Chapter 2 : Chemical Bonding 2.

1 Electrovalent bond

Explain, with the aid of Lewis diagram, the FORMATION OF IONIC BOND in sodium chloride. Sodium atom has 1 valence electron Whereas chlorine atom has 7 valence electrons The sodium atom donates an electron to form a sodium ion, Na+ The chloride atom accepts the electron from sodium atom to form a chloride ion, ClAs shown,

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One atom of sodium reacts with one atom of chlorine. The resulting oppositely charged ions are then attracted towards each other by electrostatic force which is known as ionic or electrovalent bond.

** Lithium, magnesium and aluminum forms mainly covalent compounds (large ionization energies / high polarizing power of the cation formed) ** Formation of an ionic bond involves transfer of electron between • A metal with low ionization energy (large atomic size) • A non-metal with high electron affinity (small atomic size)

2.2

Covalent bond

With the aid of a lewis diagram, explain the formation of covalent bond in aluminium chloride Aluminium atom has 3 valence electrons whereas chlorine atom has 7 valence electrons Three chlorine atoms, each contributes one electron, share electrons with one aluminium atom As shown

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The electronic force between nuclei of aluminium and chlorine atoms with the shared pair of electrons is known as covalent bond. The formation of AlCl3 molecules involves formation of three single covalent bond Aluminium atom of the AlCl3 molecules has an empty orbital And thus could accept a lone pair of electrons of the chlorine atom from the second AlCl3 molecules to form a dative bond As shown in the lewis diagram below

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Hence two AlCl3 molecules are held together by two dative bonds to form a dimer, Al2Cl6 (Dimer)

Overlapping of Orbital Explain the formation of covalent bond using overlapping of orbitals Formation of covalent bond involves overlapping of orbitals with single electron Overlapping of s-s orbitals in H2 molecule

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Overlapping of s-orbital of hydrogen atom and p-orbital of chlorine atom in HCl molecule

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Overlapping of p-orbitals to form Cl2 molecule

Lateral overlap of p-orbitals to form Π-bond

The electrostatic force between the nuclei of 2 atoms and the electron charge cloud is known as covalent bond ** Type of orbital involved in bonding is related to the position in the periodic table (the block where it is situated) Double bond

Triple bond

A covalent bond is characterized by a. Bond length The greater the degree of overlapping between 2 orbitals, the stronger the bond formed. s-s > p-p σ>Π C≡C > C=C > C-C As the 2 atoms approach each other to form the bond, the attractive forces are replaced by repulsive forces between the 2 positively charged nuclei. Hence there is an optimum distance of separation between the 2 nuclei The average distance between the nuclei of the 2 bonded atoms is called the bond length The shorter the bond length, the stronger the covalent bond b. Bond strength / bond energy (The strength of a covalent bond is measured by the bond energy. The bond energy is the amount of energy required to break a mole of covalent bond) *The shorter the bond length, the stronger the covalent bond *The greater the number of bond, the stronger the bond

c. Bond angle / shape of molecule VSEPR Theory Hybridisation Theory

VSEPR Theory

3 Principles in VSEPR Theory : a. The orbital of the electron pairs tend to become as widely separated as possible . (The electrical field of one electron pair exerts a strong repulsion on the electrical field of another electron pair)

b. Orbitals of lone pair electrons exert a bigger repulsion than those of bond pair electrons LP-LP repulsion > LP-BP repulsion > BP-BP repulsion c. Repulsion between orbitals is increased by increase of electronegativity of the central atom

Hybridisation Theory and shape of molecules

In many cases, the number of covalent bonds which an atom forms is equal to the number of unpaired electrons in the atom. However in many other cases, this is not true. The hybridization theory is used to explain this phenomenon. This theory is also used to explain the shape of molecules / bond angle 1. sp3 hybridisation a. Formation of 4 equivalent C-H bonds in the methane molecule and bond angle H-C-H 109.5o Electronic configuration of central atom carbon :

The 4 hybrid orbitals are directed towards the vertices of a regular tetrahedron. Each of these orbitals can then overlap with the s-orbital of a hydrogen atom to form C-H σ-bond

- Label orbital - Label σ, Π - Shape / Angle

b. Formation of 3 equivalent N-H bonds and bond angle H-N-H 107o in the ammonia molecule Electronic configuration of central atom nitrogen :

