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What theoretical rules are used to predict the relative strength of London Dispersion forces? Which applies to isomers?

Explain the theory behind these rules by explaining the principles of LDFs and predict which of your isomers might have the highest and lowest boiling point.

User Tayyaba
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We know that the London Dispersion force is the weakest intermolecular force. The London dispersion force is a temporary attractive force that results when the electrons in two adjacent atoms occupy positions that make the atoms form temporary dipoles. This force is sometimes called an induced dipole-induced dipole attraction. London forces are the attractive forces that cause nonpolar substances to condense to liquids and to freeze into solids when the temperature is lowered sufficiently.

So when electrons are distributed unsymmetrically about the nucleus an atom or molecule can develop a temporary dipole.

Dispersion forces are present between all molecules, whether they are polar or nonpolar.

Larger and heavier atoms and molecules exhibit stronger dispersion forces than smaller and lighter ones.

In a larger atom or molecule, the valence electrons are, on average, farther from the nuclei than in a smaller atom or molecule. They are less tightly held and can more easily form temporary dipoles.

The ease with which the electron distribution around an atom or molecule can be distorted is called the polarizability. A molecule that has a charge cloud that is easily distorted is said to be very polarizable and will have large dispersion forces; one with a charge cloud that is difficult to distort is not very polarizable and will have small dispersion forces.

More carbons means a greater surface area possible for hydrophobic interaction, and thus higher boiling points.

The shapes of molecules also affect the magnitudes of the dispersion forces between them. For example, boiling points for the isomers n-pentane, isopentane, and neopentane are 36 °C, 27 °C, and 9.5 °C, respectively. Even though these compounds are composed of molecules with the same chemical formula, C5H12, the difference in boiling points suggests that dispersion forces in the liquid phase are different, being greatest for n-pentane and least for neopentane. The elongated shape of n-pentane provides a greater surface area available for contact between molecules, resulting in correspondingly stronger dispersion forces. The more compact shape of isopentane offers a smaller surface area available for intermolecular contact and, therefore, weaker dispersion forces. Neopentane molecules are the most compact of the three, offering the least available surface area for intermolecular contact and, hence, the weakest dispersion forces.

User Mukul
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