Physical Chemistry

Solutions
(Lecture-01)

Concepts Covered in the Class:

• Solute and Solvent
• Types of Solutions
• Different Concentration Terms

Our first Chapter

• This chapter on "Solutions" will cover key topics like
Concentration Terms, Vapour Pressure, Raoult's Law,
Ideal and Non -Ideal Solutions, Colligative Properties,
and Henry's Law.

Solution
• A solution is a homogeneous (uniform) mixture
formed when two or more non -reacting substances
are combined.

[1]
• "Homogeneous" means the composition is the same
throughout the entire mixture, for example, when
sugar is completely dissolved in water.

• A key feature of a homogeneous solution is that any

sample taken from it, no matter how small, will have
the exact same concentration.

[2]
Properties of solution
• A solution exhibits the properties of all its individual
components.
• The particles of the components in a solution are
extremely small, with a size of less than 1 nanometer.
• Every solution contains one solvent and one or more
solutes.

How to identify solute and solvent in a

solution?
• The **solute** is the substance that gets dissolved.
The **solvent** is the substance that does the
dissolving and determines the physical state (solid,
liquid, or gas) of the final solution.
• **Criterion 1 (Different Phases):** When
components are in different states (e.g., solid and
liquid), the solvent is the one that has the same
physical state as the final solution.
• **Criterion 2 (Same Phase):** When all components
are in the same state (e.g., two liquids), the solvent
is the substance present in the larger amount (by
moles).

[3]
 Chemistry
Solutions
(Lecture-01)

Concepts Covered in the Class:

• Typ es of S olution
• Concentration Terms
• Mol arity

Types of solution in terms of number of

constituents
• S ol utions are cl assified by their total number of
comp onents: Binary (1 sol vent + 1 solute), Ternary
( 1 sol vent + 2 sol utes), and Quaternary ( 1 sol vent +
3 sol utes).

Types of solution in terms of its physical state

• A solution adop ts the p hysical state of its sol vent,
categoriz ed into three main typ es: Gaseous, Liquid,
and S olid solutions.

[1]
Gaseous Solution
• The solvent is alw ays a gas, but the sol ute can be a
gas (e.g. , Air: 80 % N ₂ + 20 % O ₂), a liquid (e. g.,
chl oroform in nitrogen), or a solid ( e. g. , camp hor in
nitrogen).

Liquid Solution
• The solvent is alw ays a liquid, w hile the sol ute can
be a gas (e.g. , oxygen in w ater), a liquid (e. g. ,
ethanol in w ater), or a solid ( e. g. , glucose in w ater).

[2]
Solid Solution
• The solvent is a solid, accommodating solutes that
are gas ( e.g., hydrogen in p al l adium), liquid ( e. g. ,
mercury amal gams), or solid ( e. g. , copp er dissol ved
in gol d).

Metal amalgam :-
• An amal gam is a sp ecific type of solid sol ution w here
liquid mercury ( Hg) acts as the solute and a solid
metal acts as the sol vent.
• Common exampl es incl ude Sodium amal gam (Na -Hg)
and Zinc amalgam ( Zn -Hg).

Alloys : (Solid Soln)

• All oys are sol id solutions w here both the sol ute and
the solvent are solid metal s (e.g., Brass, Bronze, and
German Sil ver all use solid Copp er as the sol vent).

[3]
Concentration Terms
• These terms define the exact composition and
p rop ortion of sol ute and solvent p resent in a given
sol ution.
• The concentration value changes w henever the
amount of either the solute or the sol vent is al tered.

Molarity (M)
• Mol arity defines the number of moles of solute
dissol ved p er 1 litre ( or 1000 mL ) of sol ution.
• Mol arity = ( No. of moles of sol ute) / (Volume of
sol ution in L )
• Mol arity depends on temp erature because it invol ves
volume; as temperature increases, volume exp ands,
causing mol arity to decrease. (F or examp le, reading
"0.1 M NaCl solution" simpl y transl ates to the English
statement: 0.1 mol es of NaCl are dissol ved in 1 L of
sol ution).

[4]
 Chemistry
Solutions
(Lecture-03)

Concepts Covered in the Class:

• Mol arity
• Mol ality
• Mole F raction

Unit of Molarity
• Concentration is exp ressed in terms of moles p er litre
( Mol /L t), Mol ar, or simp l y M.

