SOLUTIONS

Complete Formula Sheet & Notes

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Contents

1 Concentration of Solutions 3

2 Henry’s Law — Solubility of Gases 4

3 Raoult’s Law & Vapour Pressure 4

3.1 Raoult’s Law for Volatile Liquid Mixtures . . . . . . . . . . . . . . . . . . . . . . 4
3.2 Non-Ideal Solutions (Deviations from Raoult’s Law) . . . . . . . . . . . . . . . . 5

4 Colligative Properties 6
4.1 1. Relative Lowering of Vapour Pressure (RLVP) . . . . . . . . . . . . . . . . . . 6
4.2 2. Elevation of Boiling Point (∆Tb ) . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4.3 3. Depression of Freezing Point (∆Tf ) . . . . . . . . . . . . . . . . . . . . . . . . 7
4.4 4. Osmotic Pressure (Π) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

5 Thermodynamic Derivation of Kf and Kb 8

6 Van’t Hoff Factor (i) & Abnormal Molar Mass 9

6.1 Modified Colligative Property Formulae . . . . . . . . . . . . . . . . . . . . . . . 10

7 Quick Revision Formula Sheet 11

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1 Concentration of Solutions

These are the foundational formulas for quantifying how much solute is dissolved in a
solution.

All Concentration Formulae at a Glance

Measure Formula

Mass of component
Mass % (w/w) Mass % = × 100
Total mass of solution
Volume of component
Volume % (V/V) Volume % = × 100
Total volume of solution
Parts of component
ppm ppm = × 106
Total parts of all components
ni nA ∑
Mole Fraction xi = ∑ ; xA = ; xi = 1
ni nA + nB
Moles of solute
Molarity (M) M=
Volume of solution (L)
Moles of solute
Molality (m) m=
Mass of solvent (kg)

Key Differences: Molarity vs Molality

• Molarity (M) depends on volume of solution ⇒ changes with temperature.

• Molality (m) depends on mass of solvent ⇒ temperature independent.
• For dilute aqueous solutions: M ≈ m (since density of water ≈ 1 g/mL).

Unit Reminder
• Molarity: mol/L (or M)
• Molality: mol/kg (or m)
• Mole fraction: dimensionless
• ppm: mg/kg or mg/L (for very dilute solutions)

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2 Henry’s Law — Solubility of Gases

p = KH · x

• p = partial pressure of gas in the vapour phase

• x = mole fraction of gas in the solution
• KH = Henry’s Law constant (unit: pressure)

Henry’s Law Trends

• KH ↑⇒ solubility ↓ (Higher KH = gas less soluble)

• KH increases with temperature ⇒ solubility of gases decreases with tempera-
ture
• Higher pressure ⇒ more gas dissolves (soda fizz effect)

Applications of Henry’s Law

• Carbonated drinks are sealed under high CO2 pressure.

• Deep-sea divers use air diluted with He (low KH ⇒ less N2 dissolves in blood ⇒
no bends).
• Fish survive in water using dissolved O2 .

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3 Raoult’s Law & Vapour Pressure

3.1 Raoult’s Law for Volatile Liquid Mixtures

Raoult’s Law (Binary Volatile Solution)

Partial vapour pressures:

p1 = p01 · x1 p2 = p02 · x2

Total pressure (Dalton’s Law):

ptotal = p1 + p2 = p01 x1 + p02 x2

Total pressure in terms of component 2 alone:

ptotal = p01 + (p02 − p01 ) x2

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 The mole fraction of a component in the vapour phase (yi ):

pi = yi · ptotal

p1 p01 x1 p2 p02 x2
y1 = = y2 = =
ptotal ptotal ptotal ptotal

Ideal Solution Thermodynamics

For a perfectly ideal solution (obeys Raoult’s Law at all concentrations):

∆mix H = 0 ∆mix V = 0

∆mix S > 0 always (entropy increases on mixing).

