Chapter 14:

Solutions and Their Physical

Properties

Content:
 Types of Solutions: Some Terminology
 Solution Concentration
 Intermolecular Forces and the Solution Process
 Solution Formation and Equilibrium
 Solubilities of Gases
 Vapor Pressure of Solutions
 Osmotic Pressure
 Freezing-Point Depression and Boiling-Point
Elevation of Nonelectrolyte solutions
 Solutions of Electrolytes
 Colloidal Mixtures

Abdulfettah Hazuri

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 1- Types of Solutions: Some Terminology
• Solutions are homogeneous mixtures.
– Uniform throughout.
• Solvent.
– Determines the state of matter in which the
solution exists.
– Is the largest component.
• Solute.
– Other solution components said to be dissolved in
the solution.

2- Solution Concentration:
• Mass percent. (m/m)
• Volume percent. (v/v)
• Mass/volume percent. (m/v)
• Isotonic saline is prepared by dissolving
0.9 g of NaCl in 100 mL of water and is
said to be:
0.9% NaCl (mass/volume)

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Ppm, ppb, and ppt, ppb and ppt
• Very low solute concentrations are expressed as:
m/m, m/v
ppm: parts per million (μg/g, mg/L)
ppb: parts per billion (ng/g, μg/L)
ppt: parts per trillion (pg/g, ng/L)

Note that for water 1.0 L H 1.0 g/mL = 1000 g

ppm, ppb, and ppt are properly m/m or v/v.

Mole fraction and mole Percent:

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 Molarity and Molality:

EX: A 16.00 % aqueous solution of glycerol,

HOCH2CH(OH)CH2OH, by mass has a density of
1.037 g/ml. What is the mole fraction of glycerol in
this solution?
Solution:
1 mol C3H5(OH)3
# of glycerol = 16 g C3H5(OH)3 * ‫ـــــــــــــــــــــــــــ‬
92.1 g C3H5(OH)3
=0.1737 mol Glycerol.
1 mol H2O
# of water = 84 g H2O * ‫ــــــــــــــــــــــــــــ‬ = 4.661 mol H2O

18.02 g H2O
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Mole fraction = 0.1737/0.1737+4.661 = 0.03593
3- Intermolecular Forces and Solutions:
Enthalpy of Solution:

Three-step approach to ΔHsoln.

First, solvent molecules must be separated from one
another to make room for the solute molecules.
Some energy is required to overcome the forces of
attraction between solvent molecules. As a result,
this step should be an endothermic one:
ΔHsoln > 0.
Second, the solute molecules must be separated
from one another. this step, too, will take energy
and should be endothermic.
Finally, we can imagine that we allow the separated
solvent and solute molecules to be attracted to one
another. These attractions will bring the molecules
closer together and energy should be released. This
is an exothermic step: ΔHsoln < 0.
The enthalpy of solution is the sum of three
enthalpy changes, and depending on their relative
values, is either positive (endothermic) or negative
(exothermic).

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6
Intermolecular Forces in Mixtures:
•Magnitude of ΔHa, ΔHb, and ΔHc depend on
intermolecular forces.
• Ideal solution
– Forces are similar between all combinations of
components.
ΔHsoln = 0
1- If the intermolecular forces of attraction are of the
same type and of equal strength, the solute and
solvent molecules mix randomly. A homogeneous
mixture or solution result. Because properties of
solutions of this type can generally be predicted
from the properties of the pure components, they are
called Ideal solutions. There is no overall enthalpy
change in the formation of an ideal solution from is
components. ΔHsoln=0.
ΔHc in equation is equal in magnitude and opposite in
sign to the sum of ΔHa and ΔHb. Many mixture of
liquid hydrocarbons fit this description, or very nearly
so.