Resultant Molarity during dilution

• Moles of sol ute remain constant during dilution, even
as the total volume increases and the mol arity
decreases.
• Formula : M₁V₁ = M ₂V₂

[1]
Resultant Molarity during mixing of solutions of
same solute
• When mixing mul tipl e sol utions containing the
identical solute, the total moles and volumes are
added together.
• Formula: M_net = ( M ₁V₁ + M ₂V₂) / (V ₁ + V ₂) = (∑
M_iV_i) / ( ∑ V_i)

[2]
Molarity of constituent ions of solute in
solution
• The concentration of individual ions in a sol ution
depends directl y on the stoichiometry of the
dissol ved compound.
• General ionic formul a: F or a comp ound M ₓ N_y →
xM^{y+} + yN^{x -} with an initial concentration C,
the ion concentrations are [M^{y+}] = xC and [N^{x -
} ] = yC.
• Exampl e: A C mol ar solution of Ba ₃(PO₄)₂ yiel ds 3C
M of Ba² ⁺ ions and 2C M of PO ₄³⁻ ions.

Molality(m)
• Measures the number of moles of sol ute dissolved per
1 kg of solvent and is compl etel y indep endent of
temperature.
• Mol ality ( m) = ( mol of solute) / (w t of sol vent in
K g)
• In pl ain English: A "0. 2 m NaCl " sol ution simpl y
means there are exactl y 0. 2 moles of NaCl dissol ved
in 1 kg of sol vent.

[3]
Mole Fraction (X)
• Rep resents the ratio of the number of moles of one
specific comp onent to the total moles in the mixture.
• X_A = n_A / ( n_A + n_B + n_C)
• The sum of the mol e fractions for all comp onents in
any sol ution is al w ays exactly equal to 1 (X_A + X_B
+ X_C = 1).

For a binary solution

• Consists of onl y tw o comp onents ( sol ute and
sol vent), meaning X_sol ute + X_sol vent = 1. Like
mol ality, it is independent of temp erature.
• The ratio of their mole fractions strictl y equals the
ratio of their actual mol es ( X_A / X_B = n_A /
n_B).
• Practical interp retation: F or an aqueous urea solution
w here X_urea = 1/7, it implies the mixture contains
1 mol e of urea for every 6 mol es of w ater.

[4]
 Chemistry
Solutions
(Lecture-04)

Concepts Covered in the Class:

• Interconversion of Mol arity and Mol ality
• Percentage ( %) Concentration Terms

Interconversion of Molarity and Molality

• Converting betw een mol arity (volume -based) and
mol ality ( mass -based) requires knowing the density
of the sol ution.
• K ey formul a: Mol ality = ( Mol arity × 10 00) / [(1000
× density in g/mL ) - ( Molarity × Mol ar mass of
sol ute in g)]

Percentage Concentration Terms

• % w /w ( Weight by Weight): Rep resents the weight
of the solute (in grams) p resent in 100 grams of the
total solution.

[1]
• F ormul a: % w/w = (w eight of sol ute / w eight of
sol ution) × 100
• This is a temperature -indep endent concentration
term because it relies entirel y on mass, which does
not change with temperature.

% w/V
• % w /V ( Weight by Volume): Rep resents the weight
of the sol ute (in grams) present in 100 mL of the
sol ution.
• F ormul a: % w/V = (weight of solute / volume of
sol ution in mL) × 100
• This is a temperature -dependent concentration term
because it invol ves vol ume, w hich exp ands or
contracts with temp erature changes.

[2]
 Chemistry
Solutions
(Lecture-05)

Concepts Covered in the Class:

• % Concentration Terms
• Parts concentration Terms
• S trength of sol ution

Parts concentration Terms

• These concentration metrics are sp ecificall y used for
highly diluted sol utions w here the sol ute amount is
excep tionall y small.
• 1) Parts per Mil lion (pp m) = ( weight of sol ute in g
/ weight of solution in g) × 10 ⁶
• This measurement is entirel y temp erature -
independent because it rel ies strictl y on mass, not
volume.

[1]
Parts Per Billion (ppb)
• This metric is used for even more highly dil uted
sol utions to exp ress the mass of solute per one billion
p arts of the total solution.
• pp b = (w eight of sol ute in g / w eight of sol ution in
g) × 10⁹
• S imil ar to p pm, ppb is a temp erature -independent
concentration term.

[2]
 Chemistry
Solutions
(Lecture-06)

Concepts Covered in the Class:

• % Volume by Volume ( % V/V)
• S trength of a sol ution
• F ormality (F )
• Volume S trength of Hydrogen Peroxide ( H ₂O ₂)
• Percentage L abell ing of Oleum

% V/V
• Rep resents the volume of liquid solute divided by the
total vol ume of the solution, expressed as a
p ercentage.
• % V/V = ( volume of sol ute in mL ) / ( vol ume of
sol ution in mL) × 100
• F or any gaseous mixture ( like air), the % V/V is
directl y treated as the mole p ercentage.

[1]
Strength of a solution
• Defined as the w eight of solute (in grams) dissol ved
p er litre of the total sol ution; this value changes
with temp erature.
• S trength = weight of solute (g) / vol ume of sol ution
(L ) ( expressed in g/L).
• Do not confuse strength with the density of the
sol ution (w hich measures the mass of the entire
sol ution p er unit vol ume). S trength can be easil y
converted to mol arity by dividing it by the sol ute's
mol ar mass.