3.2 Non-Ideal Solutions (Deviations from Raoult’s Law)

Property Positive Deviation Negative Deviation

ptotal vs ideal > ideal < ideal

∆mix H > 0 (endothermic) < 0 (exothermic)
∆mix V > 0 (expands) < 0 (contracts)
A–B interactions Weaker than A–A/B–B Stronger than A–A/B–B
Azeotrope formed Min. boiling azeotrope Max. boiling azeotrope
Examples Ethanol + Water Chloroform + Acetone

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4 Colligative Properties

What are Colligative Properties?

Properties that depend only on the number of solute particles, not on their
nature. Subscript 1 = solvent; Subscript 2 = solute throughout this section.

4 Colligative Properties: REBD → RLV P, Elevation(BP ), Boiling → Depression(F P ), Osmosis

4.1 1. Relative Lowering of Vapour Pressure (RLVP)

RLVP Formula

p01 − p1
= x2
p01
For dilute solutions (n2 ≪ n1 ):

p01 − p1 n2 w 2 × M1
≈ =
0
p1 n1 M2 × w 1

To find molar mass of solute (M2 ):

w2 × M1 × p01
M2 =
(p01 − p1 ) × w1

4.2 2. Elevation of Boiling Point (∆Tb )

Boiling Point Elevation

∆Tb = Tb − Tb0
∆Tb = Kb · m
To find molar mass of solute:
1000 × w2 × Kb
M2 =
∆Tb × w1

• Kb = Ebullioscopic constant (mol. elevation constant) in K·kg/mol

• m = molality of solution
• w1 , w2 in grams; M2 in g/mol

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4.3 3. Depression of Freezing Point (∆Tf )

Freezing Point Depression

∆Tf = Tf0 − Tf

∆Tf = Kf · m

To find molar mass of solute:

Kf × w2 × 1000
M2 =
∆Tf × w1

• Kf = Cryoscopic constant (mol. depression constant) in K·kg/mol

• Tf0 = freezing point of pure solvent, Tf = freezing point of solution

Kf and Kb Values to Remember

Solvent Kf (K·kg/mol) Kb (K·kg/mol)

Water 1.86 0.52

Benzene 5.12 2.53
Camphor 40 —

4.4 4. Osmotic Pressure (Π)

Van’t Hoff Equation for Osmosis

n2
Π = CRT = RT
V
To find molar mass of solute:
w2 RT
M2 =
ΠV
• Π = osmotic pressure (in atm or Pa)
• C = molar concentration of solute (mol/L)
• R = 0.0821 L·atm/mol·K or 8.314 J/mol·K
• T = temperature in Kelvin

Osmosis Key Terms

• Osmosis: Flow of solvent through a semipermeable membrane from lower to

higher concentration.
• Osmotic Pressure: External pressure needed to stop osmosis.
• Isotonic: Two solutions with equal osmotic pressure (no net flow).
• Hypertonic: Higher osmotic pressure (water flows out of a cell).
• Hypotonic: Lower osmotic pressure (water flows into a cell).

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 • Reverse Osmosis: Applying pressure > Π to purify water (desalination).

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5 Thermodynamic Derivation of Kf and Kb

JEE Advanced — Critical Derivations

These formulas are derived from thermodynamic principles and tested when Kf or
Kb are not given. You must derive them from first principles.

Cryoscopic Constant (Kf ) Derivation

R × M1 × Tf∗2
Kf =
1000 × ∆fus H

• R = Gas constant = 8.314 J/mol·K

• M1 = Molar mass of solvent (g/mol)
• Tf∗ = Freezing point of pure solvent (in Kelvin)
• ∆fus H = Enthalpy of fusion of solvent (J/mol)
• Factor of 1000 converts g to kg

Ebullioscopic Constant (Kb ) Derivation

R × M1 × Tb∗2
Kb =
1000 × ∆vap H

• R = Gas constant = 8.314 J/mol·K

• M1 = Molar mass of solvent (g/mol)
• Tb∗ = Boiling point of pure solvent (in Kelvin)
• ∆vap H = Enthalpy of vaporisation of solvent (J/mol)

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 Common Mistakes
• Temperature must be in Kelvin, not Celsius.
• M1 is molar mass of solvent, not solute.
• ∆H must be in J/mol (not kJ/mol) if R is in J/mol·K.
• The 1000 factor is needed to convert M1 from g/mol to kg/mol.