Since there are 5 electrons occupying 4 orbitals, - Therefore one of the orbitals contains lone pair - Overlap of each other of the three singly filled sp3 hybrid orbitals with the 1s orbital of the hydrogen atoms - Resulting in the formation of ammonia pyramidal structure

molecule with a

c. Formation of two equivalent O-H bonds with bond angle H-O-H of 104.5o in the water molecule Electronic configuration of central atom oxygen : Since there are 6 electrons occupying 4 orbitals, 2 of them will contain lone pair of electrons. Overlap of the other two hybrid orbitals with the 1s orbital of hydrogen atom produces water molecules with v-shape. 2. sp2 hybridisation a. Formation of BF3 molecule with bond angle F-B-F 120o

The hybrid orbitals are coplanar and 120o to each other. Overlap between each of the hybrid orbitals with the 2p orbital of the fluorine atom produces BF3 molecule with a trigonal planar structure.

b. Formation of ethane molecules with bond angle H-C-H 120o

The 3 equivalent sp2 hybrid orbitals arranged symmetrically in a plane with the 2pz orbital remaining unaltered and is perpendicular to the plane. When two carbon atoms are sp2 hybridised, each carbon atom can then form a σ-bond with each other by overlapping of their sp2 hybrid orbitals and two σ- bond by overlapping of the remaining two sp2 hybrid orbitals with the 1s orbitals of two hydrogen atoms. The two 2pz orbitals can overlap laterally with each other to form a Π- bond between two carbon atoms

Thus, ethane is a flat molecule.

3. sp hybridization a. Formation of BeCl2 molecule with bond angle Cl-Be-Cl 180o Electronic configuration of central atom beryllium

Overlap the two sp hybrid orbitals of beryllium with singly filled 3p orbitals of the chlorine atom gives a liner BeCl2 molecule

b. Formation of ethyne molecule with bond angle H-C-H 180o Electronic configuration of central atom carbon

sp hybridization produces 2 equivalent sp hybris orbitals leaving 2 singly filled p orbitals lie at right angle to each other and to the axis of the 2 hybrid orbitals Lateral overlap between 2p orbitals produces Π-electron cloud with 2 lobes. If one lobe of a Π-cloud is pictured as lying above and one below the line joining the two carbon nuclei, then the two lobes of the other two Π-electron cloud lie in front and back of the line. However, overlapping between the two Π-electron cloud can also occur, that is the 4 lobes can merge to form a single cylindrical sheath of electron clouds about the line joining the two carbon nuclei.

Expanding octet and octet hindrance
Expansion of octet occurs in element in the 3rd period and above due to the presence of d-orbitals.

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Promotion of electrons to the 3d orbitals Expansion of octet can occur 2d orbital does not exist No expansion of octet

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Contain how many electron State reason why : Expansion of octet cannot occur, steric hindrance occurs due to large atom

Dative Bond (Co-ordinate bond) (This bond is similar to the covalent bond except that only one atom provides the electron pair required for bonding) Donor atom (with lone pairs of electrons) + Acceptor atom (empty orbital) A dative bond is represented by an ARROW from the donor atom to the acceptor atom

Metallic Bond The atoms in a metal are packed together closely. Each of the atom loses control over one or more of its valence electrons. These electrons are no longer associated with a particular atom but are free to move through ut the piece of metal. These electrons are said to be delocalized. 1. 2. 3. 4. Metallic bond is the attractive force between the positive metal ions with the delocalized electrons. Magnitude of the bond depends on the number of electron valence per atom and the size of the positive metal ion. The enthalpy of vaporization increases in the order : Na < Mg < Al Conductors, semiconductors and insulators – BAND THEORY

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A molecular orbital picture of solids leads to the idea that there are 2 groups of energy levels or orbitals. The lower is called the valence band and the higher the conduction band If the conduction band is partly filled with electrons, the electrons can move through, out the crystals. The difference between conductors, semiconductors and insulators depends on the energy gap between two bands. In conductors, the two bands overlap, so that the conduction band is always partly filled In semiconductors, two bands are close together so that a few high-energy electrons can jump into conduction band In insulators the gap between the bands is large and no electrons exist in the conduction Increasing the temperature of a semiconductor improves its conductivity as more electrons are able to reach the conduction band, but increasing the temperature of a metal conductor decreases its conductivity because vibrations of the lattice of ions impede the free movement of the electrons in the conduction band.

Resonance Structure

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