Unit 7:
The Solution Process
Chemistry: The Molecular Nature of Matter and Change,
7th Edition by Silberberg and Amateis
Organic Chemistry, 11th Edition by Solomons et.al.
Olivert M. Sitoy, M.Sc., R.Ch.
Chemistry Department
College of Arts and Sciences
Xavier University – Ateneo de Cagayan
Types of Solutions
▪ Saturated Solution: A solution that contains the maximum amount of solute in a given
solvent, at a specific temperature.
▪ Unsaturated Solution: A solution that contains less solute than it has the capacity to
dissolve.
▪ Supersaturated Solution: A solution that contains more solute than is present in a
saturated solution.
▪ Crystallization: The process in which dissolved solute comes out of solution and forms
crystals.
Types of Solutions
▪ General Rule of Thumb: The solvent’s phase dictates the phase of the solution
Major Types Intermolecular Forces in Solutions
Major Types Intermolecular Forces in Solutions
▪ Ion-Dipole Forces: Principal force involved
when an ionic compound dissolves in water.
▪ Forces compete – Competition between the
attraction of ions and dipole molecules with
ions and crystal structure dissolution.
▪ Hydration shells form – As ion separates,
water molecules cluster around it in
hydration shells. For small ions (e.g., Li+),
four water molecules cluster around in
tetrahedral geometry. For larger ions (Na+
and F-), six water molecules cluster around
in octahedral geometry.
▪ Hydrogen Bonding: Principal force in solutions
of polar, O- and N-containing organic and
biological compounds, such as alcohols, amines,
and amino acids.
Major Types Intermolecular Forces in Solutions
▪ Ion-Dipole Forces: Principal force involved when an ionic compound dissolves in water.
▪ Forces compete – Competition between the attraction of ions and dipole molecules
with ions and crystal structure dissolution.
▪ Hydration shells form – As ion separates, water molecules cluster around it in
hydration shells. For small ions (e.g., Li+), four water molecules cluster around in
tetrahedral geometry. For larger ions (Na+ and F-), six water molecules cluster
around in octahedral geometry.
Major Types Intermolecular Forces in Solutions
▪ Dipole-Dipole Forces: in the
absence of H bonding, polar
molecules like propanal
(CH3CH2CHO) to dissolve in polar
solvents like Dichloromethane
(CH2Cl2).
▪ Ion-Induced dipole Forces: A
type of charged-induced dipole
force, rely on polarizability. They
arise when an ion’s charge
distorts the electron cloud of a
nonpolar molecule. This type of
force initiates the binding of the
Fe2+ ion in hemoglobin to an O2
molecule entering a red blood
cell.
Major Types Intermolecular Forces in Solutions
▪ Dipole-Induced Dipole Forces: also
based on polarizability, where polar
molecule distorts the electron cloud of a
nonpolar molecule. They are weaker
than ion-induced dipole forces because
of Coulomb’s Law. The solubility in water
of atmospheric O2, N2, and noble gases,
while limited, is due to this forces. Paint
thinners and grease solvents also rely on
them.
▪ Dispersion Forces: Contributes to the
solubility of all solutes in solvents, but
they are the principal intermolecular
forces in solutions of nonpolar
substances such as petroleum and
gasoline.
Solubility
▪ Solubility: The maximum amount of solute that dissolves in a fixed quantity of a given
solvent at a given temperature, when an excess of the solute is present.
▪ Solubility is a quantitative term, but concentrated and diluted is a qualitative term.
▪ “Like dissolves Like”: Substance with similar types of intermolecular forces dissolve in
each other.
Solubility
Solubility
▪ “Like dissolves Like”: Substance with similar types of intermolecular forces dissolve in
each other.
Solubility
▪ “Like dissolves Like”: Substance with similar types of intermolecular forces dissolve in
each other.
▪ Salts are soluble in water. Ion-dipole attractions (between ions and water) are
similar in strength of ionic bonding (pure salt) and H-bonding (pure water).
▪ Salts are insoluble in hexane. Ion-induced dipole forces (between salt and hexane)
are weak to replace ionic bonding (pure salt).