Formality (F)
• A concentration unit used specificall y for ionic solids,
rep resenting the number of gram formula masses
dissol ved p er litre of sol ution.
• F ormality (F ) = (given mass of ionic sol ute / formul a
mass) / ( volume of sol ution in L )
• The term "formul a mass" for an ionic comp ound is
cal cul ated exactl y the same w ay as mol ar mass.

[2]
Volume Strength of Hydrogen Peroxide (H ₂O₂) solⁿ
• Defined as the total vol ume of O ₂ gas produced at
S TP up on the complete decomp osition of 1 mL of
H₂O₂ sol ution.

• K ey formul as linking Vol ume S trength ( V.S. ) to

Mol arity ( M): V.S. = 11. 35 × M ( at S TP: 0°C, 1 bar)
and V.S . = 11.2 × M ( at NTP: 0 °C, 1 atm).

Percentage labelling of Oleum

• Ol eum is fuming sulfuric acid ( a mixture of H ₂SO₄
and free S O ₃). Its p ercentage l abel ( e.g. , 10 9%)
indicates the total grams of H ₂SO ₄ obtained w hen
enough w ater is added to a 100 g sampl e to react w ith
all the free SO ₃.
• % L abelling = ( 100 - x) + ( x / 80 ) × 98 (w here x
is the mass of free SO ₃ in a 100 g sample).
• The percentage val ue exceeding 100 % (e. g., the "9"
in 109%) is exactl y equal to the mass of w ater in
grams required to convert the free SO ₃ completel y
into new H₂ SO₄.

[3]
 Chemistry
Solutions
(Lecture-07)

Concepts Covered in the Class:

• Percentage l abelling of Ol eum
• Normality
• Vap our Pressure of Pure Liquid

Percentage labelling of Oleum

• Ol eum (fuming sul furic acid) is a mixture of H ₂S O₄
and free SO ₃; its p ercentage label tel ls you the total
mass of H ₂SO ₄ formed w hen w ater is added to a 10 0g
sampl e to convert all free SO ₃ into H ₂SO ₄.
• % F ree S O ₃ = (( % l abelling − 100 ) × 80 ) / 18
• The theoretical l abelling val ue ranges from a
minimum of 100 % (z ero free S O ₃) to a maximum of
122. 5% (p ure S O ₃).

[1]
How to calculate the new % labelling of oleum
on addition of insufficient water
• Adding the exact required amount of w ater converts
all free SO ₃ to H₂SO₄, w hil e adding excess w ater
yiel ds a regul ar H ₂SO ₄ sol ution with l eftover w ater.
• If insufficient w ater is added, some free SO ₃ remains
unreacted, meaning the resul ting mixture is stil l an
ol eum sampl e.
• The new p ercentage l abelling is determined by
cal cul ating the remaining free SO ₃ rel ative to the
new total mass of the sample.

Normality (N)
• Normality is a temperature -dependent concentration
term defined as the number of gram equivalents of
sol ute present p er l itre of sol ution.
• Normality = (number of gram equivalents of solute)
/ ( volume of sol ution in L ) O R Normality = Mol arity
× n -factor
• The "n-factor" is determined based on the substance
typ e: it is the basicity for acids, the acidity for

[2]
 bases, and the total cationic or anionic charge for
sal ts.

Resultant normality during dilution

• When a sol ution is dil uted by adding w ater, the total
number of equival ents of the solute remains strictly
constant.
• N₁V₁ = N₂V₂

Resultant normality during mixing

• When mul tipl e solutions of the same substance are
mixed together, the final normal ity is the sum of
their individual equival ents divided by the total
combined vol ume.
• N_final = ( N ₁V₁ + N₂V₂ + N₃V₃) / (V ₁ + V₂ + V ₃)

Vapour Pressure of Pure Liquid

• Molecules at the surface of a l iquid are l ess stable
and have higher energy compared to molecul es in the
bul k, causing them to escape and form vapour.
• Vap our pressure is the pressure exerted by the
maximum (saturated) amount of vap ours in an

[3]
 encl osed sp ace w hen the rate of evap oration p erfectl y
equals the rate of condensation.
• The equil ibrium constant (Kp ) for this p hase change
is equal to the vap our p ressure, and it dep ends
excl usivel y on the temp erature.

[4]
 Chemistry
Solutions
(Lecture-08)

Concepts Covered in the Class:

• Vap our Pressure of p ure L iquid
• Vap our Pressure of sol ution

Ek Line Angrezi ki
• Mol arity ( M) and mol al ity ( m) measure moles of
sol ute p er 100 0 mL of solution and 10 00 g of sol vent,
respectivel y.
• Mole fraction ( 𝑎/𝑏) defines '𝑎' mol es of solute within
'𝑏' total moles.
• O ther terms (like %, pp m, pp b, and g/L ) express
sol ute mass or volume rel ative to the total sol ution.

