Anil’s Chemistry 1

Anil’s Chemistry
Types of Solutions & Expressing Concentration of Solutions
Types of Solutions
 Homogeneous mixtures of two or more than two components are called solutions.

Solution
In chemistry, a solution is a homogeneous mixture composed of only one phase.
In such a mixture, a solute is a substance dissolved in another substance, known as a solvent.
The solvent does the dissolving.
The solution more or less takes on the characteristics of the solvent including its phase, and the solvent is
commonly the major fraction of the mixture.
The concentration of a solute in a solution is a measure of how much of that solute is dissolved in the solvent.
Characteristics
 A solution is a homogeneous mixture
 The particles of solute in solution cannot be seen by naked eye.
 The solution does not allow beam of light to scatter.
 A solution is stable.
 The solute from the solution cannot be separated by filtration (or mechanically).
Types
Homogeneous means that the components of the mixture form a single phase.
The properties of the mixture (such as concentration, temperature, and density) can be uniformly distributed
through the volume but only in absence of diffusion phenomena or after their completion.
Usually, the substance present in the greatest amount is considered the solvent.
Solvents can be gases, liquids or solids.
One or more components present in the solution other than the solvent are called solutes.
The solution has the same physical state as the solvent.
Gas
If the solvent is a gas, only gases are dissolved under a given set of conditions. An example of a gaseous
solution is air (oxygen and other gases dissolved in nitrogen). Since interactions between molecules play almost
no role, dilute gases form rather trivial solutions. In part of the literature, they are not even classified as
solutions, but addressed as mixtures.
Liquid
If the solvent is a liquid, then gases, liquids, and solids can be dissolved. Here are some examples:
 Gas in liquid:
o Oxygen in water
o Carbon dioxide in water – a less simple example, because the solution is accompanied by a
chemical reaction (formation of ions). Note also that the visible bubbles in carbonated water are
not the dissolved gas, but only an effervescence of carbon dioxide that has come out of solution;
the dissolved gas itself is not visible since it is dissolved on a molecular level.
 Liquid in liquid:
o The mixing of two or more substances of the same chemistry but different concentrations to form
a constant. (Homogenization of solutions)
o Alcoholic beverages are basically solutions of ethanol in water.
 Solid in liquid:
o Sucrose (table sugar) in water
o Sodium chloride (table salt) or any other salt in water, which forms an electrolyte: When
dissolving, salt dissociates into ions.
Solid
If the solvent is a solid, then gases, liquids and solids can be dissolved.
 Gas in solids:
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o Hydrogen dissolves rather well in metals, especially in palladium; this is studied as a means of
hydrogen storage.
 Liquid in solid:
o Mercury in gold, forming an amalgam
o Hexane in paraffin wax
 Solid in solid:
o Steel, basically a solution of carbon atoms in a crystalline matrix of iron atoms.
o Alloys like bronze and many others.
o Polymers containing plasticizers.
Expressing Concentration
The concentration of a solution
 is a macroscopic property,
 represents the amount of solute dissolved in a unit amount of solvent or of solution, and
 can be expressed in a variety of ways (qualitatively and quantitatively).
Qualitative Expressions of Concentration
A solution can be qualitatively described as
 dilute: a solution that contains a small proportion of solute relative to solvent, or
 concentrated: a solution that contains a large proportion of solute relative to solvent.
Semi-Quantitative Expressions of Concentration
A solution can be semi-quantitatively described as
 unsaturated: a solution in which more solute will dissolve, or
 saturated: a solution in which no more solute will dissolve.
The solubility of a solute is the amount of solute that will dissolve in a given amount of solvent to produce a
saturated solution.
Quantitative Expressions of Concentration
There are a number of ways to express the relative amounts of solute and solvent in a solution.
Note that some expressions for concentration are temperature-dependent (i.e., the concentration of the solution
changes as the temperature changes), whereas others are not.
This is an important consideration for experiments in which the temperature does not remain constant.
Temperature Dependence of Several Concentration Expressions

concentration temperature
measurements required
expression dependent?

