13 Physical Properties of Solutions

13.1 Types of Solutions

13.2 A Molecular View of the Solution Process
The Importance of Intermolecular Forces
Energy and Entropy in Solution Formation
13.3 Concentration Units
Molality
Percent by Mass
Comparison of Concentration Units
13.4 Factors that Affect Solubility
Temperature
Pressure
13.5 Colligative Properties
Vapor-Pressure Lowering
Boiling-Point Elevation
Freezing-Point Depression
Osmotic Pressure
Electrolyte Solutions
13.6 Calculations Using Colligative Properties
13.7 Colloids
13.1 Types of Solutions
A solution is a homogeneous mixture of two or more substances.
A solution consists of a solvent and one or more solutes.

Solvent: Major component Solute: Minor component

 Classification of solution based on the amount of solute dissolved

Unsaturated solution: A solution contains less amount of solute than

its maximum amount to dissolve in a solvent at a specific temperature.

Saturated solution: Saturated solution is one that contains the

maximum amount of solute that will dissolve in a solvent at a specific
temperature.

Supersaturated solutions contain more dissolved solute than is

present in a saturated solution and are generally unstable.

Solubility: The amount of solute dissolved in a given volume of a

saturated solution. It is specific to temperature and solvent
 A Molecular View of the Solution Process: The
Importance of Intermolecular Forces

Solvation occurs when solute molecules are separated from one

another and surrounded by solvent molecules.

Solvation depends on three types of interactions:

1) Solute-solute interactions

2) Solvent-solvent interactions

3) Solute-solvent interactions
Intermolecular Forces in solutions

Components of a mixture can have different properties, there is a

greater variety of intermolecular forces to consider.
Energy and Entropy in Solution Formation

The entropy of a system is a measure of how dispersed or spread

out its energy is.
There is a natural tendency for the energy of a system to become
dispersed (entropy increases).

Entropy is a measure of disorder

 Predicting solubility

“Like dissolves like”

Two substances with similar type and magnitude of intermolecular
forces are likely to be soluble in each other.

Examples:
CCl4 and C6H6 nonpolar/nonpolar
CH3OH and CH3CH2OH polar/polar

Two liquids are said to be miscible if they are completely soluble in

each other in all proportions.
Worked Example 13.1
Determine for each solute whether the solubility will be greater in water, which is
polar, or in benzene (C6H6), which is nonpolar: (a) Br2, (b) sodium iodide (NaI),
(c) carbon tetrachloride, and (d) formaldehyde (CH2O).

Strategy Consider the structure of each solute to determine whether or not it is

polar. For molecular solutes, start with a Lewis structure and apply the VSEPR
theory. We expect polar solutes, including ionic compounds, to be more soluble in
water. Nonpolar solutes will be more soluble in benzene.

Solution (a) Bromine (Br2)is a homonuclear diatomic molecule and is

nonpolar. Bromine is more soluble in benzene.

(b) Sodium iodide (NaI) is ionic and more soluble in water.

Worked Example 13.1 (2)
Solution (c) Carbon tetrachloride has the following Lewis structure:

With four electron domains around the central atom, we expect a tetrahedral
arrangement. A symmetrical arrangement of identical bonds results in a
nonpolar molecule. Carbon tetrachloride is more soluble in benzene.

(d) Formaldehyde has the following Lewis structure:

Crossed arrows represent individual bond dipoles. This molecule is polar and
can form hydrogen bonds in water. Formaldehyde is more soluble in water.
Worked Example 13.1 (3)

Think About It Remember that molecular formula alone is not

sufficient to determine the shape or polarity of a polyatomic
molecule. It must be determined by starting with a correct Lewis
structure and applying VSEPR theory.
 13.3 Concentration Units
The amount of solute relative to the volume of a solution or to the
amount of solvent in a solution is called concentration.