[1]
Why V.P of pure Liquid depends only on
temperature?
• Vap oriz ation is an endothermic process; raising the
temperature increases the equilibrium constant ( 𝐾𝑝 )
and thus the vap our pressure.
• At higher temperatures, a l arger fraction of molecules
acquires the minimum kinetic energy ( 𝐸𝑜 ) required to
escape the liquid surface.

K.B. Conclusions
• Vap our p ressure is determined excl usivel y by
temperature and increases exponentiall y, not l inearl y.
• It is compl etely independent of the liquid's quantity
and the container's shap e, provided equil ibrium is
reached.

[2]
 𝑉.𝑃𝑇2 Δ𝐻 1 1
• log = [ − ]
𝑉.𝑃𝑇1 2.303𝑅 𝑇1 𝑇2

Vapour Pressure of two liquids at same

temperature
• Vap our p ressure is inversely p rop ortional to the
intermolecul ar forces of attraction in the liquid
p hase.
• S tronger attractive forces decrease the molecules'
tendency to leave the surface, resul ting in l ower
vap our p ressure.

[3]
Forces between molecules
• S trength O rder: Ionic F orce > Ion -Dip ol e > Hydrogen
Bond > Dipole -Dip ole > Dip ol e -Induced Dipol e > Van
der Waals.
• Pol ar mol ecules generall y exert stronger attractive
forces than non -pol ar molecul es.
• F or non -p ol ar substances, the force of attraction
increases with greater molecul ar siz e, surface area,
and mol ecul ar w eight.

[4]
 Chemistry
Solutions
(Lecture-09)

Concepts Covered in the Class:

• Vap our Pressure of sol utions

Vapour Pressure of a Solution of non -volatile

solute in a volatile solvent
• Adding a non -vol atil e sol ute ( one that does not
evaporate) to a vol atil e sol vent l owers the overall
vap our p ressure of the solution ( 𝑃𝑠 ) comp ared to the
p ure sol vent ( 𝑃∘ ).

[1]
• This decrease ( 𝑃𝑠 < 𝑃∘ ) hap pens because solute
p articl es occupy surface area —leaving fewer solvent
molecules to escap e —and because new sol ute -solvent
interactions restrict evap oration.

Raoult's Law
• The l aw states that the p artial vap our p ressure of
any comp onent in a solution is directl y prop ortional
to its mol e fraction within that sol ution.
• Formula: 𝑃𝑠 = 𝑃∘ 𝑋𝑠𝑜𝑙𝑣𝑒𝑛𝑡
• This p rincipl e defines the Relative L owering of Vap our
Pressure ( RL VP), showing that the rel ative drop in
p ressure equals the mol e fraction of the added sol ute:
(𝑃∘ − 𝑃𝑠 )/𝑃∘ = 𝑋𝑠𝑜𝑙𝑢𝑡𝑒 .

[2]
V.P of a solution of a volatile solute in a volatile
solvent
• F or comp letely miscible (mixabl e) sol utions w here
both liquids are vol atil e, the total vap our pressure is
the sum of their p artial p ressures, provided the
intermolecul ar forces ( A -A, B -B, and A -B
interactions) are equal.

• Total Pressure Formula: 𝑃𝑇 = 𝑃𝐴∘ 𝑋𝐴 + 𝑃𝐵∘ 𝑋𝐵

• Because the sum of mol e fractions is 1 ( 𝑋𝐴 + 𝑋𝐵 =
1), you can easil y cal cul ate total p ressure using
just one mol e fraction, for examp le: 𝑃𝑇 = 𝑃𝐵∘ + 𝑋𝐴 (𝑃𝐴∘ −
𝑃𝐵∘ ).

[3]
 Chemistry
Solutions
(Lecture-10)

Concepts Covered in the Class:

• Vap our Pressure of sol utions
• Evaporation and Condensation

RLVP (Relative Lowering of Vapour Pressure)

• The standard formul a rel ates the rel ative low ering of
vap our p ressure to the mol e fraction of the sol ute:
(𝑃0 − 𝑃𝑠 )/𝑃0 = 𝑋solute .
• A shortcut formul a useful for direct cal cul ations links
p ressure drops to the mol e ratio: (𝑃0 − 𝑃𝑠 )/𝑃𝑠 =
𝑛solute /𝑛solvent .

How to calculate the composition of vapour

phase ( 𝑌𝐴 , 𝑌𝐵 )
• According to Dal ton's L aw , a component's mole
fraction in the vap our p hase (𝑌𝐴 ) is its p artial
p ressure divided by the total p ressure.