▪ Oil is insoluble in water. Weak dipole-induced dipole forces (between oil and water)
cannot replace H-bonding (pure water) and dispersion forces (pure oil).
▪ Oil is soluble in hexane. Dispersion forces (between oil and hexane) can replace the
present dispersion forces (pure oil, and pure hexane).
▪ Substances with similar noncovalent forces are likely to be soluble in each other.
▪ Solutes do not readily dissolve in solvents whose noncovalent forces are quite different
from their own.
▪ Stronger solute-solvent attractions favor solubility. Stronger solute-solute or solvent-
solvent attraction reduce solubility.
Solubility
▪ Dual polarity and Effects on
solubility:
▪ Solubility in water is high
for smaller alcohols.
▪ Solubility in water is low for
larger alcohols.
▪ Solubility in hexane is high
for larger alcohols.
▪ Solubility in hexane is low
for smaller alcohols.
Intermolecular Forces and Solubility
Heats of Solution and Solution Cycles
Step 1: Solute particles separate from each other. Overcoming intermolecular (or ionic)
attractions is endothermic.
Heats of Solution and Solution Cycles
Step 2: Solvent particles separate from each other. Overcoming intermolecular (or ionic)
attractions is endothermic.
Heats of Solution and Solution Cycles
Step 3: Solute and solvent particles mix and form a solution. Different particles attract each
other and come together, so this step is exothermic.
Heats of Solution and Solution Cycles
Step 1-3: The overall process is called a thermochemical solution cycle. By Hess’s law, the
heat (or enthalpy) of solution (ΔHsoln) when solute and solvent form a solution:
Heats of Solution and Solution Cycles
▪ Heats of Hydration: Solvation of ions by water. This reaction is always exothermic.
ΔHsolvation = ΔHsolvent + ΔHmix
ΔHsoln = ΔHsolute + ΔHsolvent + ΔHmix
ΔHsoln = ΔHsolute + ΔHhydration
▪ Lattice Energy: ΔH involved in the formation of an ionic solid from its gaseous state.
ΔHsoln = ΔHlattice + ΔHhydration
Heats of Solution and Solution Cycles
▪ NaCl. ΔHsoln (3.9 kJ/mol) is small and
positive because ΔHlattice is slightly higher
than combined ΔHhydration. When you
dissolve NaCl in a flask, you don’t feel
temperature change.
▪ NaOH. ΔHsoln (-44.5 kJ/mol) is large and
negative because ΔHlattice is smaller than
combined ΔHhydration. When you dissolve
NaOH in a flask, the flask feels hot.
▪ NH4NO3. ΔHsoln (25.7 kJ/mol) is large and
positive because ΔHlattice is larger than
combined ΔHhydration. When you dissolve
NH4NO3 in a flask, the flask feels cold.
Heats of Solution and Solution Cycles
▪ NaCl. ΔHsoln (3.9 kJ/mol) is small and
positive because ΔHlattice is slightly higher
than combined ΔHhydration. When you
dissolve NaCl in a flask, you don’t feel
temperature change.
▪ NaOH. ΔHsoln (-44.5 kJ/mol) is large and
negative because ΔHlattice is smaller than
combined ΔHhydration. When you dissolve
NaOH in a flask, the flask feels hot.
▪ NH4NO3. ΔHsoln (25.7 kJ/mol) is large and
positive because ΔHlattice is larger than
combined ΔHhydration. When you dissolve
NH4NO3 in a flask, the flask feels cold.
Heats of Solution and Solution Cycles
▪ NaCl. ΔHsoln (3.9 kJ/mol) is small and
positive because ΔHlattice is slightly higher
than combined ΔHhydration. When you
dissolve NaCl in a flask, you don’t feel
temperature change.
▪ NaOH. ΔHsoln (-44.5 kJ/mol) is large and
negative because ΔHlattice is smaller than
combined ΔHhydration. When you dissolve
NaOH in a flask, the flask feels hot.
▪ NH4NO3. ΔHsoln (25.7 kJ/mol) is large and
positive because ΔHlattice is larger than
combined ΔHhydration. When you dissolve
NH4NO3 in a flask, the flask feels cold.
Solubility as an Equilibrium Process
▪ Saturated Solution: Undissolved solute is in equilibrium with dissolved solute.