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 If Forces of attraction between unlike molecules exceed those
between like molecules, a solution also forms. The properties
of such solutions generally cannot be predicted and they are
called nonideal solution.
Interaction between solute and solvent molecules ( ΔHc) release
more heat than the heat absorbed to separate the solvent and
solute molecules (ΔHa + ΔHb). The solution process is exothermic
(ΔHsoln <0). Solutions of acetone and chloroform fit this type.
Weak hydrogen bonding occurs between the two kinds of
molecules.
2- If forces of attraction between solute and solvent molecules
are somewhat weaker than between molecules of the same
kind, complete mixing may still occur, butt the solution
formed is nonideal. The solution has a higher enthalpy than the
pure components, and the solution process is endothermic.
This type of behavior is observed in mixture of carbon
disulfide(CS2), a nonpolar liquid, and acetone, a polar liquid.
In these mixtures, the acetone molecules are attracted to other
acetone molecules by dipole dipole interactions and hence
show a preference for other acetone molecules as neighbors.
3- Finally, if forces of attraction between unlike molecules are
much weaker than those between like molecules, the
component remain segregated in a heterogeneous mixture.
Dissolution does not occur to any significant extent.
In a mixture of water and octane (a constituent of gasoline),
strong hydrogen bonds hold water molecules together in
cluster. The nonpolar octane molecules cannot exert a strong
attractive force on the water molecules, and the two liquids do
not mix. From a thermodynamic perspective, we look at Gibbs
energy of solution, ΔsolnG = ΔsolnH – TΔS, to determine whether
the solute and solvent will mix to form a homogeneous liquid-
liquid mixture.
If ΔsolnG < 0, the solution is spontaneous.
If ΔsolnG > 0, the solution is not spontaneous.

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 By focusing on ΔsolnG, the formation of a solution can be
investigated from both and enthalpic and an entropic
perspective.

• Aqueous solutions of ionic compounds are due to ion dipole

interactions (like dissolves like)
• If strong enough to overcome interionic forces in crystal,
dissolving occurs
• “Hydration of ions”
• Hydration is exothermic
• Ionic solids are typically insoluble in non-polar solvents

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 4- Solution Formation and Equilibrium:

If in preparing a solution, we start with less solute than would be

present in the saturated solution, the solute completely dissolves, and
the solution is an unsaturated solution.
But suppose we prepare a saturated solution at one temperature and
then change the temperature to a value at which the solubility is
lower (this generally means a lower temperature). Usually, the
excess solute crystallizes from solution, but occasionally all the
solute may remain in solution. in these cases, because the quantity of
solute is greater than in a saturated solution, the solution is said to be
a supersaturated solution. A supersaturated solution is unstable,
and if a few crystals of solute are added to serve as particles on
which crystallization can occur, the excess solute crystallizes.

Solubility Curves:

• Area below curve is unsaturated

• Area above curve is supersaturated
• Solubility is a function
of temperature
• Can obtain a
supersaturated
solution by cooling a saturated one

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Solubility of Gases:
• Most gases are less
soluble in water as
temperature increases.
• In organic solvents the
reverse is often true.
• Solubility curves of Noble
gases can be complex.

Effect of pressure (Henry’s law):

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EX: Determine the partial pressure of O2 above an
aqueous solution at 0⁰ C known to contain 5 mg O2
Per 100 ml of solution. The Henrys law constant
for O2 dissolved in water is K = 2.18X10-3 M atm-1.
Solution:
C = [5X10-3 * (1 mol O2/32 g O2)] / 0.1 L =
1.5625 X 10-3 M
Pgas = 1.5625 X 10-3 M / 2.18 X 10-3 M atm-1
= 0.717 atm O2 pressure

Vapor pressure of Solution:

Ex: Calculating the Composition of Vapor in Equilibrium with

a Liquid Solution.
What is the composition of the vapor in equilibrium with
the benzene-toluene solution?
Partial pressure and mole fraction:
χbenzene = Pbenzene/Ptotal = 47.6 mm Hg/61.89 mm Hg = 0.770
χtoluene = Ptoluene/Ptotal = 14.2 mm Hg/61.89 mm Hg = 0.230

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EX: The vapor pressure of pure hexane and pentane at
25 ⁰C are149.1 mmHg and 508.5 mmHg Respectively
If a hexane pentane solution has a mole fraction of
hexane of 0.750, what are the vapor pressure of hexane
and pentane above the solution? What is the total vapor
pressure?
Solution:
Phex = X hex * P⁰hex = 0.75 * 149.1 mmHg = 112mmHg
Ppen = X pen * P⁰pen = 0.25 * 508.5mmHg = 127mmHg
Ptot = Phex + Ppen = 112 + 127 = 239 mmHg

EX: What is the composition of the vapor in

equilibrium with the hexane pentane solution
described in the last Example?
Solution:
Yhex = Phex / Ptot = 112/239 = 0.469
Ypen = Ppen / Ptot = 127/239 = 0.531

Osmotic Pressure:
Volatile solvent,
non-volatile solute
Raoult’s Law still applies
Water flows from the low
concentration
of solute side to the high side to
reduce the solute concentration
Osmotic pressure - Depends on the
number of solute particles, not the
nature of the solute
Colligative property

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(depends on number of particles present)
For dilute solutions of electrolytes, osmotic pressure,
π, obeys the following relationship (looks familiar!):
πV = nRT

π = nRT/V = M R T.

where M is molarity in mol/L.