[1]
• Formula: 𝑌𝐴 /𝑌𝐵 = (𝑃𝐴0 𝑋𝐴 )/(𝑃𝐵0 𝑋𝐵 )
• This equation all ows you to cal cul ate vap our
comp osition if the liquid mol e fractions and p ure
vap our p ressures are known.

Distillation (Ideal Solution)

• In fractional distill ation, vap our from one stage is
condensed to form the l iquid in the next,
p rogressivel y enriching the mixture with the more
vol atil e comp onent.
• The mole fraction of comp onent A in the l iquid p hase
of container 2 is exactl y equal to its mole fraction
in the vap our p hase of container 1(𝑋𝐴,2 = 𝑌𝐴,1 ).

[2]
For nth container
• By rep eatedl y appl ying the distill ation step , a
general ized formul a determines the final vap our
comp osition after 𝑛 stages.

• Formula: 𝑌𝐴,𝑛 /(1 − 𝑌𝐴,𝑛 ) = (𝑃𝐴0 /𝑃𝐵0 )𝑛 × (𝑋𝐴,1 /(1 − 𝑋𝐴,1 ))

Case of evaporation
• Evaporation in a cl osed system involves gradual ly
increasing the vol ume ( e. g. , p ull ing a piston upw ard
in steps) to force the transition from liquid to
vap our.

[3]
Q. 1 Vap. Pressure of soln when first drop of
vapour formed.
• This marks the "bubble p oint," w here vap oriz ation
just begins and the bul k liquid composition is
effectivel y unchanged .
• Formula: 𝑃𝑇 = 𝑃𝐴0 𝑋𝐴 + 𝑃𝐵0 𝑋𝐵

Q. 2 What is the composition of A and B in first

drop of vapour formed?
• The comp osition of the initial vap our bubbl e is
directl y determined from the original l iquid p hase
mole fractions.
𝑌𝐴 𝑃𝐴0 𝑋
• Formula: (1−𝑌𝐴 )
= ( 0 ) × ((1−𝑋𝐴 ))
𝑃𝐵 𝐴

Q. 3 What is the composition of Last drop of

Liquid remained ?
• At the "dew point," al most all liquid has evap orated,
so the original bul k liquid mol e fraction now equals
the total vap our mole fraction (𝑋𝐴 ≈ 𝑌𝐴′ ).

[4]
• The comp osition of the tiny remaining l iquid drop
(𝑋𝐴′ ) is cal cul ated backw ard using this newl y
established vap our comp osition.

Q. 4 What will be the V.P of Last drop of Liq.

remained?
• The total system p ressure right before the final drop
evaporates is found by pl ugging the newl y cal cul ated
liquid mole fractions (𝑋𝐴′ , 𝑋𝐵′ ) into the p ressure
equation.
• Formula: 𝑃𝑇 = 𝑃𝐴0 𝑋𝐴′ + 𝑃𝐵0 𝑋𝐵′

[5]
 Chemistry
Solutions
(Lecture-11)

Concepts Covered in the Class:

• Vap our Pressure of sol utions
• Evaporation and Condensation
• Ideal and Non -Ideal Solution

Case of Condensation
• When external pressure is ap plied to a cl osed
container of vap or ( e. g. , via a p iston), the volume
decreases until the vap or begins to condense into
liquid, starting with the first drop.
• The comp osition of this newl y condensed liquid
differs from the original vapor mixture because each
comp onent condenses at a different rate dep ending
on its respective p ure vap or p ressure.

[1]
Mixture of two volatile liquids both are
immiscible (मिलें ग े नहीं)
• Because the liquids do not dissol ve in one another,
each behaves as a pure l iquid ( 𝑋𝐴 = 1 and 𝑋𝐵 = 1 ),
meaning the total vap or p ressure is simply the sum
of their p ure vap or p ressures: 𝑃𝑇 = 𝑃𝐴∘ + 𝑃𝐵∘ .
• The ratio of the masses of the tw o components in
the vap or p hase is given by: 𝑊𝐴 /𝑊𝐵 = (𝑃𝐴∘ 𝑀𝐴 )/(𝑃𝐵∘ 𝑀𝐵 )
• S ince the total vap or p ressure is alw ays higher than
the vap or pressure of either individual liquid, the
mixture will boil at a l ower temp erature than either
p ure comp onent (w henever 𝑃𝑇 reaches 1 atm ).

[2]
 Chemistry
Solutions
(Lecture-12)

Concepts Covered in the Class:

• Azeotropes
• Ideal and Non Ideal Solutions
• Colligative Properties

Ideal Solutions
• Solutions that strictly obey Raoult’s Law over the entire range
of composition, formed when new A-B interactions exactly
match the strength of the original A-A and B-B interactions.
• P_T = P_A°X_A + P_B°X_B
• The mixing process involves no heat or volume change (ΔH_mix
= 0, ΔV_mix = 0), but mixing randomness increases entropy
(ΔS_mix > 0) making it a spontaneous process (ΔG_mix < 0).

