Valence Bond Theory Guidelines for Determining Bonding Description We will limit our discussion to sp, sp2, and

d sp3 hybridization [no d orbitals]. These hybridizations will allow a valence bond description for covalent bonding in molecules obeying the octet rule and those with less than an octet [NOT for more than an octet]. Covalent bonds are formed in the valence bond theory view of bonding by the overlap of orbitals from each of two bonded atoms. The overlap of the orbitals results in a covalent bond which is a shared orbital between the two atoms. 1. 2. 3. Draw the Lewis structure for the molecule. Count the number of electron domains around the central atom. The central atom needs one bonding hybrid orbital for each of the electron domains. The hybrid orbitals necessarily must reflect the geometry of the molecule [bond angles]. Hybrid orbitals result from the mixing of atomic orbitals; when mixing, orbitals are conserved, that is, two atomic orbitals mix to form two hybrid orbitals and three atomic orbitals mix to form three hybrid orbitals. A. If the central atom has two domains of electrons [linear molecules], two hybrid orbitals are required. This is because two identical bonding orbitals are required. In order to have two identical hybrid orbitals, two atomic orbitals need to be mixed: an s orbital and a p orbital. This yields two sp hybrid orbitals. Each sp hybrid is oriented 180o with respect to each other. This is necessary to describe the linear geometry of the molecule. See figures 9.16 and 9.17 on page 333 of the text. [Examples: BeH2, BeX3, where X = halogen, and linear molecules/ions with two domains of electrons, such as CO2 and CS2] If the central atom has three domains of electrons [trigonal planar molecules], three hybrid orbitals are required. This is because three identical bonding orbitals are required. In order to have three identical hybrid orbitals, three atomic orbitals need to be mixed: an s orbital and two p orbitals. This yields three sp2 hybrid orbitals. Each sp2 hybrid is oriented 120o with respect to each other. This is necessary to describe the trigonal planar geometry of the molecule. See figure 9.18 of the text, page 334. [Examples: BH3, BX3, where X = halogen, and Trigonal planar molecules/ions with three domains of electrons, such as NO2, O3, CO2 and CS2] If the central atom has four domains of electrons [tetrahedral molecules], four hybrid orbitals are required. This is because four identical bonding orbitals are required. In order to have four identical hybrid orbitals, four atomic orbitals need to be mixed: an s orbital and three p orbitals. This yields four sp3 hybrid orbitals. Each sp3 hybrid is oriented 109.5o with respect to each other. This is necessary to describe the tetrahedral geometry of the molecule. See figure 9.19, 9.20, and 9.21 of the text, pages 335, 335, and 337, respectively. [Examples: CH4, H2O, NH3, and PO43]

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C.

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If substituent atoms bonded to the central atom are bonded only to the central atom via a single bond and to no other atom, then the bond is formed by the overlap of an unhybridized orbital on the substituent atom with the hybrid orbital of the central atom. The resultant bond is a sigma [] bond. Read sample exercise 9.5 on page 337 of the text. If substituent atoms bonded to the central atom are bonded to the central atom and another atom or the substituent atom is bonded to the central atom via multiple bonds, then the substituent atom must also be considered as a central atom and hybridization employed. The resultant bond is a sigma [] bond. See figures 9.24 and 9.26 on pages 338 and 339 of the text and carefully read sample exercise 9.6 on pages 339 and 340.

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Multiple bonding. In multiple bonds, one of the bonds is always a sigma bond, the remaining bonds are always pi bonds. Pi [] bonds are formed from the sideways overlap of unhybridized p orbitals. Thus, if there is a double bond, one of the bonds is a sigma bond and the second is a pi bond. If there is a triple bond, one of the bonds is a sigma bond and the remaining 2 bonds are pi bonds. See figures 9.25 and 9.26 on page 339 in the text. Read carefully sample exercise 9.6 on pages 339 and 340 in the text.

Online tutorial about hybridization skip the portion referring to d orbital hybrids. http://chemistry.boisestate.edu/rbanks/inorganic/bonding%20and%20hybridization/bonding_hybridization.htm Read carefully the General conclusions on page 343 of the text. Examples: 1. Describe the bonding in Cl2O. The central atom in Cl2O is O. The Lewis structure consists of a central O atom with two Cl atoms bonded to it and two electron lone pairs. Thus the central O atom has 4 electron domains around it. This means the O atom needs 4 hybrid orbitals and therefore the hybridization is sp3 [four hybrid orbitals result from mixing four atomic orbitals, one s orbital and three p orbitals]. Th The chlorine atom has a p orbital with a single electron in it, making it suitable for bonding. Therefore the Cl atom does not undergo hybridization. The bonding in Cl2O is then described as follows: Two identical O Cl bonds each are characterized as the overlap of an O sp3 hybrid orbital with an unhybridized 3p orbital on the Cl atom. The O Cl bonds are sigma [] bonds. Each lone pair on the central oxygen sits in an sp3 hybrid. The bond angle of the Cl O Cl bond is less than 109.5o [104.5o]. 2. Describe the bonding in HCN. In the Lewis structure, H is bonded via a single bond to the central C atom and N is triple bonded to the central C atom. There are two domains of electrons around the central C atom, thus the hybridization is sp. The N atom has two domains of electrons around itself, thus it is also sp hybridized. Description of bonding: C H bond: A single sigma [] bond forms via the overlap of a H 1s orbital with a C sp hybrid orbital. CN bond: A sigma [] bond between the C and N forms via the overlap of a C sp hybrid orbital and a N sp hybrid orbital. Two pi [] bonds form between the C and N atom via the overlap of unhybridized p orbitals. Each one of the two bonds are described as: overlap of an unhybridized p orbital from the C atom with an unhybridized p orbital from the N atom.