VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR) THEORY (SHAPES AND GEOMETRY OF MOLECULES)

Molecules exist in a variety of shapes. A number of physical and chemical properties of molecules arise from and are affected by their shapes. For example, the angular shape of the water molecules explains its many characteristic properties while a linear shape does not. The determination of the molecular geometry and the development of theories for explaining the preferred geometrical shapes of molecules is an integral part of chemical bonding. The VSEPR theory (model) is a simple treatment for understanding the shapes of molecules. Strictly speaking VSEPR theory is not a model of chemical bonding. It provides a simple recipe for predicting the shapes of molecules. It is infact an extension of the Lewis interpretation of bonding and is quite successful in predicting the shapes of simple polyatomic molecules. The basic assumptions of the VSEPR theory are that: Pairs of electrons in the valence shell of a central atom repel each other 1. These pairs of electrons tend to occupy position in space that minimize repulsions and thus maximize distance between them. 2. The valence shell is taken as a sphere with the electron pairs localizing on the spherical surface at maximum distance from one another. 3. A multiple bonds are treated as a single super pair. 4. Where two or more resonance structures can depict a molecule, the VSEPR model is applicable to any such structures For the prediction of geometrical shapes of molecules with the help of VSEPR model, it is convenient to divide molecules into two categories

Regular Geometry
Molecules in which the central atom has no lone pairs

Irregular Geometry
Molecules in which the central atom has one or more lone pairs, the lone pair of electrons in molecules occupy more space as compared to the bonding pair electrons. This causes greater repulsion between lone pairs of electrons as compared to the bond pairs repulsions. The descending order of repulsion (lp lp) > (lp bp) > (bp bp) where lp-Lone pair; bp-bond pair

Regular Geometry
Number of Arrangement of Molecular geometry Examples

electron pairs electrons 2 BAB Linear 3 BF3, AlCl3 BeCl2, HgCl2

= 120 4

= 120

CH4, NH4+, SiF4

5 PCl5, PF5

SF6

Irregular Geometry No. of Molecule Bonding Type pairs 2 No. of Arrangement of lone electrons pairs pair 1 Shape (Geometry)

Examples

AB2E

Bent

SO2, O3

AB3E

Trigonal pyramidal

NH3

AB2E2

H2O Bent

AB4E

SF4 See saw

AB3E2

CIF3 T shaped

AB5E

Square pyramidal

BrF5

AB4E2

Square planar

XeF4

Solved Examples
Example:Why the bond angle of H C H in methane (CH4) is 109 28 while H N H bond angle in NH3 is 107 though both carbon and nitrogen are sp 3 hybridized

Solution:In CH4 there are 4 bond pair of electrons while in NH3 are 3 bond pair of
electrons and 1 lone pair of electrons. Since bond pair bond pair repulsion is less than lone pair bond pair repulsion, in NH3 bond angle is reduced from 10928 to 107. Example:Why bond angle in NH3 is 107 while in H2O it is 104.5? Solution:In NH3, central nitrogen atom bears only one lone pair of electrons whereas in H2O central oxygen atom bears two lone pair of electrons.

Since the repulsion between lone pair-lone pair and lone pair bond pair is more than that between bond pair-bond pair, the repulsion in H2O is much greater than that in NH3 which results in contraction of bond angle from 10928 to 104.5 in water while in NH3 contraction is less i.e. from 10928 to 107. If the electronegativity of the peripheral atoms is more, then the bond angle will be less. For example if we consider NH3 and NF3, F N F bond angle will be lower than H N H bond angle. This is because in NF3 the bond pair is displaced more towards F and in NH3 it is displaced more towards N. So accordingly the b.p. b.p. interaction is less in NF3 and more in NH3. Example:The bond angle of H2O is 104 while that that of F2O is 102. Solution:Both H2O and F2O have a lone pair of electrons. But fluorine being highly electronegative, the bond pair of electrons are drawn more towards F in F 2O, whereas in H2O it is drawn towards O. So in F2O the bond pairs being displaced away from the central atom, has very little tendency to open up the angle. But in H2O this opening up is more as the bond pair electrons are closer to each other. So bond of F2O is less than H2O.

RESONANCE
There may be many molecules and ions for which it is not possible to draw a single Lewis structure. For example we can write two electronic structures of O 3.

In (A) the oxygen - oxygen bond on the left is a double bond and the oxygen-oxygen bond on the right is a single bond. In B the situation is just opposite. Experiment shows however, that the two bonds are identical. Therefore neither structure A nor B can be correct. One of the bonding pairs in ozone is spread over the region of all the three atom rather than associated with particular oxygen-oxygen bond. This delocalised bonding is a type of bonding in which bonding pair of electrons is spread over a number of atoms rather than localised between two.

Structures (A) and (B) are called resonating or canonical structures and C is the resonance hybrid. This phenomenon is called resonance, a situation in which more than one plausible structure can be written for a species and i Chemical bonding is the major part of chemistry which is an interaction between two or more atoms that holds them together by reducing the potential energy of their electrons. In other words Bonds are the like chemists "glue" - which hold atoms together in molecules or ions. Valence electrons are the outer shell electrons of an atom which take part in chemical bonding. Atoms gain or lose electrons to attain a more stable noble gas - like electron configuration (octet rule). There are two ways in which atoms can share electrons to satisfy the octet rule: Ionic Bonding - occurs when two or more ions combine to form an electrically-neutral compound The positive cation "loses" an electron (or 2 or 3) The negative anion "gains" the electron (or 2 or 3) The anion steals the electrons from the cation. Covalent Bonding - occurs when two or more atoms combine to form an electricallyneutral compound The electrons are shared between the two atoms. Both atoms don't have charge in the beginning and the compound remains with zero charge. The chemical activity of an atom is determined by the number of electrons in its valence shell. With the help of concept of chemical bonding one can define the structure of a compound and is used in many industries for manufacturing products. n which the true structure cannot be written at all. Some other examples (i) CO32 ion

Example (ii) Carbon-oxygen bond lengths in carboxylate ion are equal due to resonance.

(iii) Benzene

(iv) Vinyl Chloride

Difference in the energies of the canonical forms and resonance hybrid is called resonance stabilization energy and provides stability to species.

Rules for Writing Resonating Structures

Only electrons (not atoms) may be shifted and they may be shifted only to adjacent atoms or bond positions. The number of unpaired electrons should be same in all the canonical form. The positive charge should reside as far as possible on less electronegative atom and negative charge on more electronegative atom. Like charge should not reside on adjacent atom The larger the number of the resonating structures greater the stability of species. Greater number of covalency add to the stability of the molecule. Example: Out of the following resonating structures for CO2 molecule, which are important for describing the bonding in the molecule and why?

Solution: Out of the structures listed above, the structure (III) is wrong since the number of electron pairs on oxygen atoms are not permissible. Similarly, the structures (II) has very little contribution towards the hybrid because one of the oxygen atoms (electronegative) is show to have positive charge. Carbon dioxide is best represented by structures (I) and (IV).