Properties of solutions

CH1071
Chemistry and Green Chemistry for Process Engineers

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Outline
• Solutions
• The solution process
• Saturated solutions
• Solubility product constant
• Colligative properties
• Real and ideal solutions
• Henry’s law

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 Solutions
Much of the world around us is
composed of solutions !!!

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4
Solute, solvent and solution

E.g.,-Salt

E.g.,-Water The component in E.g.,-Salt water

the lesser amount
The component in
the greater amount

Solute can be a solid, gas or liquid

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 The Solution Process
• Why do some substances readily mix to form solutions Solute Solute
while others do not?
• Dissolving of one substance in another substance is
largely dependent on the intermolecular forces
present in the substances. Solvent Solvent
• between the solute particles
• between the solvent particles
• between the solute and solvent particles.
Solute Solvent

Formation of solution can occur when the magnitude of all

three forces are similar

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The Solution Process
• For a solution to form,
• The solute particles must separate from each other.
• Solute particles must disperse throughout the solvent.
• The solvent may separate to make room for the solute
particles/ solute particles may occupy the space between
the solvent particles.

The general process by which a solute becomes dispersed in a

solution is known as solvation.

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 The Solution Process
• Examples:
• Ionic compounds tend to dissolve in
polar solvents.
• NaCl in water
• Nonpolar substances tend not to
dissolve in water, but they do dissolve
in nonpolar solvents
• Fats, oil, grease, and gasoline, for example,
do not dissolve in water, but they form a
layer on top of water.

When substances do not mix but form distinct

layers, they are referred to as immiscible.
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Polar and nonpolar solvents

• Polar molecules tends to dissolve in polar solvents.

• Nonpolar molecules tends to dissolve in nonpolar solvents.
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Electrolytes
• Classifying solutions based on their ability to conduct electricity.

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Electrolytes
Nonelectrolytes
• do not ionize at all, but
dissolve as whole molecules
• Sugar
Strong electrolytes
• produce ions when dissolved
in water
• soluble salts, strong acids,
and strong bases
Week electrolytes
• only partially ionize when
dissolved in water.
• weak acids and weak
bases
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Dissolving of sugar in water
• The water molecules, (polar) pull the
polar sugar molecules from the
crystal array, and the compound
dissolves.
• Polar solutes such as sugars, low-
molecular-weight alcohols, and acetone

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 Dissolving of strong acids in water

• The acid is a polar covalent compound,

• When it dissolves in water, it ionizes—that is, the hydrogen atoms break away from
the molecule, forming hydrogen ions ( + ions) and – ions.
• A total, complete ionization
• Inorganic acids, such as HCl, H2SO4, and HNO3,

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Dissolving of weak acids in water

• The acid is a polar covalent compound

• It dissolves completely in water, but only partially ionizes.
• Acetic acid (HC2H3O2)

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Solubility
• The solubility of a solute is defined as the maximum amount that
dissolves in a given amount of solvent at a specified temperature.
• Solubility of aqueous solutions is the amount of solute that will
dissolve in 100 grams of water at a specific temperature.

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Concentration of Solutions
• Mass concentration (µg/L, ng/L)
• mass of the solute per liter of solution

• Molarity mol/L (M)

• moles of solute per liter of solution

• Molality mol/kg (m)

• moles of solute per kg of solvent

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Concentration of Solutions
• Molar Fraction (x)
• mole of component interested in total number of moles present (solute + solvent)

moles of solute
Molar faction of solute (X solute ) =
moles of solute+moles of solvent
• Mass faction
• mass of the solute divided by the mass of solution multiplied by 100

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Concentration of Solutions
• Part per million (ppm)
Parts per million is obtained by multiplying the ratio of the mass of solute to mass of solution by 106 ppm
• ppm ~ mg/l (for dilute aqueous solutions)

• Part per billion (ppb)

Parts per billion is obtained by multiplying the ratio of the mass of solute to mass of solution by 109 ppm
• ppb ~ µg/L (for dilute aqueous solutions)

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Saturated solutions
• A solution is saturated, when the maximum amount of solute has
dissolved in the solvent at a particular temperature.
• A solution is unsaturated, when the solvent holds less than its
maximum amount of solute
• A solution is supersaturated, when the solution holds more than the
maximum amount.

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Saturated solutions

Solubility of NaCl in water is 36.0 g at the given temperature.

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Factors affecting solubility of solids in liquids
• Temperature
• Generally, the solubility of
solids in liquids increases
with temperature

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 Solubility product constant (Ksp)
• The solubility product constant (Ksp) is the equilibrium constant for
the dissolution of a solid substance into an aqueous solution.