Practical Applications:
Biology – electrolyte (saline) solutions to
treat dehydration.
Red Blood Cells will shrink in too salty a
solution but burst in pure water
Need to balance salinity with that of
blood (isotonic)
Hypertonic > 0.92% m/V crenation
Isotonic Saline = 0.92% m/V
Hypotonic < 0.92% m/V rupture

Apply a pressure to the salt water side B to

obtain pure water on side A Force water
through membrane but leave salts
behind Reverse osmosis pumps can be
found in emergency kits on
life boats and small open water vessels to provide
safe drinking water

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EX: what is the osmotic pressure at 25⁰C of an aqueous
solution that contains 1.5 g C12H22O11 in125 ml of solution?
Solution:
n = 1.5 g C12H22O11 * 1 mol C12H22O11 /342.3 g C12H22O11 =
4.38X10-3 mol
π = nRT/v = [(4.38X10-3 mol) * (0.08206L atm)
*(298K)]/(0.125 L) (mol K) = 0.857 atm

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EX: Creatinine is a by-product of nitrogen metabolism
and can be used to provide an indication of renal
function. A 4.04 g sample of creatinine is dissolved in
enough water to make 100 ml of solution. The osmotic
pressure of the solution is 8.73 mmHg at 298 K. what is
the molar mass of creatine?
Solution:
n = π = 8.73mmHg* (1 atm/760mmHg) = 4.7X10-4 M
v RT (0.08206 L atm/mol K) *298 K

amount of solute=0.1 L *(4.7X10-4 mol sol/ 1 L sol)=

4.7X10-5 mol solute

M = (4.04 g ) / (4.7X10-5) = 8.6 X104 g / mol

Freezing-point Depression and Boiling Point Elevation of

Nonelectrolyte Solution
• Vapor pressure is lowered when a solute is
present.
– Boiling point elevation (salt-water boils at > 100oC).
– Freezing point depression (salt-ice melts at < 0oC).
– The solution stays liquid over a wider T range.
• Colligative properties.
– Depends on the number of particles present.

Vapor Pressure Lowering:

fp0, bp0 are normal freezing
and boiling pts of puresolvent
fp and bp are observed
freezing and boiling pts of solutions
m is molality (mol solute per kg solvent)
Kf (freezing pt depression constant)
depends on mp,
ΔHfus, molar mass of solvent

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Kb (boiling pt elevation constant) depends on bp, ΔHvap, molar
mass of solvent.
Practical Application:

EX: vitamin B2 riboflavin, is soluble in water. If 0.833 g

of riboflavin is dissolved in 18.1 g H2O, The resulting
solution has a freezing point of -0.227 ⁰C.
a) What is the molality of the solution?
Molality =ΔTf /(-Kf) = (-0.227 C) / (-0.86 C mol-1 Kg)
= 0.122 mol/Kg
b) What is the molar mass of riboflavin?
Amount of rib = 18.1g H2O*(1 Kg solvent/1000g) *
(0.122mol Kg-1 /1 Kg solvent) = 2.21 X 10-3 mol ribloflavin
Molar mass = (0.833 g rib) / (2.21X10-3mol)
=377g/mol

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Solution of Electrolytes:
• Svante Arrhenius
– Nobel Prize 1903.
– Ions form when electrolytes dissolve in solution.
– Explained anomalous colligative properties

Compare 0.0100 m aqueous urea to 0.0100 m NaCl (aq)

ΔTf = -Kf X m = -186°C m-1 X 0.0100 m = -0.0186°C.
Freezing point depression for NaCl is -0.0361°C.
Why should it be different if the concentration is the same?

Van’t Hoff Factor:

Effect of ions! Ionic solutes (electrolytes) dissociate (more than
one particle per formula unit). Non-electrolytes do not.
NaCl yields two ions in solution, Na+ and Cl-.