Molarity (M) is the number of moles solute dissolved per liter

solution:
Number of moles of solute
Molarity (M) =
Number of liters of solution
Problem
If 2.0 L aqueous solution is prepared by dissolving 80 g NaOH
(molar mass of NaOH = 40 g/mol). (a) What is the molarity of
that solution?
# of moles of NaOH = 80 g/ (40 g/mol) = 2.0 mol
Volume of solution = 2.0 L

Molarity of the solution = 2 mol / 2L = 1.0 mol/L

(b) What will be the molarity of the solution if you add 500 mL
water to the above solution?
Total volume = 2 L + 0.5 L = 2.5 L
Molarity of the solution = 2 mol/ 2.5L = 0.8 mol/L
Group Problem
If 500 mL aqueous solution is prepared by dissolving 100 g
NaCl.

(a) What is the molarity of that solution?

(b) What will be the molarity of the solution if you add 500
mL water to the above solution?
 13.3 Concentration Units: molality

molality (m) is the number of moles of solute dissolved in 1 kg (1000

g) solvent:

Number of moles of solute

molality (m) =
Mass of solvent (in kg)
Problem
What is the molality of a solution prepared by dissolving 6.44 g
of naphthalene (C10H8) in 80.1 g benzene?

molality = # of moles of solute/Kg of solvent

Molar mass of naphthalene, C10H8 = 128 g/mol

# of moles of naphthalene = 6.44/128 = 0.0503 mol

molality = 0.0503 mol/0.0801 kg= 0.628 molal

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Worked Example 13.2
A solution is made by dissolving 170 g of glucose (C6H12O6) in enough water to
make a liter of solution. The density of the solution is 1.062 g/mL. what is
molality of the solution?

Strategy Use the molar mass of glucose to determine the number of moles of
glucose in a liter of solution. Use the density (in g/L) to calculate the mass of a
liter of solution. Subtract the mass of glucose from the mass of solution to
determine the mass of water. The molar mass of glucose is 180.2 g/mol.

Number of moles of solute

molality (m) =
Mass of solvent (in kg)
 Worked Example 13.2 (2)
Solution
Number of moles of solute (glucose) = (170.0 g)/(180.2 g/mol)
= 0.9434 mol glucose per liter of solution

Density = 1.062 g/mL= 1062 g/L

So, 1 liter of solution = 1 L× (1062 g/L) = 1062 g

Amount of water in solution = 1062 g – 170 g = 892 g water

= 0.892 kg water

molality of solution = (0.9434 mol glucose)/(0.892 kg water) = 1.06 m

 Worked Example 13.3
A 50: 50 mixture of isopropyl alcohol (C3H7OH) and water has a density = 0.79
g/mL at 20°C). Express the concentration of alcohol in (a) molarity and (b)
molality. The molar mass of isopropyl alcohol is 60.09 g/mol.

Strategy (a) Use density to determine the total mass of a liter of solution, and
use percent by mass to determine the mass of isopropyl alcohol in a liter of
solution. Convert the mass of isopropyl alcohol to moles, and divide moles by
liters of solution to get molarity.

(b) Subtract the mass of C3H7OH from the mass of solution to get the mass of
water. Divide moles of C3H7OH by the mass of water (in kg) to get molality.
Solution
The mass of a liter of alcohol solution = 1000 mL × 0.79 g /mL
= 790 g
(a) 790 g solution 50 g 395 g C3H7OH
× =
L solution 100 g solution L solution

395 g 1 mol 6.57 mol

× = = 6.57 M
L solution 60.09 g L solution

(b) 790 g solution – 395 g C3H7OH = 395 g water = 0.395 kg water

Molality= (6.57 mol C3H7OH)/(0.395 kg) = 16.63 molal

.