▪ Unsaturated Solution: Contains less than equilibrium concentration of dissolved solute.
▪ Supersaturated Solution: Contains more than equilibrium concentration of dissolved
solute.
Solubility as an Equilibrium Process
▪ General Rule of Thumb: As temperature increases, solubility (for most ionic
compounds) also increases.
▪ Exceptions: Ce2(SO4)3 is an example, and most of other sulfates.
Solubility as an Equilibrium Process
▪ Since gases are already separated molecules, so ΔHsolute ≈ 0. Because hydration is
exothermic (ΔHhydration < 0), the sum of these two will be negative (ΔHsoln < 0)
▪ General Rule of Thumb: Gas solubility in water decreases with rising temperature
(addition of heat).
▪ Gases have weak intermolecular forces with water. When temperature rises, the
average kinetic energy increases, allowing the gas particles to easily overcome these
forces and re-enter the gas phase.
Thermal Pollution: Water from river and lakes used for cooling
by industrial plants, and the warmed water is returned to the
source. At high temperature, metabolic rates of fish and other
aquatic animal increases (high demand for oxygen). However,
due to high temperature of the returned water, dissolved
oxygen is lower leading to oxygen deprivation.
Solubility as an Equilibrium Process
▪ 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
▪ Where kH is the Henry’s law constant and is specific for a gas-solvent combination at a
given temperature. With Sgas in mol/L and Pgas in atm, kH is in mol/L·atm or mol·L-1·atm-1
Solubility as an Equilibrium Process
Example 1: The partial pressure of carbon dioxide gas inside a bottle of cola is 4 atm at 25
°C. What is the solubility of CO2? The Henry’s law constant for CO2 (carbon dioxide) in
water is 3.3x10-2 mol/L·atm at 25 °C.
SOLUTION:
𝑆𝑔𝑎𝑠 = 𝑘𝐻 × 𝑃𝑔𝑎𝑠
𝑚𝑜𝑙
𝑆𝑔𝑎𝑠 = 3.3 × 10−2 × 4 𝑎𝑡𝑚
𝐿 ∙ 𝑎𝑡𝑚
𝑆𝑔𝑎𝑠 = 0.1 𝑚𝑜𝑙ൗ𝐿
Solubility as an Equilibrium Process
Example 2: If air contains 78% N2 by volume, what is the solubility of N2 in water at 25 °C
and 1 atm (kH for N2 in H2O at 25 °C = 7x10-4 mol/L·atm)?
SOLUTION:
𝑆𝑔𝑎𝑠 = 𝑘𝐻 × 𝑃𝑔𝑎𝑠
−4
𝑚𝑜𝑙
𝑆𝑔𝑎𝑠 = 7 × 10 × (1 𝑎𝑡𝑚 × 0.78)
𝐿 ∙ 𝑎𝑡𝑚
𝑆𝑔𝑎𝑠 = 5.46 × 10−4 𝑚𝑜𝑙ൗ𝐿
Unit 7:
Colligative Properties
of Solutions
Chemistry: The Molecular Nature of Matter and Change,
7th Edition by Silberberg and Amateis
Organic Chemistry, 11th Edition by Solomons et.al.
Olivert M. Sitoy, M.Sc., R.Ch.
Chemistry Department
College of Arts and Sciences
Xavier University – Ateneo de Cagayan
Concentration Terms
Concentration of solution: Relative quantity of solute and solvent contained in a solution.
Concentration Terms
Molarity (M): number of moles of solute dissolved in 1 L of solution.
▪ Effect of Temperature: A liquid expands when heated, so a unit volume of hot
solution contains less solute than one of a cold solution.
▪ Effect of Mixing: Due to solute-solvent interaction that are difficult to predict,
volumes may not be additive (i.e., 500 mL of solute + 500 mL of solvent ≠ 1 L
solution)
Molality (m): number of moles of solute dissolved in 1000 g (1 kg) of solvent.
▪ Effect of Temperature: Molal solutions are based on masses of components. Since
mass is constant does not change with temperature, neither is molality.