[1]
Example
• Ideal solutions typically form between molecules with similar
structures and intermolecular forces.
• Common examples include Hexane + Heptane, Benzene +
Toluene, and Ethyl bromide + Ethyl Iodide.

Hexane and Heptane

• Both liquids are non-polar and interact strictly via Van der Waals
forces, allowing them to mix perfectly without altering
interaction strengths.

Non-Ideal Solution
• Solutions that do not obey Raoult’s Law over the entire
concentration range because the new molecular interactions
differ in strength from the original ones.
• P_T ≠ P_A°X_A + P_B°X_B

Positive Deviation
• Occurs when the newly formed A-B interactions are weaker than
the pure A-A or B-B interactions, causing a higher-than-
expected vapor pressure.

[2]
• Because pure bonds are harder to break than the new bonds are
to form, the mixing absorbs heat (ΔH_mix > 0) and expands in
volume (ΔV_mix > 0).

Example
• Examples of positively deviated mixtures include Ethanol +
Cyclohexane, Ethanol + Acetone, and CCl4 + Benzene.

Ethanol + Cyclohexane

• Adding cyclohexane breaks apart and reduces the extent of

strong hydrogen bonding between pure ethanol molecules, leading
to a positively deviated system.

Ethanol + Water

[3]
• Mixing ethanol and water results in an overall hydrogen bonding
structure that is weaker than the bonding found in the pure
individual components.

Ethanol + Acetone
• Acetone molecules disrupt and reduce the strong hydrogen bond
networks naturally present in pure ethanol.

CCl4 + Benzene
• The resulting Van der Waals forces between the mixed non-polar
molecules are weaker than those in their pure states, creating
positive deviation.

Negative Deviation
• Occurs when the newly formed A-B interactions are stronger
than the original A-A and B-B interactions, keeping molecules
tightly bound and lowering total vapor pressure.
• This stronger attraction releases heat (ΔH_mix < 0) and
decreases overall volume (ΔV_mix < 0).

[4]
Example
• Common negative deviation systems include Chloroform +
Acetone, Chloroform + Benzene, and Strong Acids + Water.

Chloroform CHCl3 + Acetone CH3COCH3

• Mixing these polar molecules creates a new, strong intermolecular
hydrogen bond between them, limiting evaporation and driving
negative deviation.

Chloroform + Benzene
• Intermolecular interactions increase significantly due to a strong
attraction between the hydrogen atom in chloroform and the
dense pi-electron cloud of benzene.

[5]
HCl + water & HNO3 + H2O
• Strong acids act as strong electrolytes in water, existing largely
as non-volatile ions rather than intact molecules.
• Because these ions do not evaporate, the overall vapor pressure
of the solution heavily decreases.

[6]
 Chemistry
Solutions
(Lecture-13)

Concepts Covered in the Class:

• Azeotropes
• Ideal and Non-Ideal Solutions
• Colligative Properties

Learn Acetone + Aniline

• Acetone (polar) and aniline undergo distinct intermolecular
hydrogen bonding.
• The extent and strength of the hydrogen bond depend heavily
on the electronegativity difference between the interacting
atoms.

[1]
Learn Phenol + Aniline
• Phenol and aniline form a very strong intermolecular hydrogen
bond between the –OH and –NH₂ groups.
• This cross-interaction (HB3) is stronger than the self-
association hydrogen bonds found in pure phenol (HB1) or pure
aniline (HB2).

Distillation of an Ideal Solution of Liq A and Liq B

• Fractional distillation separates ideal solutions by continuously
enriching the vapor phase with the more volatile liquid.
• Relative vapor composition formula: y_A / (1 - y_A) = (Pº_A
/ Pº_B) × [x_A / (1 - x_A)]
• In an ideal mixture, this repeated boiling and condensing process
allows for the complete separation of both components.

[2]
Pressure Composition Curve For Ideal Solution
• The pressure-composition curve plots both liquid and vapor
compositions against vapor pressure.
• It graphically illustrates how the vapor phase is always richer in
the more volatile component compared to the liquid phase.

Distillation of a non-ideal Solution of Liq A and Liq B

• When distilling a non-ideal solution, the liquid and vapor phases
eventually reach the exact same composition.

[3]
• At this specific concentration point, further separation by
fractional distillation becomes impossible, resulting in an
azeotrope.

Pressure-Composition Curve For Non-Ideal Solutions

• Non-ideal solutions exhibit either positive or negative deviations
from Raoult’s Law.
• Strong deviations lead to distinct peaks (maxima or minima) on
the pressure curve, which correspond to the formation of an
azeotrope.