Think About It Note the large difference between molarity and molality in this
case. Molarity and molality are the same (or similar) only for very dilute
aqueous solutions.
Concentration Units: Percent by mass

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Determine the percent by mass of KCl in a solution prepared by

dissolving 1.18 g of KCl in 86.3 g of water

Mass of KCl = 1.18 g

Total mass of solution = 1.18 + 86.3 = 87.48 g

Percent mass of KCl = (1.18/87.48) * 100 = 1.35%

 Concentration Units
Mole fraction:

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A
Determine the mole fraction of KCl in a solution prepared by
dissolving 1.18 g of KCl in 86.3 g of water.
molar mass of KCl =74.55 g/mol

# moles of KCl = 1.18 g/74.55 gmol-1 = 0.016 mol

# moles of H2O = 86.3 g/18 gmol-1 = 4.79 mol

Mole fraction of KCl =0.016/(4.79 + 0.016) = 0.0033

Mole fraction of Water =4.79/(4.79 + 0.016) = 0.9966

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Comparison of Units

Concentration choice is based on the experiment.

Molarity
Titration
Gravimetric analysis
(easiest in a lab situation)

Mole Fraction
Gases
Vapor pressure

Molality and Percent by Mass

Independent of temperature
 Factors That Affect Solubility: Temperature

Temperature affects the solubility of most substances.

Increase in temperature usually,
increase the solubility of solids
decreases the solubility of gases
Pressure

Pressure greatly influences the solubility of a gas.

Henry’s law states that the solubility of a gas in a liquid is

proportional to the pressure of the gas over the solution.

c = kP

c molar concentration
(mol/L)
P pressure (atm)
k proportionality
constant called
Henry’s law constant
Electrolyte Solutions

Electrolytes undergo dissociation when dissolved in water.

The van’t Hoff factor (i) accounts for this effect.

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Electrolyte Solutions (2)

The van’t Hoff factor (i) is 1 for all nonelectrolytes:

H2O
C12H22O11(s) C12H22O11(aq)

1 particle dissolved, i = 1

For strong electrolytes i should be equal to the number of ions:

NaCl(s) H2O
Na+(aq) + Cl–(aq)

2 particles dissolved, i = 2

Na2SO4(s) H2O
2Na+(aq) + SO42–(aq)

3 particles dissolved, i = 3
Electrolyte Solutions (3)

The van’t Hoff factor (i) is usually smaller than predicted due to the
formation of ion pairs.
An ion pair is made up of one or more cations and one or more
anions held together by electrostatic forces.
Electrolyte Solutions (4)

The van’t Hoff factor (i) is usually smaller than predicted due to the
formation of ion pairs.
An ion pair is made up of one or more cations and one or more
anions held together by electrostatic forces.
13.5 Colligative Properties

Colligative properties are properties that depend on the number of

solute particles in solution.

Colligative properties do not depend on the nature of the solute

particles.

The colligative properties are:

 freezing-point depression
 boiling-point elevation
 osmotic pressure
 vapor-pressure lowering
Freezing-Point Depression
Solutions freeze at a temperature lower than the pure solvent.

∆Tf = Tf° – Tf

∆Tf = iKfm

ΔTf: freezing point depression

Kf: freezing point depression constant (°C/m)
m: molality
i: van’t Hoff factor
Worked Example 13.6
Ethylene glycol [CH2(OH)CH2(OH)] is a common automobile antifreeze. It is
water soluble and fairly nonvolatile (b.p. 197°C). Calculate (a) the freezing
point of a solution containing 685 g of ethylene glycol in 2075 g of water. The
molar mass of ethylene glycol (C2H6O2) is 62.07 g/mol.
Kf for water is 1.86°C/m.
Strategy Convert grams of ethylene glycol to moles, and divide by the mass of
water in kilograms to get molal concentration. Use molal concentrations and
ΔTf = iKfm.

Solution
(685 g C2H6O2)/(62.07 g/mol) = 11.04 mol C2H6O2
(11.04 mol C2H6O2)/(2.075 kg water) = 5.32 m C2H6O2
ΔTf = iKfm = (1.86°C/m)(5.32 m) = 9.89°C
The freezing point of the solution is (0 – 9.89)°C = – 9.89°C
Boiling-Point Elevation

Solutions boil at a higher

temperature than the pure
solvent.

