Monday, August 27, 2018

Theories of co-valent bonding


In this post, valence bond theory of covalent bonding is discussed in a basic level. small videos are also posted to understand atomic orbital overlapping concept and hybridization concept.

VALENCE BOND THEORY

The valence bond theory states that "atoms in a covalent bond share electron density through the overlapping (ஒன்றுடன் ஒன்று படிதல்)of their valence atomic orbitals".This creates an area of electron pair density between the two atoms.

EXAMPLE:  Hydrogen molecule

The 1s orbitals of the two hydrogens approach each other and overlap to form a bond  known as a sigma bond (σ bond) It is also known as s-s overlapping.


Figure #.#. A diagram illustrating the overlap of s orbitals of two hydrogen atoms to form H2.
Thus, according to valence bond theory, a covalent bond results when two conditions are met: 
(1) an orbital on one atom overlaps an orbital on a second atom and 
(2) the single electrons in each orbital combine to form an electron pair.

Figure below shows the energy changes of H2 molecule when bonding occurs.
A pair of diagrams are shown and labeled “a” and “b”. Diagram a shows three consecutive images. The first image depicts two separated blurry circles, each labeled with a positive sign and the term “H atom.” The phrase written under them reads, “Sufficiently far apart to have no interaction.” The second image shows the same two circles, but this time they are much closer together and are labeled, “Atoms begin to interact as they move closer together.” The third image shows the two circles overlapping, labeled, “H subscript 2,” and, “Optimum distance to achieve lowest overall energy of system.” Diagram b shows a graph on which the y-axis is labeled “Energy ( J ),” and the x-axis is labeled, “Internuclear distance ( p m ).” The midpoint of the y-axis is labeled as zero. The curve on the graph begins at zero p m and high on the y-axis. The graph slopes downward steeply to a point far below the zero joule line on the y-axis and the lowest point reads “0.74 p m” and “H bonded to H bond length.” It is also labeled “ negative 7.24 times 10 superscript negative 19 J.” The graph then rises again to zero J. The graph is accompanied by the same images from diagram a; the first image correlates to the point in the graph where it crosses the zero point on the y-axis, the third image where the graph is lowest.
(a) The interaction of two hydrogen atoms changes as a function of distance. (b) The energy of the system changes as the

 the atoms interact. The lowest (most stable) energy occurs at a distance of 74 pm, which is the bond length observed for the H2 molecule.

Similarly a atomic orbital with a p atomic orbital overlaps to form sigma bond (s-p overlaping). Example: Hydrogen fluoride (HF)


A sigma bond can also be formed by the overlap of two orbitals.  The covalent bond in molecular fluorine, F2, is a sigma bond formed by the overlap of two half-filled 2p orbitals, one from each fluorine atom. 


HYBRIDIZATION

Hybridization was introduced to explain molecular structure when the valence bond theory failed to correctly predict them.
The concept involves the "cross breeding" of atomic orbitals to create "new" orbitals. Hence the use of the term "hybrid" : think of a hybrid animal which is a cross breed of two species. 
The intermixing of two or more pure atomic orbitals of an atom with almost same energy to give same number of identical and degenerate new type of orbitals is known as hybridization. The new orbitals formed are also known as hybrid orbitals.
Image result for sp hybridization
The above diagram shows a sp-hybrid orbital formed by inter-mixing of s and p atomic orbital. Look the two newly formed hybrid orbitals are identical in shape. The sp hybrid orbitals are arranged linearly (180 degree). They posses 50% s and 50% p character.

Example: Formation of BeCl2  using sp-hybridization is shown in the following video.


References:
1. https://opentextbc.ca/introductorychemistry/chapter/valence-bond-theory-and-hybrid-orbitals-2/
2. https://opentextbc.ca/chemistry/chapter/8-1-valence-bond-theory/#CNX_Chem_08_01_sigma
3. https://chem.libretexts.org
4.https://chem.libretexts.org/Textbook_Maps/Organic_Chemistry/Supplemental_Modules_(Organic_Chemistry)/Fundamentals/Hybrid_Orbitals
5.http://www.chem.ucalgary.ca/courses/350/Carey5th/Ch02/ch2-3.html

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