) decompressor
are needed to see this picture.
2.2 Concentration Based on Mass
6
• Concentration - amount of solute dissolved
in a given amount of solution
• Concentration of a solution has an effect on
– Physical properties
• Melting and boiling points
– Chemical properties
• Solution reactivity
2.2 Concentration Based on
Weight/Volume Percent
• Amount of solute = mass of solute in grams
• Amount of solution = volume in milliliters
amount of solute
concentration
Mass
amount of solution
• Express concentration as a percentage by
multiplying ratio by 100% = weight/volume
percent or % (W/V)
W grams of solute
% 100%
V milliliters of solution
2.2 Concentration Based on Calculating Weight/Volume
Percent
Calculate the percent composition or % (W/V) of
2.00 x 102 mL containing 20.0 g sodium chloride
20.0 g NaCl, mass of solute
Mass
2.00 x 102 mL, total volume of solution
% (W/V) = 20.0g NaCl / 2.00 x 102 mL x 100%
= 10.0% (W/V) sodium chloride
Calculate Weight of Solute from
2.2 Concentration Based on
Weight/Volume Percent
Calculate the number of grams of glucose in
7.50 x 102 mL of a 15.0% solution
Mass
W grams of solute
% 100%
V milliliter s of solution
15.0% (W/V) = Xg glucose/7.50 x 102 mL x 100%
Xg glucose x 100% = (15.0% W/V)(7.50 x 102 mL)
Xg glucose = 113 g glucose
2.2 Concentration Based on Weight/Weight Percent
W grams solute
% 100%
W grams solutions
• Weight/weight percent is most useful for
Mass
solutions of 2 solids whose masses are
easily obtained
• Calculate % (W/W) of platinum in gold
ring with 14.00 g Au and 4.500 g Pt
[4.500 g Pt / (4.500 g Pt + 14.00 g Au)] x 100%
= 4.500 g / 18.50 g x 100% = 24.32% Pt
2.2 Concentration Based on Parts Per Thousand (ppt) and
Parts Per Million (ppm)
• As percentage is the number of parts of
solute in 100 parts of solution, ppt and
Mass
ppm change the calculation only by orders
of magnitude
– ppt = g solute / g solution x 103 ppt
– ppm = g solute / g solution x 106 ppm
– ppt and ppm are most often used for very
dilute solutions
2.3 Concentration of Solutions:
Moles and Equivalents
• Chemical equations represent the relative
number of moles of reactants producing
products
• Many chemical reactions occur in solution
where it is most useful to represent
concentrations on a molar basis
2.3 Moles and Equivalents Molarity
• The most common mole-based
concentration unit is molarity
• Molarity
– Symbolized M
– Defined as the number of moles of solute per
liter of solution
moles solute
M
L solution
2.3 Moles and Equivalents Calculating Molarity from Moles
• Calculate the molarity of 2.0 L of
solution containing 5.0 mol NaOH
• Use the equation moles solute
M
L solution
• Substitute into the equation:
MNaOH = 5.0 mol solute
2.0 L solution
= 2.5 M
2.3 Moles and Equivalents Calculating Molarity From Mass
• If 5.00 g glucose are dissolved in 1.00 x 10 2 mL of
solution, calculate molarity, M, of the glucose solution
• Convert from g glucose to moles glucose
– Molar mass of glucose = 1.80 x 102 g/mol
5.00 g x 1 mol / 1.80 x 102 g = 2.78 x 10-2 mol glucose
– Convert volume from mL to L
1.00 x 102 mL x 1 L / 103 mL = 1.00 x 10-1 L
• Substitute into the equation:
moles solute
M
L solution
Mglucose = 2.78 x 10-2 mol glucose
1.00 x 10-1 L solution
= 2.78 x 10-1 M
2.3 Moles and Equivalents Dilution
Dilution is required to prepare a less
concentrated solution from a more
concentrated one
– M1 = molarity of solution before dilution
– M2 = molarity of solution after dilution
– V1 = volume of solution before dilution
– V2 = volume of solution after dilution
moles solute
M moles solute = (M)(L solution)
L solution
2.3 Moles and Equivalents Dilution
• In a dilution will the
number of moles of
solute change?
– No, only fewer per unit
volume
• So, M1V1 = M2V2
• Knowing any three terms
permits calculation of the
fourth
2.3 Moles and Equivalents Calculating Molarity
After Dilution
• Calculate the molarity of a solution made by
diluting 0.050 L of 0.10 M HCl solution to a
volume of 1.0 L
– M1 = 0.10 M molarity of solution before dilution
– M2 = X M molarity of solution after dilution
– V1 = 0.050 L volume of solution before dilution
– V2 = 1.0 L volume of solution after dilution
• Use dilution expression M1V1 = M2V2
• X M = (0.10 M) (0.050 L) / (1.0 L)
0.0050 M HCl OR 5.0 x 10-3 M HCl
2.4 Concentration-Dependent
Molality
• Solute concentration is expressed in
Solution Properties
mole-based units
– Number of particles is critical, not the mass
of solute
• Molality (m) = moles of solute per kg of
solvent
– The denominator is in kg solvent, not in kg
solution
moles solute
Molality
kg solvent
2.4 Concentration-Dependent
Solution Properties
• Colligative properties - properties of
solutions that depend on the concentration
of the solute particles, rather than the
identity of the solute
• Four colligative properties of solutions
1. vapor pressure lowering
2. boiling point elevation
3. freezing point depression
4. osmotic pressure
2.4 Concentration-Dependent Vapor Pressure of a Liquid
Consider Raoult’s law in molecular
terms
Solution Properties
• Vapor pressure of a solution
results from escape of solvent
molecules from liquid to gas
phase
• Partial pressure of gas phase
solvent molecules increases
until equilibrium vapor
pressure is reached
• Presence of solute molecules
hinders escape of solvent
molecules, lowering
equilibrium vapor pressure
2.4 Concentration-Dependent Vapor Pressure Lowering
• Raoult’s law - when a nonvolatile solute is
Solution Properties
added to a solvent, vapor pressure of the solvent
decreases in proportion to the concentration of
the solute
• Solute molecules (red below) serve as a barrier to
the escape of solvent molecules resulting in a
decrease in the vapor pressure
2.4 Concentration-Dependent Freezing Point Depression and
Solution Properties Boiling Point Elevation
• Freezing point depression may be explained
considering the equilibrium between solid and
liquid states
– Solute molecules interfere with the rate at which
liquid water molecules associate to form the solid
state
• Boiling point elevation can be explained
considering the definition as the temperature at
which vapor pressure of the liquid equals the
atmospheric pressure
– If a solute is present, then the increase in boiling
temperature is necessary to raise the vapor pressure
to atmospheric temperature