percent composition mass of solute no

(by mass) mass of solution (mass does not change
with temperature)

molarity moles of solute yes

volume of solution (volume changes with
temperature)

molality moles of solute no

mass of solvent (neither mass nor moles
changes with temperature)

mole fraction moles of solute no

moles of solvent (moles does not change
with temperature)
Percent Composition (by mass)
We can consider percent by mass (or weight percent, as it is sometimes called) in two ways:
 The parts of solute per 100 parts of solution.
 The fraction of a solute in a solution multiplied by 100.
We need two pieces of information to calculate the percent by mass of a solute in a solution:
 The mass of the solute in the solution.
 The mass of the solution.
Use the following equation to calculate percent by mass:

Molarity
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Molarity tells us the number of moles of solute in exactly one liter of a solution. (Note that molarity is spelled
with an "r" and is represented by a capital M.)
We need two pieces of information to calculate the molarity of a solute in a solution:
 The moles of solute present in the solution.
 The volume of solution (in liters) containing the solute.
To calculate molarity we use the equation:

Molality
Molality, m, tells us the number of moles of solute dissolved in exactly one kilogram of solvent. (Note that
molality is spelled with two "l"'s and represented by a lower case m.)
We need two pieces of information to calculate the molality of a solute in a solution:
 The moles of solute present in the solution.
 The mass of solvent (in kilograms) in the solution.
To calculate molality we use the equation:

Mole Fraction
The mole fraction, X, of a component in a solution is the ratio of the number of moles of that component to the
total number of moles of all components in the solution.
To calculate mole fraction, we need to know:
 The number of moles of each component present in the solution.
The mole fraction of A, XA, in a solution consisting of A, B, C, ... is calculated using the equation:

To calculate the mole fraction of B, XB, use:

Relation between molarity (M) and molality (m)

Molality (m) = Molarity / ( Density - Molarity X molecular mass / 1000 )
Molarity (M) = Molality X density / (1+ Molality X molecular mass / 1000 )
Example, a 0.2 molal ( 0. 2m ) solution of glucose means a solution obtained by dissolving 0.2 mole of
Normality:
There is a relationship between normality and molarity. Normality can only be calculated when we deal with
reactions, because normality is a function of equivalents.
The example below uses potassium hydroxide (KOH) to neutralize arsenic acid. By studying the reaction it is
possible to determine the proton exchange number to determine the normality of the arsenic acid.
Look at the equation H3AsO4 + 2KOH --> K2HAsO4 + 2H2O:
Equivalent weight = molar mass/(H+ per mole)
Equivalent = mass of compound / Equivalent weight
And Normality = (equivalents of X)/Liter
And the part that is of interest to you is that
Normality = molarity x n (where n = the number of protons exchanged in a reaction).
You probably remember that when a hydrogen atom is ionized and loses its electron, you are left with only a
proton. So a hydrogen ion is basically a proton.
Let's assume that we have a 0.25 M solution of H3AsO4 and want to determine the normality of it if it participates
in the reaction
H3AsO4 + 2KOH --> K2HAsO4 + 2H2O
When H3AsO4 is neutralized by KOH, H3AsO4 provides two protons to form 2H2O.
Note that H3AsO4 has three hydrogens, but K2HAsO4 only has one hydrogen. That means that 2 protons were
exchanged,
Again Normality = molarity * n
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Remember that normality of the solution is 0.25 mol H3AsO4 and there were two protons exchanged (2
equivalents/mole)

So, in short, while there is a relationship between the normality of a solution and the molarity of a solution, the
normality can only be determined by examining reaction, determining the proton exchange and multiplying
molarity by that number.
Normality is particularly useful in titrations calculations.
Where N = normality, V = volume, a = the substance on the left of the equation involved in proton exchange,
and b=substance on the right of the equation involved in proton exchange:
N aV a = N b V b
Percentages are easy to calculate because they do not require information about the chemical nature of the
substance. Percentages can be determined as percent by weight or percent by volume.
Solubility
 Solubility of a substance is the maximum amount of the substance that can be dissolved in a
specified amount of a solvent at a given temperature.
 Factors on which solubility depends:
o Nature of solute and solvent
o Temperature
o Pressure
Solubility of a Solid in a Liquid
When a solute is dissolved in a solvent, the following dynamic equilibrium is established.
Solute + Solvent Solution
This equilibrium follows Le Chatelier’s Principle.
 Effect of temperature:
According to Le Chatelier’s principle, in a nearly saturated solution, if the dissolution process is −
 Endothermic (ΔsolH > 0), then the solubility will increase with the increase in temperature
 Exothermic (ΔsolH < 0), then the solubility will decrease with the increase in temperature
 Effect of pressure:
 Pressure has no significant effect on the solubility of solids in liquids.
 Reason − Solids and liquids are negligibly affected by pressure as they are highly incompressible.
Solubility of a Gas in a Liquid
 The solubility of gases in liquids increases with the increase in pressure.
 Henry’s law − The solubility of a gas in a liquid is directly proportional to the pressure of the gas.
Or
The partial pressure of a gas in vapour phase (p) is directly proportional to the mole fraction of the gas (x) in the
solution, i.e.,
p = KH x
Where, KH = Henry’s law constant
The plot of the partial pressure of HCl vs. its mole fraction in a solution of cyclohexane is given below.

