Acidity and Basicity of Organic Molecules

Many important intermediates in chemical reactions are formed as a result of modifying a molecule or ion by the removal or addition of a proton. The ease with which this can be done is described by the acidity or basicity constant (Ka or Kb) of the molecule. It is possible to estimate Ka or pKa values for molecules that are quite non-acidic from a knowledge of the energy needed to remove a proton. Thus, whereas the Ka of acetic acid is 1.9E-5, the Ka of ethane (CH3CH3) is about 1E-60. This means that it is about 1055 times harder to remove a proton from ethane than it is to remove the proton from the carboxyl group of acetic acid. Even though we can assign an acidity constant to ethane, we would never describe it as 'an acid'. A molecule is not described as being 'acidic' or 'basic' just because acidity or basicity constants are given for it!

Factors Affecting Acidity and Basicity

There are four important factors that help increase the ease with which a proton (H+) can be removed from a molecule HA: 1. 2. 3. 4. the electronegativity of the atom to which the H is attached the electronegativity of the atom(s) adjacent to the site of the H the hybridisation of the conjugate base the extent to which the negative charge on the conjugate base (A-) can be delocalised (resonance stability). The Higher the Electronegativity, The more acidic the proton. 1. Rank these molecules according to their relative pKa values on the scale shown below.

2. Indicate which of the hydrogens would be easier to remove as a proton by clicking on the molecule showing the appropriate highlighted hydrogen. CH3COOH CH3COOH

The H on the COOH is attached to a highly electronegative O and another O is attached to the adjacent carbon, therefor it is a clearly acidic H. The H on the CH3 atoms are attached to the C atoms which are only slightly more electronegative compared to H. Therefore they are slightly harder to remove, nonacidic.
The property of an acid is to : Donate a proton. "easier to remove"

Effect of Carbon Hybridisation 1

The effective electronegativity of a C atom in an organic molecule depends on its hybridisation state. The greater the degree of p character in a hybrid orbital, the further away from the C nucleus will be the 'centre of gravity' of the electron density.

Conversely, the greater the s character of a hybrid orbital, the closer will be the 'centre of gravity' of the electron density to the C nucleus. There fore a greater
electronegativity.

Charge Delocalisation Effects on Acidity

1.

2.

Bond Making and Breaking

When a covalent bond in a molecule is broken, two outcomes are possible: 1) Homolytic Cleavage formation of radicals 2) Heterolytic Cleavage formation of ions

Determining which atom retains the two electrons from the covalent bond in heterolytic cleavage depens on the polarization of the bond.

Mechanistic Arrows
Chemists use a special arrow notation to show the movement of electrons during a reaction. These arrows are called mechanistic arrows. A single-sided curved arrow while A double-sided curved arrow represents the movement of only one electron

represents the movement of two electrons.

The correct way to draw mechanistic arrows is to show the arrow beginning from a region of high electron density (such as a bond or a lone pair of electrons) and

terminating at the new resting-place of the electrons, thereby forming a new bond or breaking an existing bond.

Types of Reagent
Most chemical reactions involve the interaction of nucleophiles and electrophiles. * Nucleophiles - (nucleus-loving) - ions or molecules that are able to donate a pair of electrons. Often these species have a lone pair of electrons, however, sometimes they do not (e.g. the double bonds in alkenes are electron rich and often act as nucleophiles). * Electrophiles - (electron-loving) - ions or molecules that can accept a pair of electrons. Often these species are positively charged (or +) or are electron deficient (e.g. AlCl3).

Mechanistic arrows often begin at a nucleophile, or terminate at an electrophile.