∆Tb = Tb – Tb°

∆Tb = iKbm

ΔTb: boiling point elevation

Kb: boiling point elevation
constant (°C/m)
m: molality
i : van’t Hoff factor
 Worked Example 13.6
Ethylene glycol [CH2(OH)CH2(OH)] is a common automobile antifreeze. It is
water soluble and fairly nonvolatile (b.p. 197°C). Calculate the boiling point of
a solution containing 685 g of ethylene glycol in 2075 g of water.

Strategy Use molal concentration and the equation, ΔTb = iKbm.

The molar mass of ethylene glycol (C2H6O2) is 62.07 g/mol.
Kb for water is 0.52°C/m.

Solution
(685 g C2H6O2)/(62.07 g/mol) = 11.04 mol C2H6O2
(11.04 mol C2H6O2)/(2.075 kg water) = 5.32 m C2H6O2

ΔTb = iKbm = (0.52°C/m)(5.32 m) = 2.8°C

The boiling point of the solution is (100.0 + 2.8)°C = 102.8°C
Osmotic Pressure

Osmosis is the selective passage of solvent

molecules through a porous membrane from a
more dilute solution to a more concentrated one.
Osmotic Pressure (2)

Osmotic pressure (π) of a solution is the pressure required to stop

osmosis.

π = iMRT

π Osmotic pressure (atm)

M molarity (moles/L)
R gas constant (0.08206 L·atm/mol·K)
T absolute temperature (kelvin)
Worked Example 13.7
The osmotic pressure of a 0.0100 M potassium iodide (KI) solution at 25°C is
0.465 atm. Determine the experimental van’t Hoff factor for KI at this
concentration.

Strategy Use osmotic pressure to calculate the molar concentration of KI, and
divide by the nominal concentration of 0.01000 M. R = 0.08206 L·atm/K·mol,
and T = 298 K.

Solution Solving π = MRT for M,

M = π/RT = (0.465 atm)/(0.08206 L·atm/K·mol)(298 K) = 0.0190 M

i = (0.0190 M)/(0.0100 M) = 1.90

The experimental van’t Hoff factor for KI at this concentration is 1.90.

Vapor-Pressure Lowering
Raoult’s law states that the partial pressure of a solvent over a
solution is given by the vapor pressure of the pure solvent times the
mole fraction of the solvent in the solution.

P1 = χ1P1° ∆P = χ2P1°

P1 partial pressure of solvent over solution

P1° vapor pressure of pure solvent
χ1 mole fraction of solvent
ΔP = P1° – P1
χ2 mole fraction of solute
Worked Example 13.5
Calculate the vapor pressure of water over a solution made by dissolving 225 g of
glucose in 575 g of water at 35°C. (At 35°C, P°water = 42.2 mmHg.)

Strategy Convert the masses of glucose and water to moles, determine the mole
fraction of water, and use P1 = χ1P°1 to find the vapor pressure over the solution.
The molar masses of glucose and water are 180.2 and 18.02 g/mol, respectively.

Solution
(225 g glucose)/(180.2 g/mol) = 1.25 mol glucose

(575 g water)/(18.02 g/mol) = 31.9 mol water

χwater = (31.9 mol water)/(1.25 mol glucose + 31.9 mol water) = 0.962

Pwater = χwater P°water = 0.962 × 42.4 mmHg = 40.6 mmHg

The vapor pressure of water over the solution is 40.6 mmHg.

Vapor-Pressure Lowering (2)

If both components of a solution

are volatile, the vapor pressure of
the solution is the sum of the
individual partial pressures.

PA = χAPA° PB = χBPB°

PT = χAPA° + χBPB°

Benzene Toluene
Group
Calculate the vapor pressure of a solution prepared by mixing 20
moles of methanol (CH3OH) and 40 moles of ethanol (C2H5OH) at
25 °C. Partial pressure of pure ethanol and pure methanol are 0.166
atm and 0.82 atm respectively at 25 °C.