Mnemonic for Kf and Kb

R · Msolvent · Tpure
2
K=
1000 · ∆H
“RMT-squared over 1000∆H” — same structure for both, just swap Tf with Tb
and ∆fus H with ∆vap H.

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6 Van’t Hoff Factor (i) & Abnormal Molar Mass

When to Use Van’t Hoff Factor?

Use i whenever the solute dissociates (ionises) or associates (dimerises) in the
solvent. Without i, colligative property calculations give incorrect molar masses.

Observed colligative property Theoretical molar mass Total moles of particles afte
i= = =
Theoretical colligative property Observed molar mass Moles before dissociation/assoc

Degree of Dissociation (α) and Association (α) Formulae

For Dissociation (e.g., AB → A+ + B − , n particles formed):

i−1
i = 1 + (n − 1)α ⇒ α=
n−1
For Association (e.g., nA → An , dimer/trimer formed):
( )
1 1−i
i=1− 1− α ⇒ α=
n 1 − n1

where n = number of particles formed/associated, α = degree of dissocia-

tion/association.

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6.1 Modified Colligative Property Formulae

All Four Colligative Properties with Van’t Hoff Factor

Property Modified Formula

p01 − p1 n2
RLVP 0 =i·
p1 n1

Boiling Point Elevation ∆Tb = i · Kb · m

Freezing Point Depression ∆Tf = i · Kf · m

n2
Osmotic Pressure Π=i· · RT
V

i Values for Common Electrolytes

Electrolyte Dissociation i (ideal, complete dissoc.)

NaCl Na+ + Cl− 2

CaCl2 Ca2+ + 2Cl− 3
AlCl3 Al3+ + 3Cl− 4
K2 SO4 2K+ + SO2−
4 3
Non-electrolyte No dissociation 1
Acetic acid dimer 2 CH3 COOH → (CH3 COOH)2 0.5

Abnormal Molar Mass

• Dissociation ⇒ more particles ⇒ i > 1 ⇒ observed molar mass < theoretical.
• Association ⇒ fewer particles ⇒ i < 1 ⇒ observed molar mass > theoretical.
• i = 1 for non-electrolytes (no association/dissociation).

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7 Quick Revision Formula Sheet

ALL FORMULAE — SOLUTIONS CHAPTER

Topic Formula

nsolute
Molarity M=
Vsoln (L)
nsolute
Molality m=
wsolvent (kg)
ni ∑
Mole Fraction xi = ∑ , xi = 1
ni
Henry’s Law p = KH · x

Raoult’s Law pi = p0i · xi

Total Pressure pT = p01 + (p02 − p01 )x2

p01 − p1 n2
RLVP 0 = x2 ≈
p1 n1
1000 w2 Kb
∆Tb ∆Tb = Kb m, M2 =
∆Tb w1
1000 Kf w2
∆Tf ∆Tf = Kf m, M2 =
∆Tf w1
n2 RT w2 RT
Osmotic Pressure Π = CRT = , M2 =
V ΠV
RM1 Tf∗2
Kf derivation Kf =
1000 ∆fus H
RM1 Tb∗2
Kb derivation Kb =
1000 ∆vap H
n2 RT
Van’t Hoff i ∆Tb = iKb m, ∆Tf = iKf m, Π=i
V
Dissociation i = 1 + (n − 1)α

Association i = 1 − (1 − 1/n)α

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