--%>

Molecular Diameters

The excluded volume b, introduced by vander Wall's as an empirical correction term, can be related to the size gas molecules. To do so, we assume the excluded volume is the result of the pairwise coming together of molecules. This assumption is justified when b values are obtained from second viral coefficient data. Fitting values for the empirical constants are derived from van der Waal's equation. Some b values obtained in this way are given in table.


So that we need to deal with a single molecular size parameter, we treat molecules as spherical particles. The diameter of a molecule is d. the volume of a molecule is v

The volume in which a pair of molecules cannot move because of each other's presence is indicated by the lightly shaded region. The radius of this excluded volume sphere is equal to the molecule diameter d. the volume excluded to the pair of molecules is 4/3πd3. We thus obtain,

= 4[4/3π (d/2)]3

The expression in brackets is the volume of a molecule.vander Waal's b term is the excluded volume per mole of the molecules. Thus we have, with N representing Avogadro's number,

B= 4n [4/3π (d/2)3] = 4N (vol. of molecule)

Molecular size and Lennard Jones intermolecular Attraction term based on second virial coefficient data:

Gas Excluded volume B, L mol-1 Molecular diam. D, pm ELJ, J × 10-21
He 0.021 255 0.14
Ne 0.026 274 0.49
Ar 0.050 341 1.68
Kr 0.058 358 2.49
Xe 0.084 405 3.11
H2 0.031 291 0.52
N2 0.061 364 1.28
O2 0.058 358 1.59
CH4 0.069 380 1.96
C(CH3)4 0.510 739 3.22


Van der Waal's equation and the Boyle temperature:

Gas Tboyle, K Tboyle/TC
H2 110 3.5
He 23 4.5
CH4 510 2.7
NH3 860 2.1
N2 330 2.6
O2 410 2.7


Example: calculate the radius of the molecule from the value of 0.069 L mol-1 for the excluded volume b that is obtained from the second virial coefficient data.

Solution: the volume of 1 mol of methane molecules is obtained by dividing the b value of 0.069 L mol-1 = 69 × 10-6 m3 mol-1 value by 4. Then division by Avogadro's number gives the volume per molecule. We have:

Volume of methane molecule = 69 × 10-6 m3/4 × 6.022 × 1023 

= 2.86 × 10-29 m
3

The volume is equal to 4/3∏r3 and on this basis we calculate:

r = 1.90 × 10-10 m and d = 3.80 × 10-10 m = 380 pm

   Related Questions in Chemistry

  • Q : Mass percent Help me to go through this

    Help me to go through this problem. 10 grams of a solute is dissolved in 90 grams of a solvent. Its mass percent in solution is : (a) 0.01 (b) 11.1 (c)10 (d) 9

  • Q : P block bif3 is ionic while other

    bif3 is ionic while other trihalides are covalent in nature

  • Q : Mole fraction of water Give me answer

    Give me answer of this question. A solution contains 25%H2O 25%C2H5OH , and 50% CH3 COOH by mass. The mole fraction of H2O would be: (a) 0.25 (b) 2.5 (c) 0.503 (d) 5.03.

  • Q : Explain Rotational Vibrational Spectra

    The infrared spectrum of gas samples shows the effect of rotational-energy changes along with the vibrational energy change.As we know from the interpretations given to thermodynamic properties of gases, gas molecules are simultaneously rotating and vibrating. It follows that an absor

  • Q : Question based on maximum vapour

    Provide solution of this question. Which has maximum vapour pressure: (a) HI (b) HBr (c) HCl (d) HF

  • Q : Iso-electronic species Which ion has

    Which ion has the lowest radius from the following ions(a) Na+  (b) Mg2+  (c) Al3+  (d) Si4+ Answer: (d) All are the iso-electronic species but Si

  • Q : Laws of Chemical Combination Laws of

    Laws of Chemical Combination- In order to understand the composition of the compounds, it is necessary to have a theory which accounts for both qualitative and quantitative observations during chem

  • Q : Define the term oxidizing agent Briefly

    Briefly define the term oxidizing agent?

  • Q : What do you mean by the term tripod

    What do you mean by the term tripod? Also state its uses?

  • Q : Theory of three dimensional motion

    Partition function; that the translational energy of 1 mol of molecules is 3/2 RT will come as no surprise. But the calculation of this result further illustrates the use of quantized states and the partition function to obtain macroscopic properties. The partition fu