 Some important applications of Henry’s law

(i) Bottles are sealed under high pressure to increase the solubility of CO 2 in soft drinks and soda water.
(ii) Henry’s law states that the solubility of gas increases with an increase in pressure. Therefore, when a scuba
diver dives into the sea, the increased sea pressure causes the nitrogen present in air to dissolve in his blood in
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great amounts. As a result, when he comes back to the surface, the solubility of nitrogen again decreases and
the dissolved gas is released, leading to the formation of nitrogen bubbles in the blood. This results in the
blockage of capillaries and leads to a medical condition known as ‘bends’, which are painful and dangerous to
life. Hence, the oxygen tanks used by scuba divers are filled with air and diluted with helium to avoid bends.
(iii) The concentration of oxygen is low in the blood and tissues of climbers or people living at high altitudes. This
is because at high altitudes, the partial pressure of oxygen is less than that at ground level. Low blood oxygen
causes climbers to become weak and prevents them from thinking clearly. These are symptoms of ‘anoxia’.
 Effect of temperature
Solubility of gases in liquids decreases with the increase in temperature.
Vapour Pressure of Liquid Solutions
 Let p1, p2 = Partial vapour pressure of two volatile components 1 and 2 of a mixture

= Vapour pressure of pure components 1 and 2

x1, x2 = Mole fractions of the components 1 and 2
ptotal = Total vapour pressure of the mixture
Raoult’s law
For a solution of volatile liquids, the partial vapour pressure of each component in the solution is directly
proportional to its mole fraction.

p1∝ x1
That is, for component 1,

And,
For component 2,

According to Dalton’s law of partial pressures,

 From the above equation, it can be concluded that:

o can be related to mole fraction of any one component.

o varies linearly with x2.

o Depending upon and , increases or decreases with the increase of x1.

 The plot of vapour pressure and mole fraction of an ideal solution at
constant temperature is shown below.

Here, maximum value of

Minimum value of

Here, because it is assumed that component 1 is less volatile than

component 2.
 The component of vapour phase in equilibrium with the solution is
determined by the partial pressures of the components.
Let y1, y2 = Mole fractions of the components 1 and 2 respectively in the
vapour phase
According to Dalton’s law of partial pressures, In general, we can write

Raoult’s Law as a Special Case of Henry’s Law

 According to Raoult’s law, the vapour pressure of a volatile component in a given solution is
 According to Henry’s law, the partial vapour pressure of a gas (the component is so volatile that it exists
as gas) in a liquid is
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p = KH x
 It can be observed that in both the equations, the partial vapour pressure of the volatile component

varies directly with its mole fraction. Only the proportionality constantsKH and are different. Thus,

Raoult’s law becomes a special case of Henry’s law in which KH is equal to .

Vapour Pressure of Solutions of Solids in Liquids
 When a non-volatile solute is added to a solvent, the vapour pressure of the liquid decreases.
 Reason: The number of solvent molecules on the surface decreases and as a result, number of solvent
molecules escaping from the surface decreases.
 Raoult’s law in general form: For any solution, the partial vapour pressure of each volatile component in
the solution is directly proportional to its mole fraction.
 Let us take a binary solution made by dissolving a non-volatile solute in a solvent. Since the solute is non-
volatile, only the solvent molecules contribute to vapour pressure.