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Colligative properties
• Properties that depend on the collective number of particles present in the solution
rather than the types of particles.
• These are found for mixtures containing a solvent and a non-volatile solute.

• Lowering of vapour pressure

• Elevation of boiling point
• Depression of freezing point
• Osmotic pressure

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Lowering of vapour pressure
• In a solution, solute particles at the surface reduce the amount of solvent that
can enter the vapor phase resulting in a lower vapor pressure.

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Vapou Pressure Lowering
• The vapour pressure of a 2-component system is less
than that of the corresponding pure solvent by an
amount proportional to the mole fraction of solute

 P1 = X 2P10
• We can use this effect to determine the molar mass of
a solute.

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Example:
• The vapour pressure of pure benzene at 298K is 0.1252 atm.
• If 6.40 g of an unknown compound is added to 78 g of benzene (78 g/mol), the pressure drops to
0.1192 atm.
• Estimate M, the molar mass of the unknown.

The pressure drops by

0.1252 - 0.1192 = 0.006 atm
ΔP1=- X2P01
X2 = 0.006/ 0.1252 = 0.048

From the definition of mole fraction:

n2 ; n1= 78 (g)/ 78 (g/mol)
0.048 =
1 + n2
This gives n2 = 0.05 mol and M = 128 g mol-1

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Elevation of boiling point
• The boiling point is defined as the temperature
at which the vapor pressure of a liquid is equal
to the external pressure.
• Adding a solute lowers the vapor pressure.
• Then a higher temperature is required to reach
the point where the vapor pressure of the liquid
is equal to the external pressure.
• Therefore, the boiling point is higher for a
solution as compared to its pure solvent.

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Elevation of boiling point

ΔT = K m
b b

where
ΔTb is the increase in boiling point for the solution
Kb is the molal boiling point elevation constant
m is the molality of the solution.

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Example
• Determine the boiling point of sugar solution of 2.0 molality. Water’s
Kb is equal to 0.51 °C/m. The boiling point of water is 100°C.
ΔTb = Kbm
= 0.51 * 2
= 1.02

Boiling point of sugar solution = 100 + 1.02 = 101.2 °C

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Depression of freezing point

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Depression of freezing point

ΔT = K m
f f

where
ΔTf is the decrease in freezing point for the solution
Kf is the molal freezing point depression constant
m is the molality of the solution.

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Addition of Antifreeze to the Radiator Water:

A common antifreeze agent is “ethylene glycol”; 1,2-ethanediol CH2(OH)CH2 (OH)

(62 g mol-1).
What volume of this substance (ρ = 1.11 g cm-3), would be needed to add into 6.5 L
of water to provide the freezing protection down to -20°C?
Water’s Kf value is 1.86°K/ kg mol -1.

The molality of the solution needed will be given by,

ΔTf = Kfm

20 K = 1.86°(K/ kg mol -1 ) m
m = 10.75 mol/kg

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Since we have 6.5 L = 6.5 kg of water, we will require
6.5 × 10.7 = 69.9 mol of antifreeze.
The corresponding mass is
(62 g mol-1)(69.9 mol) = 4330 g.

Using the density given we will need approx 3.9 L of antifreeze.

Note that measurements of ΔTb and/or Δ Tf can give values for

the molar masses of substances, if the respective solvent Kb or Kf
values are known.

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 Osmotic pressure
• A semipermeable membrane allows of solvent particles
to pass through, but it blocks solute particles.
• Osmosis occurs when solvent molecules move through a
semipermeable membrane from the pure solvent or
diluted solution to a more concentrated solution.
• Solvent particles pass through the membrane in both
directions.
• There is a net movement of solvent from a region of
higher concentration to a region of lower concentration.
• The pressure required to stop the net movement of
solvent particles across the semipermeable membrane is
called the osmotic pressure of the solution.

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Osmotic pressure

Π= MRT
Where,
Π is the osmotic pressure in atmospheres
M is the molarity of the solution
R is the ideal gas law constant
T is the absolute temperature

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Reverse osmosis
• Example: “Freshwater is obtained from saltwater by forcing water
from a region of low freshwater concentration to a region of high
freshwater concentration”

Semipermeable membrane

Freshwater Seawater

Natural process Reverse osmosis

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Reverse osmosis
• In reverse osmosis process external
pressure P greater than the osmotic
pressure Π is used.

Reverse osmosis

A pressure of approximately 30 atmospheres is required to

force freshwater to move from seawater across a
semipermeable membrane

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Colligative properties of electrolytes
• When electrolyte solutions are considered, colligative properties are
dependent on the number of particles in the solution.
• 1 m concentration of a nonelectrolyte, such as sugar, yields 1 mole of particles
per kg of solvent.
• An electrolyte such as NaCl theoretically dissociates to give 1 mole of sodium
ions and 1 mole of chloride ions.