Solution

PT = χAPA° + χBPB°
Group
Calculate the vapor pressure of a solution prepared by mixing 25%
methanol (CH3OH) and 75% ethanol (C2H5OH) at 25 °C. Density
of methanol and ethanol are 0.792 g/mL and 0.789 g/mL
respectively. Partial pressure of pure ethanol and pure methanol are
0.166 atm and 0.82 respectively at 25 °C.
Solution

PT = χAPA° + χBPB°
13.6 Calculations Using Colligative Properties

Colligative properties (nonelectrolyte) may be used to find solution

molarity, molality, and/or a solute’s molar mass.

Percent dissociation is the percentage of dissolved molecules (or

formula units, in the case of an ionic compound) that separate into
ions in a solution and this can be found using colligative properties.
Strong electrolytes should have complete, or 100%, dissociation,
however, experimentally determined van’t Hoff factors indicate that
this is not the case.
Percent dissociation of a strong electrolyte is more complete at lower
concentration.
Percent ionization of weak electrolytes is also dependent on
concentration.
Worked Example 13.8
Quinine was the first drug widely used to treat malaria, and it remains the
treatment of choice for severe cases. A solution prepared by dissolving 10.0 g of
quinine in 50.0 mL of ethanol has a freezing point 1.55°C below that of pure
ethanol. Determine the molar mass of quinine. (The density of ethanol is 0.789
g/mL.) Assume that quinine is a non-electrolyte. Kf for ethanol is 1.99°C/m.
Strategy Use ΔTf = Kfm to determine the molal concentration of the solution.
Use the density of ethanol to determine the mass of the solvent. The molal
concentration of quinine multiplied by the mass of ethanol (in kg) gives moles of
quinine. The mass of quinine (in grams) divided by moles of quinine gives the
molar mass.

Solution mass of ethanol = 50.0 mL × 0.789 g/mL = 39.5 g or 3.95×10-2 kg

Solving ΔTf = Kfm for molal concentration

m = ΔTf/Kf = (1.55°C)/(1.99°C/m) = 0.779 m

 Worked Example 13.8 (2)

Solution The solution is 0.779 m in quinine (i.e., 0.779 mol of quinine/kg

ethanol solvent.)
molality = # moles of solute/Kg solvent

0.779 = # moles/0.0395 Kg of ethanol

# moles of quinine = 0.779 x 0.0395 = 0.0308 mol quinine

molar mass of quinine = weight/#moles

(10.0 g quinine)/(0.0308 mol quinine) = 325 g/mol

Think About It Check the result using the molecular formula of quinine:
C20H24N2O2 (324.4 g/mol). Multistep problems such as this one require careful
tracking of units at each step.
What is the boiling point of a solution prepared by dissolving
100 gm of MgCl2 in 900 mL water. Kb of MgCl2 = 0.52 Cmol-1

ΔTb = Kbm

82
13.7 Colloids

A colloid is a dispersion of particles of one substance throughout

another substance. Colloid particles are much larger than the normal
solute molecules.

Categories of colloids:
 aerosols
 foams
 emulsions
 sols
 gels
Colloids (2)

Examples of colloids
Colloids (3)

Colloids with water as the dispersing medium can be categorized as

hydrophilic (water loving) or hydrophobic (water fearing).

Hydrophilic groups on the

surface of a large molecule
stabilize the molecule in
water.
Stabilzation of hydrophobic Colloids

Negative ions are adsorbed onto the surface of hydrophobic colloids.

The repulsion between like charges prevents aggregation of the

articles.
 Stabilzation of hydrophobic Colloids

Hydrophobic colloids can be stabilized by the presence of

hydrophilic groups on their surface.

Soap
Colloids (6)

Emulsification is the process of stabilizing a colloid that would

otherwise not stay dispersed.