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Gaseous State
This is one of the most important small chapters with good weightage physical chemistry chapter Questions were asked regularly in the previous exams Mostly questions came from Behaviour of real gases and Vander Waal’s equation. Problems and theoretical questions came with almost same priority in the recent four years papers Areas to be focused: (i) Vander Waal’s equation with proper understanding of all the terms and their physical significance (ii) Molecular velocities and Graham’s law of diffusion Equation of State: The combination of Boyle’s law, Charles law and Avogadro’s law leads to the expression PV = nRT. R = 0.0821 L atm K-1 mol-1 = 8.314 J K-1 mol-1 = 8.314 × 105 Pa m3 K-1 mol-1 = 8.314 × 102 kPa dm3 K-1 mol-1 = 8.314 Mpa cm3 K-1 mol-1 = 1.987 cal K-1 mol-1
Graham’s Law of Diffusion: Mathematically, it is expressed as, r ∝
1 ρ or ∝ 1 M

Comparison of the rate of diffusion of two gases under identical conditions provides the relation r1 P1 d2 r1 P1 M2 = or = where d1 and d2 are vapour density of two gases r2 P2 d1 r2 P2 M1 M1 and M2 are molecular mass of two gases
Root Mean Square Speed
urms
2  u1 + u2 2 + =  N  2  + uN    1 2

urms =

3RT M

Average Speed

u av =

u1 + u 2 + N 8RT u av = . πM
2RT M

+ uN

Most Probable Speed

ump =

Comparing the three speeds listed above, we find that urms : uav : ump : : 3 : 8 / π : 2 urms > uav > ump Average Kinetic Energy
KE = 3pVm 3RT 3 = = kT 2NA 2NA 2

Where k = R/NA is known as Boltzmann constant. Van der waal’s Equation of State: Van der Waal pointed out that the deviations shown by real gases are due to the following two facts. 1. The volume occupied by the molecules is not negligible in comparison to the total volume of the gas. 2. There exist forces of attraction between the molecules.

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P = pressure. 2. greater will be the value of ‘a’.ǁǁǁ͘ƐĂŬƐŚŝĞĚƵĐĂƚŝŽŶ͘ĐŽŵ Van der Waal systematically corrected the ideal gas equation in the light of the above two corrected equation for one mole of gas is a    p + 2  (V − b) = RT V   facts. l= kT 2 πσ 2 P k = Boltzmann constant. The There constant ‘a’ depends on intermolecular force of attraction between gas molecules. 3. D 2. C A sample of gas contains N1 molecules. Another sample of gas at 27oC has total kinetic energy as 2E ergs. Model Questions 1. Ti = ؊ ‹ Mean Free Path It is the average distance travelled by a gas molecule between two successive collisions. Statement-2: All gases behave ideally at their Boyle’s temperatures over a wide range of pressure. 4 b = 4 × πr 3 × N 4 Where r = radius of one molecule. TC = Š Řŝ ‹ Ř ŞŠ . Assuming gas to be ideal. if RT = 2 Pa . the number of gas molecules in the 2nd sample will be (B) N1/2 (C) 2N1 (D) 4N1 (A) N1 A Statement-1: Hydrogen and helium show positive deviation at all temperatures and pressures. 3 When the Pressure is not too High: When the Pressure is too High: Boyle Temperature: TB = Š ‹ PV = RT – a/V PV = RT + Pb Critical Phenomenon It is the temperature above which gases can never be liquefied however high may be the pressure applied. its total kinetic energy at -123oC is E ergs. The constant ‘b’ depends on size of molecules. T = temperature. ǁǁǁ͘ƐĂŬƐŚŝĞĚƵĐĂƚŝŽŶ͘ĐŽŵ . VC = 3b Inversion Temperature: The temperature below which a gas on subjecting to Joule-Thomson effect shows cooling effects and above which it shows heating effects is called inversion temperature (Ti). Řŝ ‹ Critical Pressure: The pressure just required to liquify a gas at critical temperature is called critical pressure. then the volume occupied by a real gas is (A) 2RT/P (B) 2P/RT (C) RT/2P (D) RT/P 1. Greater the attraction. At low pressure. 3. s = collision diameter. PC = Critical Volume: The volume of a gas at the critical temperature and critical pressure is called critical volume.