[4]
Azeotropic Mixture
• An azeotrope is a binary solution of two volatile liquids where
both the liquid phase and the vapor phase share the exact same
composition.
• Because the condensed vapor has the same makeup as the
boiling liquid, the mixture boils at a constant temperature and
cannot be separated by fractional distillation.

Minimum Boiling Azeotrope

• Formed by non-ideal solutions that exhibit a large positive
deviation from Raoult’s Law.
• The boiling point of this specific azeotropic mixture is lower than
the boiling point of either individual pure component (e.g., 95%
ethanol and 5% water).

[5]
Maximum Boiling Azeotrope
• Formed by non-ideal solutions that exhibit a large negative
deviation from Raoult’s Law.
• The boiling point of this azeotropic mixture is strictly higher
than that of either individual pure component (e.g., 68% HNO₃
and 32% water).

Colligative Properties
• These are specific properties of a solution that depend strictly
on the total number of solute particles, not on their chemical
identity.
• For a property to be colligative, the solute must be strictly non-
volatile and the solution must be highly dilute.

[6]
Relative Lowering of Vapour Pressure

• Adding a non-volatile solute obstructs the surface, lowering the

solvent’s overall vapor pressure.

• RLVP Formula: (Pº - P_s) / Pº = n_solute / (n_solute +

n_solvent)

• For rapid calculations in dilute solutions, an exact alternative is

often used: (Pº - P_s) / P_s = n_solute / n_solvent.

Elevation in Boiling Point

• Since a non-volatile solute lowers the vapor pressure, more heat
is required to force the vapor pressure to match atmospheric
pressure, meaning the boiling point rises.
• Formula: ΔT_b = K_b × m (where m is the molality of the
solution).
• The ebullioscopic constant (K_b) is a unique characteristic of
the solvent alone and does not depend on the solute.

[7]
[8]
 Chemistry
Solutions
(Lecture-14)

Concepts Covered in the Class:

• Depression in F.P
• Osmotic Pressure

Explaination - 3
• The boiling point is reached when the liquid and vapor phases
Δ𝐻𝑣𝑠
are in equilibrium ( Δ𝐺 = 0 ), giving the relationship 𝑇𝑏 = .
Δ𝑆𝑣𝑠

• The ebullioscopic constant (𝐾𝑏 ) is a characteristic property of

the pure solvent only:

𝑴𝑹𝑻𝟐𝒃
𝑲𝒃 = 𝚫𝑯 .
tap ×𝟏𝟎𝟎𝟎

• Because a solution has higher initial entropy than a pure solvent,

it requires a higher temperature to boil, resulting in boiling point
elevation.

[1]
Oswalt-Walker Experiment
• This experiment measures the Relative Lowering of Vapour
Pressure (RLVP) by passing dry air sequentially through a
solution, a pure solvent, and anhydrous CaCl2 .
𝑃∞ −𝑃1 𝑤2
• 𝑅𝐿𝑉𝑃 = =
𝑃∞ 𝑤1 +𝑤2

• The RLVP is directly calculated by taking the ratio of the weight

loss in the pure solvent ( 𝑤2 ) to the total weight gain in the
dehydrating CaCl2 tube ( 𝑤1 + 𝑤2 ).

[2]
Depression in Freezing Point
• The freezing point is the temperature where the liquid and solid
phases are in dynamic equilibrium (their vapor pressures are
equal), and only the solvent undergoes freezing.
• Δ𝑇𝑓 = 𝐾𝑓 ⋅ 𝑚
• The cryoscopic constant ( 𝐾𝑓 ) is a property of the solvent,
𝑀𝑅𝑇𝑓2
determined by its heat of fusion: 𝐾𝑓 = .
Δ𝐻𝑓𝑢 ×1000

Explaination 1
• Adding a non-volatile solute lowers the liquid's vapor pressure,
causing it to intersect the solid's vapor pressure curve at a much
lower temperature.
• Since this drop in freezing point increases as more solute is
added, depression in freezing point is considered a colligative
property.

[3]
Explaination - 2
• Freezing involves a decrease in entropy as liquid turns to solid;
Δ𝐻𝑓𝑎𝑠
at equilibrium, the freezing temperature is defined by 𝑇𝑓 = .
Δ𝑆
• Because a solution has higher entropy than a pure solvent, a
larger temperature drop is required to overcome this and reach
the highly ordered solid phase.
• Consequently, the freezing point of a solution will always be
lower than that of the pure solvent.

[4]
 Chemistry
Solutions
(Lecture-15)

• Osmotic pressure (π) is the extra pressure applied to the

solution side to stop osmosis.
• Osmotic Pressure formula: π = CRT, where C is the molar
concentration, R is the gas constant (0.0821 atm·L/(K·mol)),
and T is the absolute temperature.