Let = Vapour pressure of the solvent

= Vapour pressure of the solvent in pure state

x1 = Mole fraction of the solvent
Then, according to Raoult’s law,

Here, the proportionality constant is equal to the vapour pressure of the solvent in pure state.
The plot of vapour pressure vs. mole fraction of the solvent, which is linear, is shown below.

Idealand Non-Ideal Solutions

IdealSolution
 Solutions which obey Raoult’s law over the entire range of concentrations
 For ideal solution:
 Enthalpy of mixing of the pure components to form the solution,
Δmix H
=0
 Volume of mixing, Δmix V = 0
 An ideal solution will be formed when intermolecular forces of attraction between the molecules of solute
(A − A) and those between the molecules of solvent (B − B) are nearly equal to those between solute and
solvent molecules (A − B).
 Examples: n-Hexane and n-heptane, bromoethane and chloroethane, benzene and toluene
Non-Ideal Solutions
 Solutions which do not obey Raoult’s law over the entire range of concentration
 The vapour pressure of a non-ideal solution is either higher or lower than that predicted by Raoult’s law.
 Positive deviation from Raoult’s law − When vapour pressure of solution is higher
 Negative deviation from Raoult’s law − When vapour pressure of solution is lower
 Solution showing positive deviation from Raoult’s law
 The plot of vapour pressure of two component solutions as a function of mole fraction is shown below.
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 The intermolecular forces of attraction between solute-solvent molecules are weaker than those between
solute-solute molecules and solvent-solvent molecules. Therefore, solvent molecules can easily escape,
resulting in increase in vapour pressure.
 Example: Ethanol and acetone mixture.
 Solution showing negative deviation from Raoult’s law
 The plot of vapour pressure of two component solutions as a function of mole fraction is shown below.

 The intermolecular forces of attraction between solute-solute molecules and solvent-solvent molecules
are weaker than those between solute-solvent molecules. This results in the decreasing of vapour
pressure.
 Example − Chloroform and acetone mixture
The intermolecular attractive forces between solute-solvent molecules increase due to the formation of H-bond.

Azeotropes
 Binary mixtures which have the same composition in liquid and vapour phase, and have constant boiling
points
 Not possible to separate the components by fractional distillation
 Two types − Minimum boiling azeotrope
Maximum boiling azeotrope
 Minimum boiling azeotrope − Solution showing a large positive deviation from Raoult’s law of specific
composition
Example: Ethanol-water mixture containing ethanol approximately 95% by volume
 Maximum boiling azeotrope − Solution showing a large negative deviation from Raoult’s law at
specific composition
Example: Nitric acid-water mixture containing 68% nitric acid and 32% water by mass
The boiling point of this azeotrope is 393.5 K.
Colligative Properties and Determination of Molar mass
 Properties which depend upon the number of solute particles present in the solution irrespective of their
nature, relative to the total number of particles present in the solution
 Examples: Relative lowering of vapour pressure of the solvent, depression of freezing point of the
solvent, elevation of boiling point of the solvent, osmotic pressure of the solution
Relative Lowering of Vapour Pressure
 Relative lowering of vapour pressure is equal to the mole fraction of the solute.
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i.e.,
Where,

= Vapour pressure of the solvent

p1 = Vapour pressure of the solution
x2 = Mole fraction of the solute

However,
Where, n2 = Number of moles of solute
n1 = Number of moles of solvent

Now,
For dilute solution, n1 >> n2

Therefore,

Or,

Or,
Where,
w2 = Mass of solute
M2 = Molar mass of solute
w1 = Mass of solvent
M1= Molar mass of solvent
Elevation of Boiling Point
 With addition of non-volatile solute, vapour pressure decreases and hence, boiling point increases.

 Here, = Elevation of boiling point

Where,
Tb = Boiling of solution

 ΔTb ∝ m (for dilute solution)

= Boiling point of solvent

⇒ΔTb = Kbm
Where,
m = Molality
Kb = Proportionality constant known as Boiling Point Elevation Constant or Molal Elevation Constant or
Ebullioscopic constant (Unit = K kg mol−1)
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However,
Where,
w2 = Mass of solute
M2 = Molar mass of solute
w1 = Mass of solvent

Now,

Or,
Depression of Freezing point
 With addition of non-volatile solute, vapourpressure decreases, which leads to a decrease in freezing
point.

