PHYSICAL CHEMISTRY ( DAS 12303)

CHAPTER 4:
SOLUTIONS

Lecturer:
Nurul Izzati Mohd Ismail
Department of Science and Mathematics
Centre for Diploma Studies (CeDS)
Universiti Tun Hussein Onn Malaysia (UTHM)
OVERVIEW
4.1 Solutions and solubility
4.2 Solution concentration
4.3 Henry’s Law
4.4 Raoult’s Law
4.5 Properties of solution (Colligative Properties)
IN THIS CHAPTER YOU WILL BE ABLE TO:
Identify types of solutions
Identify and calculate the concentration of a solution in
terms of Molarity, Molality, Percentage (v/v%, w/v%,
w/w%) and Mole fraction.
Understand Henry’s Law and Roult’s Law
 INTRODUCTION
Solutions are all around us. Our atmosphere is a solution of gases in
gases, carbonated beverages are solutions of gases in liquids, sweetened
drinks are solutions of solids in liquids, and solder is a solution of solids in
solids.
Reactions are normally carried out in solutions of gases or liquids
because the particles in these solutions are free to move and to collide.
 In this chapter, we define several terms relevant to the study of solutions
and discuss some solution properties.
4.1 SOLUTION AND SOLUBILITY
SOLUTION
Mixtures—samples of matter containing two or more substances physically combined
Homogeneous mixtures, -meaning that the composition of the mixture (and
therefore its properties) is uniform throughout its entire volume.
Solvent -may be viewed as the medium in which the other components are dispersed
A solution in which water is the solvent is called an aqueous solution
Solute -is a component of a solution which is dissolved in the solvent.

Solute + Solvent = Solution

Solute + Solvent = Solution
 SOLUBILITY
Solubility is a chemical property
Which is describe as the ability for a given substance
(solute) to dissolve in a solvent.

Immiscible : two liquids that are insoluble (e.g. Oil and
Vinegar)
Miscible : Two liquids that are soluble in each other (e.g.
alcohol and water)
FACTORS AFFECTING SOLUBILITY
Temperature
Polarity
Pressure (Henry’s Law)
SOLUBILITY CHANGES IN TEMPERATURE

Solubility of gas in H2O Solubility of solid in H2O

 SOLUBILITY OF GAS
Solubility of gas decreases with the increasing of temperature
At low temperature, gas molecules interact with solvent molecule by attractive
force.
Heat is released when attractive force formed between gas and solvent
molecules
Thus, this process is an exothermic???endothermic?? process.
As external heat is supplied (temperature increases), the gas molecules will be in
its excited state and will overcome the attractive forces between the gas and
solvent
Resulting in the decreasing solubility of gas molecules in solvent.
 SOLUBILITY OF SOLID
Generally, the solubility of solid solute
increases with the increasing of
temperature.
Addition of heat breaks down the bond
which holds the solid (solute) molecules
intact due to the increasing of kinetic
energy of the molecule of solvent.
The average kinetic energy of the solute
molecules also increases with temperature,
and it destabilizes the solid state.
The increased vibration (kinetic energy) of the
solute molecules causes them to be less able
to hold together, and thus they dissolve more
readily.
At the same time, the formation of solid-
solvent attractive force forms which makes the
solid to dissolve in the solvent.
Example of solid solutes are salts such as
Potassium salts, Sodium salts, Ammonium salts,
Nitrate salts etc.
 SOLUBILITY OF SALTS IN WATER
The general rules for predicting the solubility of salts in water:
1. All common Sodium, Potassium and Ammonium salts are soluble
2. All Nitrates are soluble
3. Common Chlorides are soluble, except Silver Chloride
4. Common Sulphates are soluble, except those of Barium and Calcium
5. Common Carbonates are insoluble, except those of Sodium, Potassium
and Ammonium
SOLUBILITY RULES
1. A salt is soluble in water if it contains any one of the
following ions:
NH4+ Li+ Na+ K+ or NO3-

Examples:
soluble salts
LiCl Na2SO4 KBr Ca(NO3)2
CL- SALTS
2. Salts with Cl- are soluble, but not if the

positive ion is Ag+, Pb2+, or Hg22+.

