Physical Chemistry

Gaseous State

Gas Laws, Kinetic Theory, and Real Gases

High Weightage in JEE Main

Introduction

The gaseous state is the simplest state of matter where molecular forces of attraction between particles are minimum. Gases show great uniformity in behavior and have several characteristic properties.

Gaseous State is characterized by minimum intermolecular forces, infinite expansibility, high compressibility, and random molecular motion with high kinetic energy.

Characteristics of Gases

Compressibility
High compressibility due to large intermolecular spaces
Infinite expansibility
Pressure
Exert pressure on container walls
Pressure ∝ Temperature
Diffusion
High diffusibility
Mix spontaneously
Shape & Volume
No definite shape
No definite volume

Measurable Properties of Gases

Gases are described by four measurable properties: Volume (V), Pressure (P), Temperature (T), and Amount (mass or moles).

Volume
Units: L, mL, cm³, m³
1 L = 1000 mL = 1 dm³ = 10⁻³ m³
1 m³ = 10³ L = 10⁶ mL
Mass
Moles (n) = Mass / Molar mass
n = m/M
Temperature
K = °C + 273
°C/5 = (F° - 32)/9
SI unit: Kelvin (K)
Pressure
P = Force/Area
SI unit: Pascal (Pa)
1 atm = 1.01325 × 10⁵ Pa
1 bar = 10⁵ Pa

Pressure Units Conversion

Unit Symbol Value in Pa
Bar bar 1 bar = 10⁵ Pa
Atmosphere atm 1 atm = 1.01325 × 10⁵ Pa
Torr Torr 1 Torr = 133.322 Pa
mm of Hg mm Hg 1 mm Hg = 133.322 Pa
Absolute Pressure = Gauge Pressure + Atmospheric Pressure

Gas Laws

Boyle's Law

At constant temperature, the volume of a fixed amount of gas is inversely proportional to its pressure.

P ∝ 1/V or PV = constant or P₁V₁ = P₂V₂

Graph between P and V at constant temperature is an isotherm (rectangular hyperbola).

Charles' Law

At constant pressure, the volume of a fixed amount of gas is directly proportional to its absolute temperature.

V ∝ T or V/T = constant or V₁/T₁ = V₂/T₂

Volume coefficient: αᵥ = 1/273.15 = 3.661 × 10⁻³ °C⁻¹

Gay-Lussac's Law

At constant volume, the pressure of a fixed amount of gas is directly proportional to its absolute temperature.

P ∝ T or P/T = constant or P₁/T₁ = P₂/T₂

Pressure coefficient: αₚ = 1/273.15 = 3.661 × 10⁻³ °C⁻¹

Avogadro's Law

Equal volumes of all gases at the same temperature and pressure contain equal number of molecules.

V ∝ n or V/n = constant or V₁/n₁ = V₂/n₂

Molar volume at STP = 22.414 L mol⁻¹

Ideal Gas Equation

Ideal Gas Equation combines Boyle's, Charles', and Avogadro's laws: PV = nRT

Gas Constant (R) Values

Values of Gas Constant R
R = 0.0821 L atm mol⁻¹ K⁻¹
R = 8.314 J mol⁻¹ K⁻¹ (SI unit)
R = 8.314 × 10⁷ erg mol⁻¹ K⁻¹
R = 1.987 cal mol⁻¹ K⁻¹

Boltzmann Constant

k = R/N₀ = 1.38 × 10⁻²³ J K⁻¹ (per molecule)

Gas Density Calculations

M = mRT/PV (Molecular weight from gas equation)
d = PM/RT (Gas density)
d₁T₁/P₁ = d₂T₂/P₂ (For different conditions)

Dalton's Law of Partial Pressures

Dalton's Law states that the total pressure exerted by a mixture of non-reacting gases is equal to the sum of the partial pressures of individual gases.