For urea (non-electrolyte) i = 1, for NaCl i = 2, for MgCl2 i = 3

Therefore, previous equations should be changed to:

EX: predict the freezing point of aqueous 0.00145 m

MgCl2?

Solution:

Tf = - i * Kf * m = -3 * -1.86 * 0.00145 = 8.1X10-3

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Interionic Attraction: Debye and Huckel
• Arrhenius theory does not correctly predict the
conductivity
of concentrated electrolytes.
• 1923
– Ions in solution do not behave independently.
– Each ion is surrounded by others of opposite charge.
– Ion mobility is reduced by the drag of the ionic
atmosphere (interionic attractions).
– i is not exactly 2.00 for NaCl.

Examples:

EX1: Which one of the following would you expect

to be most soluble in water?

Answer is 2

EX2: Of the solvent/solute pairs given to the right,

which of the solutes would you expect to be least soluble
in the solvent.
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answer is 1

EX3: In the process of refining crude oil, the fraction at

the top of the column is the one with the highest
molecular weight.
1. True
2. False

EX4: If a diver surfaces too quickly from a dive, N2(g)

dissolved in the divers blood will be released quickly
resulting in a painful and dangerous condition called the
bends. This is the same phenomenon as taking the top of
of a pop bottle as depicted to the right.

1. True
2. False

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EX5: The number of moles of CO2(g) above an aqueous
solution of CO2 decreased by two. The volume of gas
above the solution is concurrently decreased by a factor
of two. The concentration of CO2 in solution

1. Decreases by a factor of 4.
2. Decreases by a factor of 2.
3. Remains the same.
4. Increases by a factor of 2.
5. Increases by a factor of 4.

EX6: To the right is a diagram of a closed system

containing two salt water solutions. The solution labeled
A is more concentrated than the one labeled B. Which of
the diagrams below best represents the
system at an infinite time after
preparation?

Answer is 1

EX7: Which of the following aqueous solutions will

have the highest boiling point?

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1. 3 molal glucose
2. 4 molal ethanol
3. 2.5 molal NaCl
4. 2.5 molal CaCl2
5. Cannot tell without Kb for water

EX8: A 2.0 molal aqueous solution of glucose

(C6O6H12) is found to boil at 101 oC. What would the
boiling point of a 2.0 molal solution of
sucrose be?

1. 102 oC
2. 100.5 oC
3. 101 oC
4. Slightly higher than 100.5 oC
5. Cannot determine without Kb

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EX9: The freezing point of a solution is lower than that
of the pure solvent because

1.The addition of solute to the liquid increases the rate of

escape of molecules from the solid phase to the liquid
phase. At lower temperature these rates can again
become equal.

2.The addition of solute to the liquid decreases the

rate at which solvent molecules enter the solid phase.
By lowering the temperature the rate of escape of
molecules from the solid to liquid phase is also
lowered and become equal.

EX10: As the water evaporates from this saturated

solution

1.the vapor pressure above the solution

increases.
2.the vapor pressure above the solution
decreases.
3. the vapor pressure above the solution
remains constant.
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EX11: Two aqueous solutions of equal volume, one
containing 20 g of lactic acid (C3H6O3) and one
containing 10 g of glucose (C6H12O6) are separated by a
semi permeable membrane (allowing only H2O to pass).
The net flow of water through the membrane is?
1. Left.
2. Right.
3. There is no net flow.
4. Cannot tell without knowing the
exact volume of the solutions.

EX12: The table to the right shows the experimental

van’t Hoff factor, i, for three electrolytes at 1.0 m and the
expected value at infinite dilution. Which of the
following is the best explanation for the increase in the
difference in i at for the salts shown?

1.The higher the charge on the ion, the

smaller the radius so only a fraction of
the oppositely charged ions are
separated in solution. The rest are bound to one another.
2. The higher the charge on the ions, the greater
attraction for ions of opposite charge. The greater the
attraction the less they dissolve.
3. The higher the charge on the ion, the greater
attraction for oppositely charged ions. The greater
the attraction the more they act like a single
particle rather than separate particles.

EX13: The table to the right shows the experimental

van’t Hoff factor, i, for three electrolytes at various
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dilutions. Which of the following is the best explanation
for the increase in i at greater dilution.