 Here, = Depression of freezing point

Where,

= Freezing point of solvent

Tf= Freezing point of solution

ΔTf ∝ m
 For dilute solution (ideal solution),

⇒ΔTf = Kf m
Where,
m = Molality
Kf = Proportionality constant known as Freezing Point Constant or Molal Depression Constant or Cryoscopic
constant (Unit = K kg mol−1)

However,
Where,
w2 = Mass of solute
M2 = Molar mass of solute
w1 = Mass of solvent

Now,

Or,
 The value of Kb and Kf can be determined by the following relations:
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Where,
M1 = Molar mass of the solvent
R = Gas constant
ΔvapH = Enthalpy of vaporisation
ΔfusH = Enthalpy of fusion
Osmosis and Osmotic Pressure
 The process of flow of solvent molecules from pure solvent to solution or from solution of lower
concentration to solution of higher concentration through a semi-permeable membrane is called osmosis.
 The pressure required to just stop the flow of solvent due to osmosis is called osmotic pressure (π) of the
solution.
 The osmotic pressure π has to be applied to the solution to prevent osmosis.

 For dilute solution, osmotic pressure is directly proportional to the molarity C of the solution at a given
temperature T.
That is, π = CRT (R = Gas constant)

Where,
n2 = Number of moles of solute
V= Volume of the solution in litres

Again,
Where, w2 = Mass of the solute
M2 = Molar mass of the solute

Now,

Or,

Or,
Now, osmosis does not occur between two isotonic solutions.

Isotonic solutions − Solutions having same concentration of solute These solutions have same osmotic

pressure.
 Hypotonic solution − Solution having a low concentration of solute relative to another.
 Hypertonic solution − Solution having a high concentration of solute relative to another.
Reverse Osmosis and Water purification
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 If the pressure applied on the solution is greater than its osmotic pressure, then the direction of osmosis
is reversed i.e., the solvent starts passing from solution to solvent. The phenomenon is called reverse
osmosis.
 This phenomenon is used in purification (desalination) of sea water.

 Colligative property ∝ 1/ molar mass of solute

Abnormal Molar Masses

 Due to association or dissociation of molecules, the molar mass of a substance calculated from its
colligative property is either lower or higher than the expected or normal value. Such molar mass is
called abnormal molar mass.
Dissociation:
KCl K+ + Cl−
Association:
2CH3COOH (CH3COOH)2

 To account for the extent of dissociation or association, van’t Hoff introduced a factor i, known as the
van’t Hoff factor.

 Value of i:
For association, i < 1
For dissociation, i > 1
No association or dissociation, i = 1
 Modified equations for colligative properties after inclusion of van’t Hoff factor
 Relative lowering of vapour pressure of solvent,

 Elevation of boiling point, ΔTb = iKbm

 Depression of freezing point, ΔTf = iKfm
 Osmotic pressure of solution, π = in2RT/V
Degree of dissociation

Degree of dissociation = No. of moles of the substance dissociated / Total no of moles of the
substance taken
Suppose a molecule of an electrolyte gives ‘m’ ions after dissociation. Then if we starts with one mole of the
solute, and 
is the degree of dissociation, then at equilibrium

No. of moles of solute left undissociated = 1 - 

No. of moles of ions formed = m
Total no of moles of partical = 1 - m
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Van't Hoff factor = Observed no of moles of solute / Normal no of moles of solute

i = 1 - m

or  = i – 1 / m – 1

But i = Normal Molar mass / Observed molar mass

Knowing the value of ‘i’, degree of dissociation can be calculated.

Degree of association

Degree of association = No. of moles of the substance associated / Total no of moles of the
substance taken

Suppose ‘nA’ simple molecule of the solute associate to form the associated molecule ‘A n’.

nA = An

if we start with one mole of A and is the degree of association, the concentration of the species
after association is

[An] =  / n
[A] = 1 - 
Total no of moles after dissociation = 1 - /n

Van't Hoff factor = Observed no of moles of solute / No of moles of solute assuming no association

i = 1 - /n/

or  = i – 1 / (1/n – 1)
Knowing the value of ‘i’, degree of association can be calculated.