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Aniline does not undergo Friedel craft's reactions because the reagent AlCl3 (the Lewis acid which is used as a catalyst in friedel crafts reaction), being electron deficient acts as a Lewis base.
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To be miscible with water, the solute-water force of attraction must be stronger than the solute-solute and water-water forces of attraction. Alkyl halides are polar molecules and so held together by dipole-dipole interactions. Similarly, strong H-bonds exist between the water molecules. The new force of attraction between the alkyl halides and water molecules is weaker than the alkyl halide-alkyl halide and water-water forces of attraction. Hence, alkyl halides (though polar) are immiscible with water.
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NO2 is an odd electron (7+2×8=23) molecule. In the valence shell, N has seven electrons and hence is stable. To become stable by having 8 number electrons in the valence shell, it undergoes dimerisation to form N2O4.
2NO2 ═ N2O4

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