1.These ionic compounds don’t fully dissolve unless

under very dilute conditions.
2.At greater dilution, there are less interactions
between oppositely charged ions so they act like
completely separate entities.
3.At greater dilution, there are less forces holding the
oppositely charged particles together so they act like
completely separate entities.

EX14: The freezing point depression and boiling point

depression constants for a number of liquids are given in
the table below. Without using a calculator, which of the
following solutions’ freezing point is decreased by the
greatest amount when 1 mole of solute is dissolved in 1
kg of the solvent?

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Examples From Final Exam 6/1/2017:

1* Commercial perchloric acid is 70 % by mass,

HClO4(aq). Calculate the mole fraction of perchloric acid
in the solution. (Atomic weights: H:1.01, O:16 Cl:35.45)
A- 0.845
B- 0.295
C- 0.498
D- 0.420
E- 0.915

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Examples from Second midterm 16/12/2016:

1* A mixture of benzene and toluene has a

total vapor pressure at 25 C of 45 .06mmHg.
What is the partial pressure of benzene in this
solution? the vapor pressure of pure benzene
and pure toluene at 25C are 95.03 mmHg and
28.40 mmHg respectively?
A- 5.75 mmHg
B- 23.76 mmHg
C- 12.17 mmHg
D- 31.3 mmHg
E- 15.40 mmHg

2* Exactly 375 mg of an unknown protein is

dissolved in enough water to give 50 ml of solution
and the osmotic pressure determined as 3.25
mmHg at 298 K. Estimate the molar mass of this
protein (R = 0.082057 atm.L / mol.K)
A- 112000 g/mol
B- 139000g/mol
C- 56400 g/mol
D- 3600 g/mol
E- 42900 g/mol

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3* Which of the solution pairs are more likely to
form a solution?
A- Chloroform (CHCL3) and acetone
(CH3COCH3)
B- Water and octane (C8H18)
C- Methanol (CH3OH) and hexane (C6H14)
D- Water and octyl alcohol (C8H17OH)
E- Acetone(CH3COCH3) and octane (C8H13)

Examples from Second midterm 8/12/2017:

1* An aqueous solution is 6.00 % methanol

(CH3OH) by mass, with d= 0.988 g/ml. what is the
molarity of CH3OH in this solution? (molar mass
of methanol is 32.04 g/mol).
Solution:
1 liter (1000 mL) has a mass of 988 g (1000 mL x 0.988 g/mL = 988 g)
6% of the mass is CH3OH (0.0600 x 988 = 59.3 g CH3OH)
59.3 g / 32.04 g/mol = 1.85 mol CH3OH
1.85 mol / liter = 1.85 M

A- 0.75 M
B- 1.05 M
C- 1.45 M
D- 1.85 M
E- 2.25 M

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2* How many grams of Iodine, I2, must be dissolved
in725ml of carbon disulfide, CS2 (d=1.261 g/ml), to
produce a 0.236 m(molality) solution? (Molar mass of
iodine,I2,is a 0.253.8 g/mol).
A- 54.8 g
B- 66.8 g
C- 78.8 g
D- 60.8 g
E- 72.8 g
3* Calculate the vapor pressure at 25 ⁰C of a solution
containing 165 g of the nonvolatile solute, glucose,
C6H12O6, in 685 g H2O. The vapor pressure of water at
25 ⁰C is 23.8 mmHg. (C:12.01 g/mol, O:16.0 g/mol,
H:1.01 g/mol)
Solution:
Moles glucose = 165 g/180 g/mol = .917 mol Glucose
Moles Water = 685 g / 18.0 g/mol = 38.1 mol Water
Total moles = 38.1 + .9 = 39.0 moles
P = 23.8 mmHg (38.1 / 39.0) = 23.25 mmHg
A- 14.0 mmHg
B- 14.8 mmHg
C- 17.9 mmHg
D- 23.2 mmHg
E- 24.3 mmHg

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4* 1.10 g of an unknown compound reduced the freezing
point of 75.22 g benzene from 5.53 to 4.92 ⁰C. what is
the molar mass of the compound? (Kf(benzene)=5.12 ⁰C
mol-1 Kg)

A- 2.73 g/mol
B- 12.5 g/mol
C- 35.2 g/mol
D- 95.2 g/mol
E- 122 g/mol

End of chapter 14
Abdulfettah Hazuri

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