▪ Effect of Mixing: Unlike volumes, masses are additive (i.e., 500 g of solute + 500 g of
solvent = 1 kg solution)
Concentration Terms
Molarity (M): number of moles of solute dissolved in 1 L of solution.
Molality (m): number of moles of solute dissolved in 1000 g (1 kg) of solvent.
0.10 M K2CrO4 – 19.4 g of K2CrO4 was placed in the flask
and added enough water to make exactly 1 L of solution.
0.10 m K2CrO4 – 19.4 g of K2CrO4 was placed in the flask
and adding 1000 g (1 kg) water.
Concentration Terms
Example 1: Automobile lead storage battery contain an aqueous solution of sulfuric acid.
The solution as a density of 1.230 g/mL at 25 °C and contains 368 g H2SO4 per liter.
Calculate (a) the molarity of sulfuric acid in the solution, and (b) the molality of sulfuric
acid in the solution
SOLUTION:
𝑚𝑜𝑙 𝑠𝑜𝑙𝑢𝑡𝑒
a) 𝑀=
𝑉𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
1 𝑚𝑜𝑙 𝐻2 𝑆𝑂4
368 𝑔 𝐻2 𝑆𝑂4 × 98.1 𝑔 𝐻 𝑆𝑂
2 4
=
1𝐿
𝑚𝑜𝑙
= 3.75 𝑜𝑟 3.75 𝑀
𝐿
Concentration Terms
Example 1: Automobile lead storage battery contain an aqueous solution of sulfuric acid.
The solution as a density of 1.230 g/mL at 25 °C and contains 368 g H2SO4 per liter.
Calculate (a) the molarity of sulfuric acid in the solution, and (b) the molality of sulfuric
acid in the solution
SOLUTION:
𝑔 𝑠𝑜𝑙𝑢𝑡𝑒 + 𝑔 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 = 𝑔 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
b) 𝑔 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 = 𝑔 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 − 𝑔 𝑠𝑜𝑙𝑢𝑡𝑒
𝑔 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 = 1230 𝑔 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 − 368 𝑔 𝑠𝑜𝑙𝑢𝑡𝑒 = 0.862 𝑘𝑔 𝑤𝑎𝑡𝑒𝑟
1 𝑚𝑜𝑙 𝐻2 𝑆𝑂4
368 𝑔 𝐻2 𝑆𝑂4 × 98.1 𝑔 𝐻 𝑆𝑂
2 4
𝑚=
0.862 𝑘𝑔 𝑠𝑜𝑙𝑣𝑒𝑛𝑡
𝑚𝑜𝑙 𝐻2 𝑆𝑂4
= 4.35 𝑜𝑟 4.35 𝑚
𝑘𝑔 𝑠𝑜𝑙𝑣𝑒𝑛𝑡
Colligative Properties of Solutions
Colligative Properties: A solute (with different physical properties) makes a difference on
the physical properties of a pure solvent.
Electrolytes: An aqueous solution of an electrolyte conducts a current because the solute
separates into as it dissolves.
▪ Strong Electrolytes (e.g., soluble salts, strong acids, and strong bases) dissociates
completely, so their solutions conduct well.
▪ Weak Electrolytes (e.g., weak acids, and weak bases) dissociates very little, so their
solutions conduct poorly.
Non-electrolytes: Compounds such as sugar and alcohol do not dissociate ions at all. They
are non-electrolytes because their solutions do not conduct a current.
Strong Weak Non-
Electrolytes Electrolytes Electrolytes
Colligative Properties of Solutions
Vapor Pressure Lowering: The vapor pressure of a nonvolatile nonelectrolytes solution is
always lower than the vapor pressure of the pure solvent.
Raoult’s Law: The vapor pressure of solvent above the solution (Psolvent) equals the mole
fraction of solvent (Xsolvent) times the vapor pressure of the pure solvent (P°solvent).
Pure Solvent.
Solvent and
Equilibrium
dissolved
between a
solute. Solute
liquid and its
molecules
vapor occurs
increase the
when equal
entropy, so
numbers of
equilibrium
molecules
occurs at a
vaporize and
lower vapor
condense in a
pressure
given time.
Colligative Properties of Solutions
Example 1: Find the vapor pressure lowering, ΔP, 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 density is 0.988 g/mL. The density of glycerol is 1.26 g/mL.
