H2 Chemistry: Organic Chemistry!

Factors influencing: 1. Boiling and melting point:

Number of C atoms: Increase in number of C atoms >>increase in number of electrons>>Electron cloud of molecule more polarisable >> Stronger van der Waals forces >> Higher bp / mp Branched / straight-chain molecules: Straight-chain molecules >> Larger surface area >> Greater extensiveness of van der Waals interactions >> Higher bp / mp Cis / Trans isomers: If substituents are polar, holding them in the cis -conformation will give rise to a net dipole moment, allowing them to form PD -PD interactions which are stronger than the ID-ID ones in trans-conformation>> Higher bp But cis-isomers cannot pack as well into a crystalline structure as the trans-isomer >> Less effective intermolecular forces >> Lower mp Symmetry (methylbenzene vs. benzene only): Methylbenzene is less symmetrical >> Less efficient packing >> Weaker intermolecular forces >> Methylbenzene has lower mp1 Presence (and number) of halogen atom(s): Presence of halogen atom >>Larger number of electrons in HD molecule >>Electron cloud of molecule more polarisable >> Stronger van der Waals forces >> Higher bp / mp Size of halogen atom (if any) 2:

Methylbenzene has a higher bp though due to its higher number of C atoms

Dominant factor (over changes in polarity of carbon halogen bond) in determining bp / mp in halogen derivatives as effect of increases in ID-ID (due to increased number of electrons in halogenoalkane molecule) outweighs the effect of decreases in PD-PD (due to decreased bond polarity of C-halogen bond) from alkyl fluoride to alkyl iodide.

Increase in size of halogen atom >> Increase in number of electrons (in molecule) >> Electron cloud of molecule more polarisable >>Stronger van der Waals forces >> Higher bp / mp Presence of polar C=O group (carbonyl compounds, acyl chlorides, esters ): Presence of polar C=O group >> Stronger PD-PD interactions (relative to ID-ID interactions) >> More energy required to overcome stronger PD-PD interactions >> Higher bp / mp

Presence (and number) of OH groups (alcohols, phenols, carboxylic acids): Presence of OH group >> Presence of hydrogen bonds 34 in addition to ID-ID interactions >> More energy required to overcome stronger hydrogen bonds in addition to ID -ID interactions >> Greater mp / bp Dimerisation(only in primary and secondary amides, and sometimes, carboxylic acids) Dimerisation>> Hydrogen bonds formed >> Higher bp / mp Primary / Secondary / Tertiary Amines (amines only): Primary and secondary amines >> Able to form strong hydrogen bonding between their molecules >> Higher bp / mp than tertiary ones (which can only form weak van der Waals forces) Presence of zwitterions (only in amino acids) : Presence of zwitterions >> Strong electrostatic attraction between oppositely charged groups of zwitterions formed >> Higher bp / mp

2. Solubility in water / polar solvents:

Presence of non-polar hydrocarbon chains / benzene rings Presence of non-polar hydrocarbon chains / benzene rings>>Cannot form effective polar interactions with water molecules for dissolving to occur >> Insoluble5

Hydrogen bonds are stronger than PD-PD interactions (such as those in carbonyl compounds)

Hydrogen bonds in carboxylic acids are stronger than those in alcohols as OH groups in COOH is more polar due to presence of electron withdrawing carbonyl group. Note: Phenols, though having benzene rings, are still slightly soluble in cold water (emulsion formed) as hydrogen bonds can form between OH groups and water molecules (though slightly hindered by benzene ring)
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Length of non-polar hydrocarbon chains Longer hydrocarbon chains >> Hinder formation of hydrogen bonds with water molecules >> Decreased solubility Presence of polar OH, -COOH or C=O groups 6 Presence of polar OH, -COOH or C=O groups >> Can form hydrogen bonds with water molecules >> Increased solubility ~ Presence of N atom (amines and amides only) Presence of N atom >> Presence of lone pair of electrons on N atom >> N can form hydrogen bonds with water molecules>> Soluble Presence of zwitterions (amino acids only) Presence of zwitterions >> Can form ion-dipole interactions with water molecules for dissolving to occur >> Soluble Presence of polar R-groups (proteins only) Presence of polar R-groups >> Can form ion-dipole interactions or hydrogen bonds with water molecules for dissolving to occur >> Soluble Note: Even though HD molecules have the polar carbon-halogen bond, they are still insoluble as they cannot form hydrogen bonds with water

3. Acidity (Stability of anion of the dissociated acid)

Increased stability of anion will lead to an increased acid strength Presence of electron-withdrawing substituents Presence of electron-withdrawing substituents >> Delocalise the negative charge about the anion >> Increased stability of anion >> Increased acid strength Presence of electron-donating substituents Presence of electron-donating substituents >> Intensify the negative charge about the anion >> Decreased stability of anion >> Decreased acid strength Number of electron-donating / withdrawing substituents Increased number of electron-donating / withdrawing substituents >> Negative charge about the anion dispersed / intensified to a greater extent

Except acyl chlorides since they hydrolyse rapidly in water.

>> Increased / decreased stability of anion >> Increased / decreased acid strength Proximity of electron-donating / withdrawing substituents Electron-donating / withdrawing substituents located more closely to negatively charged group >> Negative charge about anion dispersed / intensified more effectively >> Increased / decreased stability of anion >> Increased / decreased acid strength Presence of benzene ring Presence of benzene ring >> Negative charge will be delocalised into the benzene ring >> Increased stability of anion >> Increased acid strength

4. Basicity (Availability of lone pair of electrons for protonation) Aliphatic amines are stronger bases (than NH 3) Electron-donating alkyl groups >> Lone pair of electrons on N atom of amine more available for protonation >> Increased basicity Phenylamine is a weaker base (than NH 3) Lone pair of electrons on N atom delocalised into the benzene ring, making it less available for protonation >>Decreased basicity Presence of electron-withdrawing substituents Presence of electron-withdrawing substituents make the lone pair of electrons on N atom less available for protonation >> Decreased basicity