Reverse Osmosis.
• If an external pressure (π’) greater than the osmotic pressure
(π) is applied to the solution side, the solvent flows from the
solution to the solvent side. This process is called reverse
osmosis.

[1]
Osmotic Pressure of the solution having two or more Solutes
• The total osmotic pressure of a solution containing multiple
solutes is the sum of the partial osmotic pressures of each
solute.
• Formula for total osmotic pressure: πnet = π1 + π2 = (nA + nB)RT
/ V.

Osmotic Pressure of a resultant solution when two solutions

of same substance of different osmotic Pressure are mixed
• When two solutions of the same substance with different
osmotic pressures are mixed, the osmotic pressure of the
resulting solution is given by: πnet = (π1V1 + π2V2) / (V1 + V2).

Hypertonic, Hypotonic and Isotonic Solutions

• A hypertonic solution has a higher osmotic pressure compared to
another solution.
• A hypotonic solution has a lower osmotic pressure compared to
another solution.
• Isotonic solutions have the same osmotic pressure (π1 = π2). If
the temperature is the same, then their concentrations are also
equal (C1 = C2).

Van’t Hoff Factor (i)

• The Van’t Hoff factor (i) accounts for the association or
dissociation of solute particles in a solvent, causing the observed
colligative property to differ from the theoretically calculated
one.
• It is defined as: i = (Observed Colligative Property) /
(Theoretical Colligative Property).
• The Van’t Hoff factor modifies colligative property formulas:

[2]
i) Tb = i Kb m (elevation in boiling point)

ii) T_f = i Kf m (depression in freezing point)

iii) π = i CRT (osmotic pressure)

iv) RLVP (relative lowering of vapor pressure) = i nsolute / (i

nsolute + nsolvent) ≈ i nsolute / nsolvent (for dilute solutions where i
nsolute << nsolvent)

v) i = Mcal / Mobs (ratio of calculated molar mass to

observed molar mass)

[3]
 Chemistry
Solutions
Lecture-16

Concepts Covered in the Class:

• Van’t Hoff Factor
• Henry’s Law

Van’t Hoff Factor (i)

• Solute association or dissociation causes the observed colligative
property to differ from its theoretical (calculated) value.
• i = (observed colligative property) / (theoretical colligative
property)
• Core formulas are modified to include this factor (e.g., ΔTb =
i·Kb·m, π = i·C·R·T).

In case of dissociation
• Occurs when a solute breaks into multiple particles in the solvent
(e.g., acetic acid in water).
• i = 1 + (n - 1)α (where ‘n’ is the number of particles the solute
breaks into, and ‘α’ is the degree of dissociation).

[1]
• Because particles multiply, the Van’t Hoff factor is always
greater than 1 (i > 1).

In case of association
• Occurs when multiple solute particles combine to form a single
larger unit (e.g., benzoic acid forming dimers in benzene).
• i = 1 - (1 - 1/n)β (where ‘n’ is the number of particles joining
together, and ‘β’ is the degree of association).
• Because the total number of particles decreases, the Van’t Hoff
factor is always less than 1 (i < 1).

Solubility of gas in liquid

• Solubility is defined as the maximum amount of gas that can
be dissolved in a solvent per litre at a specific temperature.

[2]
Factors Affecting solubility of gas
• As temperature increases, the solubility of solids generally
increases, whereas the solubility of gases decreases.
• Dissolving a gas is an exothermic (heat-releasing) process
similar to condensation; therefore, heating the solution drives
the dissolved gas out (which is why aquatic life prefers cold
water).

Henry’s Law
• The solubility of a gas in a particular solvent is directly
proportional to the partial pressure of that gas above the liquid.
• P_gas = K_H × X_gas (where K_H is Henry’s Constant and
X_gas is the mole fraction of the gas).

[3]
3. Nature of Gas
• Following the rule “like dissolves like,” polar gases dissolve much
more readily in polar solvents (like water) compared to non-
polar gases.

Application of Henry’s Law

• Explains real-world observations, such as the difficulty of
breathing at higher altitudes and why scuba divers must ascend
slowly to avoid illness.

Henry’s Constant (K_H)

• K_H is inversely proportional to solubility: a lower K_H value
means higher gas solubility.
• Gases with stronger attractive intermolecular forces are more
soluble and consequently have lower K_H values.

Curve between Pgas Vs Xgas

• Plotting the partial pressure of the gas against its mole fraction
yields a straight line passing through the origin.
• The slope of this line directly represents Henry’s constant
(K_H).

[4]
Curve between Pgas and Xsolvent
• Plotting the partial pressure of the gas against the mole fraction
of the solvent produces a downward-sloping straight line.
• The equation is P_gas = -K_H(X_solvent) + K_H, meaning the
graph has a negative slope (-K_H) and a y-intercept of K_H.

[5]