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Exercise · Q26

Q.Write the van der Waals equation for nn moles of a real gas, and explain the physical significance of the constants aa and bb.

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The van der Waals equation for nn moles of a real gas is (P+an2V2)(V−nb)=nRT\left(P + \frac{an^2}{V^2}\right)(V - nb) = nRT It corrects the ideal gas equation for the two kinetic-theory assumptions that fail for real gases. The pressure correction, an2V2\dfrac{an^2}{V^2}, is added to the measured pressure PP because intermolecular attractive forces pull molecules near the container wall slightly inward, so the gas strikes the walls a little less forcefully than it would without attraction — the measured pressure is therefore somewhat lower than the "true" value, and adding this term compensates. The constant aa quantifies the strength of intermolecular attraction: larger for gases with stronger dispersion forces or permanent dipoles (e.g. NH3\text{NH}_3, CO2\text{CO}_2), smaller for weakly attracting gases (e.g. H2\text{H}_2, He\text{He}). The volume correction, nbnb, is subtracted from the measured volume VV because the gas molecules themselves occupy real, non-zero space, so the volume actually avai …

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