Valence Bond Theory

Valence Bond Theory

As we know the Lewis approach helps in writing the structure for molecules but it fails to explain the formation of chemical bond. It also does not give any reason for the difference in bond dissociation enthalpies and bond lengths in molecules like H₂ (435.8 kJ mol^-1, 74 pm) and F₂ (150.6 kJ mol^-1, 42 pm), although in both the cases a single covalent bond is formed by the sharing of an electron pair between the respective atoms. It also gives no idea about the shapes of polyatomic molecules.

Similarly the VSEPR theory gives the geometry of simple molecules but theoretically, it does not explain them and also it has limited applications. To overcome these limitations the two important theories based on quantum mechanical principles are introduced. These are valence bond (VB) theory and molecular orbital (MO) theory.

Valence bond theory was introduced by Heitler and London (1927) and developed further by Pauling and others. A discussion of the valence bond theory is based on the knowledge of atomic orbitals, electronic configurations of elements, the hybridization of atomic orbitals and the principles of variation and superposition. A rigorous treatment of the VB theory in terms of these aspects is beyond the scope of this book. Therefore, for the sake of convenience, valence bond theory has been discussed in terms of qualitative and non-mathematical treatment only. To start with, let us consider the formation of hydrogen molecule which is the simplest of all molecules.

Consider two hydrogen atoms A and B approaching each other having nuclei N_A and N_B and electrons present in them are represented by e_A and e_B. When the two atoms are at large distance from each other, new attractive and repulsive forces begin to operate.

Attractive forces arise between:

Nucleus of one atom and its own electron that is N_A – e_A and N_B –e_B.

Nucleus of one atom and electron of other atom i.e., N_A – e_B, N_B – e_A.

Similarly repulsive forces arise between

(i)                Electrons of two atoms like e_A – e_B

(ii)              Nuclei of two atoms N_A – N_B

Attractive forces tend to bring the two atoms close to each other whereas repulsive forces tend to push them apart.

Experimentally it has been found that the magnitude of new attractive force is more than the new repulsive forces. As a result, two atoms approach each other and potential energy decreases. Ultimately a stage is reached where the net force of attraction balances the force of repulsion and system acquires minimum energy. At this stage two hydrogen atoms are said to be bonded together to form a stable molecule having the bond length of 74 pm.

Since the energy gets released when the bond is formed between two hydrogen atoms, the hydrogen molecule is more stable than that of isolatded hydrogen atoms. The energy so released is called as bond enthalpy, which is corresponding to minimum in the curve depicted in the below figure. Conversely, 435.8 kJ of energy is required to dissociate one mole of H₂ molecule.

                                              H₂(g) + 435.8 kJ mol^-1  -  H(g) + H(g)