Examples:
soluble not soluble(will not dissolve)
MgCl2 AgCl PbCl2 HgCl2
SO42- SALTS

3. Salts with SO42- are soluble, but not if the positive ion is
Ba2+, Pb2+, Hg2+ or Ca2+.
Examples:
soluble not soluble
MgSO4 BaSO4 PbSO4 HgSO4 CaSO4
POLARITY
Solutes dissolve in solvent with the same polarity
Polar solvent will dissolves polar solute
Non-polar solvent will dissolve non-polar solute
Polar solvent WILL NOT DISSOLVE non-polar solute or vice versa

‘LIKE DISSOLVES LIKE’

4.2 SOLUTION CONCENTRATION
QUANTITATIVE & QUALITATIVE
QUANTITATIVE
Molarity
Molality
Mole fraction
Mass percentage
Volume percentage
Mass-volume percentage
MOLARITY (M)
Molarity is defined as the number of moles of solute in
exactly 1 liter (1 L) of the solution:

𝒎𝒐𝒍 𝑠𝑜𝑙𝑢𝑡𝑒
𝑀=
𝑳 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
 MOLALITY
The fraction of moles of solute per unit mass (kg) of
solvent is referred to the term Molality of solution.

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 (𝑚𝑜𝑙)

Molality, m =
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 (𝑘𝑔)
EXAMPLE 1:
A 355-mL soft drink sample contains 0.133 mol of sucrose (table
sugar). Find the molar concentration of sucrose in the beverage
SOLUTION
𝒎𝒐𝒍 𝑠𝑜𝑙𝑢𝑡𝑒 𝟎. 𝟏𝟑𝟑 𝒎𝒐𝒍
𝑀= = = 0.375 𝑀
𝑳 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 1𝐿
𝟑. 55 𝑚𝐿 ×
1000 𝑚𝐿
 MOLE FRACTION, X
The mole fraction can be defined as the number of moles of one component
in a mixture divided by the total number of moles for all substance present
in the mixture.

𝑛𝑖
𝑋𝑖 =
𝑛𝑡𝑜𝑡𝑎𝑙

where
𝑋𝑖 = the ith component of a mixture.
𝑛𝑖 = the number of moles of component i in mixture X.
𝑛𝑡𝑜𝑡𝑎𝑙 = the total moles of all substance present in the mixture.
EXAMPLE 2
CuSO4 is prepared by dissolving 30g of CuSO4 in 200g of
H2O. Find the mole fraction of CuSO4. (Ar; Cu=63.5 ,
S=32.0, O=16.0, H=1.0 )
SOLUTION
The total components made up the solution is CuSO4 and H2O

30 𝑔
Mole of CuSO4 = = 0.188 mol
159.5 𝑔

200 𝑔
Mole of H2O= = 11.11 mol
18 𝑔

0.188 𝑚𝑜𝑙
Mole fraction of CuSO4 = = 0.017
( 0.188 +11.11 𝑚𝑜𝑙)
MASS PERCENTAGE
mass percentage of a solution component is defined as the
ratio of the component’s mass to the solution’s mass

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡
𝑚𝑎𝑠𝑠 𝑝𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 = × 100%
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

Mass percentage is also referred to by similar names such as

percent mass, percent weight, and weight/weight percent.
Symbols are often used including %mass, %weight,
and (w/w)%.
EXAMPLE 4
A 5.0-g sample of spinal fluid contains 3.75 mg
(0.00375 g) of glucose. Find the percent by mass of
glucose in spinal fluid?
SOLUTION

1𝑔
3.75 𝑚𝑔 𝑔𝑙𝑢𝑐𝑜𝑠𝑒 ×
1000 𝑚𝑔
% 𝑔𝑙𝑢𝑐𝑜𝑠𝑒 = = 0.075 %
5.0 𝑔 𝑠𝑝𝑖𝑛𝑎𝑙 𝑓𝑙𝑢𝑖𝑑
VOLUME PERCENTAGE
concentration of a solution formed by dissolving a liquid
solute in a liquid solvent is often expressed as a volume
percentage, %vol or (v/v)%:

𝑣𝑜𝑙𝑢𝑚𝑒 𝑠𝑜𝑙𝑢𝑡𝑒
𝑣𝑜𝑙𝑢𝑚𝑒 𝑝𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 = × 100%
𝑣𝑜𝑙𝑢𝑚𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
 EXAMPLE 5
Rubbing alcohol (isopropanol) is usually sold as a 70% vol aqueous solution. If
the density of isopropyl alcohol is 0.785 g/mL, calculate how many grams of
isopropyl alcohol are present in a 355 mL bottle of rubbing alcohol?
SOLUTION
By multiplying the isopropanol volume by its density yields the requested mass:

70 𝑚𝐿 𝑖𝑠𝑜𝑝𝑟𝑜𝑝𝑦𝑙 𝑎𝑙𝑐𝑜ℎ𝑜𝑙 0.785 𝑔 𝑖𝑠𝑜𝑝𝑟𝑜𝑝𝑦𝑙 𝑎𝑙𝑐𝑜ℎ𝑜𝑙

355 𝑚𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
100 𝑚𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 1 𝑚𝐿 𝑖𝑠𝑜𝑝𝑟𝑜𝑝𝑦𝑙 𝑎𝑙𝑐𝑜ℎ𝑜𝑙
= 195 𝑔 𝑖𝑠𝑜𝑝𝑟𝑜𝑝𝑦𝑙 𝑎𝑙𝑐𝑜ℎ𝑜𝑙
MASS-VOLUME PERCENTAGE
A mass-volume percent is a ratio of a solute’s mass to the solution’s volume
expressed as a percentage
For example, physiological saline solution, used to prepare intravenous fluids, has a
concentration of 0.9% mass/volume (w/v), indicating that the composition is 0.9 g of
solute per 100 mL of solution.
The concentration of glucose in blood (commonly referred to as “blood sugar”) is also
typically expressed in terms of a mass-volume ratio. Though not expressed explicitly
as a percentage, its concentration is usually given in milligrams of glucose per
deciliter (100 mL) of blood.
QUALITATIVE CONCENTRATION
Solute concentrations are often described with qualitative terms
such as:
Dilute (of relatively low concentration)
Concentrated (of relatively high concentration).
DILUTION OF SOLUTIONS
Dilution is the process whereby the concentration of a solution is lessened by the
addition of solvent

+ = Diluted tea
Dilution is also a common means of preparing solutions of a
desired concentration.
By adding solvent to a measured portion of a more concentrated
stock solution, we can achieve a particular concentration.
Mathematical relationship can be used to relate the volumes and concentrations of a
solution
According to the definition of molarity, the molar amount of solute in a solution is
equal to the product of the solution’s molarity and its volume in liters:

𝑛 = 𝑀𝐿
The expression for solution before and after dilution can be written as

𝑛1 = 𝑀1 𝐿1
𝑛2 = 𝑀2 𝐿2

where “1” and “2” represent the condition “before” and “after” dilution process.
Since the dilution process does not change the amount of solute in the solution, thus
n1 = n2
Therefore the equation for dilution become:

𝑀1 𝐿1 = 𝑀2 𝐿2

Dilution equation can also be written as

𝐶1 𝑉1 = 𝐶2 𝑉2
where C and V referred to the term concentration and volume
EXAMPLE 3
Calculate volume of 1.59 M Potassium Hydroxide, KOH required to prepare 5.00 L of
0.100 M KOH?
SOLUTION
Refer the dilution equation:
𝐶1 𝑉1 = 𝐶2 𝑉2
Rearrange the equation
𝐶2 𝑉2
𝑉1 =
𝐶1

(0.100 𝑀)(5.00 𝐿)
𝑉1 =
(1.59 𝑀)

𝑉1 = 0.314 𝐿
4.3 HENRY’S LAW
PRESSURE AND SOLUBILITY
When gas above liquid keep increased in pressure, the gas will
partially dissolved in the solution.
For example, CO2 and water.

For example, CO2 dissolved in water as the

pressure increased in process of making carbonated
drink.
As the pressure of CO2 keep increasing, the solubility of CO2
with water also increased.
This relation is given by Henry’s Law
 HENRY’S LAW
Henry’s law states that the quantity of an ideal gas that dissolves in a definite volume of liquid is
directly proportional to the partial pressure of the gas above the liquid.
In simpler words: Solubility of a gas in a liquid is directly proportional to the partial pressure of the
gas above the liquid
=> More gas dissolves into liquid at high pressure

Sg=kPg

Sg=solubility (g/L) or Cg (mol/L)

k= Henry’s constant that depend on identities of the gaseous solute and solvent, and on the solution
temperature
P=Partial Pressure (atm)
SOME OF HENRY’S LAW CONSTANT
SOLUBILITY OF A GAS IN A LIQUID IS DIRECTLY
PROPORTIONAL TO THE PARTIAL PRESSURE OF THE GAS
ABOVE

The henry’s Law can be used to identify the solubility of

the gas when we Pressurized or dePressurized the gas
above solution.