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Example
• What would be the change in the freezing point of 1m NaCl solution? The molal
freezing point depression constant for water is 1.86°(K/ kg mol -1 ) .

ΔTf = Kfm
ΔTf = 1.86°(K/ kg mol -1 ) Χ 1 (mol/kg) Χ 2
= -3.72 K

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Ideal and non ideal solutions

Pure A A mixture of A and B

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Ideal and non ideal solutions
Ideal mixture
• Solutions that obey Raoult’s law
are called “ideal” solutions
• The escaping tendency of
molecules ‘A’ in a mixture of A
and B is the same as that in pure
A. (presence of B has no effect
on the forces between A
molecules in the mixture.)
• Intermolecular forces of
attraction between A – A, B – B
and A – B are nearly equal.
Non ideal (real) mixture
• The escaping tendency of
molecules ‘A’ in a mixture of A and
B is not same as that in pure A.
• The Intermolecular forces of
attraction between A-A and B-B are
different from that of A-B
interaction.
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Raoult’s law
• Raoult’s law
• When the vapour and liquid are in equilibrium, the partial pressure of a component
in a vapor mixture is equal to the product of the vapour pressure of pure
component and the mole fraction of the component in liquid phase.

For two-component system: A mixture of A and B

pA = XA poA pB = XB poB YA YB
pA - partial pressure of A PA PB
pB - partial pressure of B
poA -vapour pressure of pure A
poB -vapour pressure of pure B XA XB

Raoult's Law only applies for ideal solutions. 42

Positive deviation from Raoult’s Law
Vapor pressure is higher than expected by Raoult’s Law

ptot (real) > ptot (Raoult)

The Intermolecular forces of attraction between A-B are

weaker than that of A-A and B-B interaction.

YA YB
PA PB

XA XB

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Negative deviation from Raoult’s Law
Vapor pressure is lower than expected by Raoult’s Law

ptot (real) < ptot (Raoult)

The Intermolecular forces of attraction between A-B are

stronger than that of A-A and B-B interaction.

YA YB
PA PB

XA XB

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Henry’s law
• For real (non ideal) solutions, at low concentrations, although the vapour
pressure of the solute is proportional to its mole fraction in the liquid phase, the
constant of proportionality is not the vapour pressure of the pure substance.

pB = KHXB xB → 0 (B is the “solute”)

KH - Henry’s law contant

Depends on the solvent/solute mixture and the temperature.

Henry’s law predicts the solubility of gases in liquid when

the solute is a gas.
Solute - B

In ideal solutions, the solute, as well as the solvent, obeys Raoult’s law. 45
Solubility of gases in liquids
Henry’s Law states that the solubility of a gas is directly proportional to the
partial pressure of that gas over the solution.

Pgas,1
Pgas,2

Xgas,2
Xgas,1

pgas = KHCgas
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 Factors affecting the gas solubility in liquids
1. Partial pressure of gas

P1CO2 > P2CO2

C1CO2
> C2CO2

P1CO2- CO2 partial pressure in bottle 1

P2CO2- CO2 partial pressure in bottle 2
X1CO2 - CO2 concentration in bottle 1
X2CO2- CO2 concentration in bottle 2

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Pgas ↑ Cgas↑
Factors affecting the gas solubility in liquids
2. Temperature

• The solubility of all gases

decrease with increasing
temperature.

T1gas < T2gas

T1gas –Temperature of liquid at condition 1
T2gas- Temperature of liquid at condition 2 C1gas > C2gas
C1gas-Gas concentration in the liquid at condition 1
C2gas-Gas concentration in the liquid at condition 2

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Tgas↑ Cgas↓
49
When the partial pressure of nitrogen over a
sample of water at 19.4 oC is 9.20 atm, then the
concentration of nitrogen in the water is 5.76 x 10-3
mol L-1. Compute Henry’s law constant for nitrogen
in water at this temperature.

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When the partial pressure of nitrogen over a
sample of water at 19.4 oC is 9.20 atm, then
the concentration of nitrogen in the water is
5.76 x 10-3 mol L-1. Compute Henry’s law
constant for nitrogen in water at this
temperature.
nN 5.76x10 −3 mol/l
XN  2
=
2 nH  1000g/l 
2O 
 18g/mol 

 
= 1.0378 x 10 − 4
PN Given 9.20 atm
kN = 2
= =
2 XN Find 1.0378x10 − 4
2

= 8.86 x 10 4 atm 51