Ptotal = P₁ + P₂ + P₃ + ...
P₁ = (n₁/ntotal) × Ptotal = X₁ × Ptotal

Applications

Mole Fraction
X₁ = P₁/Ptotal
Dry Gas Pressure
Pdry gas = Pmoist gas - Aqueous tension
Relative Humidity
RH = (Partial pressure of water/Vapor pressure of water) × 100

Graham's Law of Diffusion

Graham's Law states that at constant temperature and pressure, the rate of diffusion or effusion of a gas is inversely proportional to the square root of its density or molar mass.

r ∝ 1/√d or r₁/r₂ = √(d₂/d₁) = √(M₂/M₁)

Diffusion vs Effusion

Diffusion
Spontaneous mixing of gases
Through entire volume
Example: Perfume spreading in room
Effusion
Escape through small opening
Through pinhole
Example: Gas escaping from balloon

Rate of Diffusion

r₁/r₂ = V₁/V₂ (when time is constant)
r₁/r₂ = t₂/t₁ (when volume is constant)
r ∝ P/√M (when pressure is not constant)

Kinetic Theory of Gases

Kinetic Theory explains gas behavior in terms of molecular motion. It's based on several postulates about gas molecules.

Postulates of Kinetic Theory

Gas molecules are in continuous random motion
Volume of molecules is negligible compared to container volume
Molecular collisions are perfectly elastic
No intermolecular forces except during collisions
Average kinetic energy ∝ Absolute temperature

Kinetic Gas Equation

PV = (1/3) mnu²

Where m = mass of molecule, n = number of molecules, u = root mean square velocity

Kinetic Energy Calculation

Average KE per mole = (3/2) RT
Average KE per molecule = (3/2) kT

Molecular Speeds

Gas molecules have different speeds described by Maxwell-Boltzmann distribution.

RMS Velocity
urms = √(3RT/M) = √(3P/d)
u₁/u₂ = √(T₁/T₂) = √(M₂/M₁)
Average Velocity
vav = √(8RT/πM)
vav = 0.9213 × urms
Most Probable Velocity
αmp = √(2RT/M)
αmp = 0.816 × urms

Relationship Between Velocities

αmp : vav : urms = 1 : 1.128 : 1.224
αmp < vav < urms

Real Gases and Deviations

Real gases deviate from ideal behavior due to intermolecular forces and molecular volume. These deviations increase at high pressures and low temperatures.

Compressibility Factor (Z)

Z = PV/nRT = PVm/RT
Z = 1
Ideal gas behavior
At Boyle temperature
Z > 1
Positive deviation
Less compressible
Repulsive forces dominant
Z < 1
Negative deviation
More compressible
Attractive forces dominant

Van der Waals Equation

Van der Waals equation modifies the ideal gas equation to account for molecular volume and intermolecular attractions.

(P + an²/V²)(V - nb) = nRT

Van der Waals Constants

Constant 'a'
Measure of intermolecular attraction
Units: atm L² mol⁻²
Higher for easily liquefiable gases
Constant 'b'
Excluded volume
Units: L mol⁻¹
b = 4N₀ × (4/3)πr³

Critical Constants

Tc = 8a/(27Rb) (Critical temperature)
Pc = a/(27b²) (Critical pressure)
Vc = 3b (Critical volume)
Zc = PcVc/RTc = 3/8 = 0.375

Important Points to Remember

Key Points for JEE Main

  • Ideal gases obey PV = nRT at all temperatures and pressures
  • Real gases show deviations at high pressures and low temperatures
  • RMS velocity is the highest, most probable velocity is the lowest
  • Average kinetic energy depends only on temperature, not on nature of gas
  • Van der Waals equation accounts for molecular size and attractions
  • Critical temperature is the temperature above which gas cannot be liquefied
  • Diffusion rate is inversely proportional to square root of molar mass

Do's

Memorize values of R in different units
Practice gas law numerical problems
Understand the concept of partial pressures
Learn to calculate molecular speeds

Don'ts

Don't confuse different molecular speeds
Don't forget units in calculations
Don't apply ideal gas equation to real gases without corrections
Don't mix up diffusion and effusion

JEE Main Weightage

This chapter typically carries 2-3 questions in JEE Main, making it a high-weightage chapter. Questions often focus on gas laws, kinetic theory, molecular speeds, and real gas behavior.

Chapter Weightage in JEE Main

Weightage High (2-3 questions)