𝑆1 𝑆2
=
𝑃1 𝑃2
TEST YOUR UNDERSTANDING
The solubility of a gas in water is 0.16 g/L at 104 kPa. Find
the solubility when pressure of the gas increased to 288 kPa.
Assume the temperature remain constant.
SOLUTION
Use Henry’s law

𝑆1 𝑆2
=
𝑃1 𝑃2
0.16 𝑔/𝐿 𝑆2
=
104 𝑘𝑃𝑎 288 𝑘𝑃𝑎

𝑆2 = 4.4 𝑥 10−1 𝑔/𝐿

4.4 RAOULT’S LAW
 VAPOUR PRESSURE
Vapour pressure is referred to the pressure that is present at the surface of the liquid.
Vapour pressure is not affected by the surface area but it is affected by factors such as
humidity, intermolecular bond, and boiling point.
Liquid with high vapour pressure is referred to volatile (evaporated readily).

Low High
vapor vapor
pressure pressure
 RAOULT’S LAW
The partial pressure of each component of an ideal mixture of liquids is equal to the vapour
pressure of the pure component multiplied by its mole fraction in the mixture.
Raoult's law states that the vapour pressure of a solvent above a solution is equal to the vapour
pressure of the pure solvent at the same temperature scaled by the mole fraction of the solvent
present

This is known as Raoult’s Law

0
𝑃𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 𝑋𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑃𝑠𝑜𝑙𝑣𝑒𝑛𝑡

0
𝑃𝑠𝑜𝑙𝑣𝑒𝑛𝑡 =vapour pressure of pure solvent
𝑛𝑠𝑜𝑙𝑣𝑒𝑛𝑡
𝑋𝑠𝑜𝑙𝑣𝑒𝑛𝑡 =mol fraction of the solvent= ( )
𝑛𝑠𝑜𝑙𝑣𝑒𝑛𝑡 +𝑛𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

𝑃𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 =final vapour pressure of the solution

At any given temperature for a particular solid or liquid, there is a
pressure at which the vapour formed above the substance is in dynamic
equilibrium with its liquid or solid form.
This is the vapour pressure of the substance at that temperature.
At equilibrium, the rate at which the solid or liquid evaporates is equal
to the rate that the gas is condensing back to its original form.
All solids and liquids have a vapour pressure, and this pressure is
constant regardless of how much of the substance is present
A solution that obeys Roult’s Law is called Ideal Solution
COLLOIDS
COLLOID
Colloids contain some particles that are intermediate between those in
a solution and those in a suspension.
Examples include peanut butter, pudding, Jello, whipped cream, and
even fog
PROPERTIES OF COLLOIDS
Do not separate into layers.
Particles will not become trapped by a filter.
Scatter light.
Colloids and suspensions appear cloudy; unlike solutions which
are much clearer.
EXAMPLE OF COLLOIDS
(a) homogeneous mixture (water and salt)-appear clear
(b) Colloid (milk)-particle remain disperse and did not settle
(c) Suspension (mud)-heteogenous mixture
light is scattered by colloidal-size particles in the air (fog, smoke, etc.).
4.5 PROPERTIES OF SOLUTION :
COLLIGATIVE PROPERTIES
COLLIGATIVE PROPERTIES
Changes in the properties of a solution due to the addition
of solute
Four vital colligative properties
1. Vapour pressure depression
2. Boiling point elevation
3. Freezing point depression
4. Osmotic pressure
1. VAPOUR PRESSURE DEPRESSION
Vapour pressure is the pressure produced due to the
evaporation of a substance.
The presence of solute in a solution reduces the rate of
evaporation.
The presence of solute particles blocks some of the ability for
liquid particles to evaporate.
Lower evaporation properties results in lower vapour pressure.
 Thus, solutions of solid solutes typically have a lower vapour
pressure than the pure solvent.
 2. BOILING POINT ELEVATION
Boling points of pure solvent reduces with the presence of
solute.
This is due to the presence of solute particles which decreases
the vapour pressure of the liquid solvent
Thus, a higher temperature is needed to reach the boiling
point.
 3. FREEZING POINT DEPRESSION
When a solution freezes, only the solvent particles come together to form
a solid phase, and the presence of solute particles interferes with that
process.
Therefore, for the liquid solvent to freeze, more energy must be removed
from the solution, which lowers the temperature.
Thus, solutions have lower freezing points than pure solvents do.
 OSMOTIC PRESSURE
Osmosis is defined as a process which solvent molecules travels trough a
semi-permeable membrane without the existence of solute.
Solvent with more dilute concentration tend to move towards to the more
concentrated concentration of solution until it reaches equilibrium of the
concentration.
This situation is called osmotic pressure.
External pressure can be exerted on a solution to counter the flow of
solvent; the pressure required to halt the osmosis of a solvent is equal to
the osmotic pressure of the solution.
REMINDER
END OF CHAPTER 4
WOHOOOO..