SOLUTION:
Colligative Properties of Solutions
Boiling Point Elevation: A solution
boils at a higher temperature than
the pure solvent. This property
results from vapor pressure
lowering.
Freezing Point Depression: A
solution freezes at a lower
temperature than the pure solvent.
This property also results from
vapor pressure lowering.
Colligative Properties of Solutions
Colligative Properties of Solutions
Example 2: You add 1.00 kg of ethylene glycol (C2H6O2) antifreeze to 4450 g of water in
your car’s radiator. What are the boiling point and freezing point of the solution?
SOLUTION:
Colligative Properties of Solutions
Osmotic Pressure: The pressure that must be applied to the solution to stop osmosis from
a sample of pure solvent.
Osmosis: Net flow of a
solvent through a
semipermeable
membrane from a
region of higher solvent
concentration (lower
solute concentration) to
a region of lower
solvent concentration
(higher solute
concentration)
Colligative Properties of Solutions
Osmotic Pressure: The pressure that must be applied to the solution to stop osmosis from
a sample of pure solvent.
Colligative Properties of Solutions
Example 3: Biochemist have discovered more than 400 mutant varieties of hemoglobin,
the blood protein that binds O2 and carries it to the body’s cell. 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?
SOLUTION:
Colligative Properties of Electrolyte Solutions
Colligative Properties: A solute (with different physical properties) makes a difference on
the physical properties of a pure solvent.
▪ For electrolyte solutions, the compound formula tells us how many particles are in
the solution
▪ The van’t Hoft factor, i, tells us what the “effective” number ions are in the solution.
Colligative Properties of Electrolyte Solutions
Colligative Properties: A solute (with different physical properties) makes a difference on
the physical properties of a pure solvent.
▪ If strong electrolyte solutions behaved ideally,
the factor I would be 2 for KBr, 3 for Mg(NO3)2,
and so on.
▪ However, most strong electrolyte solutions are
not ideal, and the measured value of i is typically
lower than the value expected from the formula.
Colligative Properties of Electrolyte Solutions
Colligative Properties: A solute (with different physical properties) makes a difference on
the physical properties of a pure solvent.
▪ If strong electrolyte solutions behaved ideally,
the factor I would be 2 for KBr, 3 for Mg(NO3)2,
and so on.
▪ However, most strong electrolyte solutions are
not ideal, and the measured value of i is typically
lower than the value expected from the formula.
▪ Ionic Atmosphere. Each type of ion acts “tied up”
so its actual concentration seems lower. The greater
the charge, the stronger the attractions, explaining
higher deviation for multiply-charged ions.
Colligative Properties of Electrolyte Solutions
Colligative Properties: A solute (with different physical properties) makes a difference on
the physical properties of a pure solvent.
▪ If strong electrolyte solutions behaved ideally,
the factor I would be 2 for KBr, 3 for Mg(NO3)2,
and so on.
▪ However, most strong electrolyte solutions are
not ideal, and the measured value of i is typically
lower than the value expected from the formula.
▪ As the ions move about in solution, ions of
opposite charge collide and “stick together” for
brief moments. While in together, they behave as
a single particle called an ion pair.
Colligative Properties of Electrolyte Solutions
Example 4: A 0.952 g sample of magnesium chloride is dissolved in 100. g of water in a
flask.
(a) Which scenes depict the solution best?
(b) Assuming the solution is ideal, what is the freezing point (at 1 atm)?
SOLUTION:
Scene A has 4 Mg2+ spheres and 8 Cl- spheres; Scene B has 8 Mg2+ spheres and 4 Cl-
spheres; Scene C has 4 MgCl2 spheres.
(a) Since, the formula is MgCl it is expected to dissociate in 1 Mg2+ ions and 2 Cl- ions; only
scene A has 1 Mg+ for every 2 Cl-.
Colligative Properties of Electrolyte Solutions
Example 4: A 0.952 g sample of magnesium chloride is dissolved in 100. g of water in a
flask.
(a) Which scenes depict the solution best?
(b) Assuming the solution is ideal, what is the freezing point (at 1 atm)?
SOLUTION:
