Unit 1 : Chemical Bonding and Molecular Structure (sem 2) Q 1: Explain KOSSEL-LEWIS approach to chemical bonding.

In order to explain the formation of chemical bond in terms of electrons, a number of attempts were made, but it was only in 1916 when Kossel and Lewis succeeded independently in giving a satisfactory explanation. They were the first to provide some logical explanation of valence which was based on the inertness of noble gases. Lewis pictured the atom in terms of a positively charged Kernel (the nucleus plus the inner electrons) and the outer shell that could accommodate a maximum of eight electrons. According to him these eight electrons occupy the corners of a cube which surround the Kernel. Thus the single outer shell electron of sodium would occupy one corner of the cube, while in the case of a noble gas all the eight corners would be occupied. This octet of electrons represents a particularly stable electronic arrangement. Lewis postulated that atoms achieve the stable octet when they are linked by chemical bonds. In the case of sodium and chlorine, this can happen by the transfer of an electron from sodium to chlorine thereby giving the Na+ and Cl ions. In the case of other molecules like Cl2, H2, F2, etc., the bond is formed by the sharing of a pair of electrons between the atoms. In the process each atom attains a stable outer octet of electrons. Q 2: Write a note on Lewis Symbols. In the formation of a molecule, only the outer shell electrons take part in chemical combination and they are known as valence electrons. The inner shell electrons are well protected and are generally not involved in the combination process. G.N. Lewis, an American chemist introduced simple notations to represent valence electrons in an atom. These notations are called Lewis symbols. For example, the Lewis symbols for the elements of second period are as under:
Li Be B C N O F Ne

Q 3: What is the significance of Lewis Symbols? The number of dots around the symbol represents the number of valence electrons. This number of valence electrons helps to calculate the common or group valence of the element. The group valence of the elements is generally either equal to the number of dots in Lewis symbols or 8 minus the number of dots or valence electrons. Q 4: State octet rule. Kossel and Lewis in 1916 developed an important theory of chemical combination between atoms known as electronic theory of chemical bonding. According to this, atoms can combine either by transfer of valence electrons from one atom to another (gaining or losing) or by sharing of valence electrons in order to have an octet in their valence shells. This is known as octet rule. Q 5: On the basis of Kossel-Lewis postulates, explain the formation of sodium chloride Kossel, in relation to chemical bonding, drew attention to the following facts: In the periodic table, the highly electronegative halogens and the highly electropositive alkali metals are separated by the noble gases. The formation of a negative ion from a halogen atom and a positive ion from an alkali metal atom is associated with the gain and loss of an electron by the respective atoms. The negative and positive ions thus formed attain stable noble gas electronic configurations. The noble gases (with the exception of helium which has a duplet of electrons) have a particularly stable outer shell configuration of eight (octet) electrons, ns2np6. The negative and positive ions are stabilized by electrostatic attraction. For example, the formation of NaCl from sodium and chlorine, according to the above scheme, can be explained as: Na Na+ + 1e Cl + e Cl 1 0 2 5 [Ne]3s [Ne]3s [Ne] 3s 3p [Ne] 3s23p6

Na+ + ClNaCl The bond formed, as a result of the electrostatic attraction between the positive and negative ions was termed as the electrovalent bond. The electrovalence is thus equal to the number of unit charge(s) on the ion. Hence sodium is assigned a positive electrovalence of one, while chlorine a negative electrovalence of one. Kossels postulations provide the basis for the modern concepts regarding ion-formation by electron transfer and the formation of ionic crystalline compounds. This theory proved to be of great value in the understanding and systematisation of the ionic compounds. At the same time it is necessary to recognise the fact that a large number of compounds (covalent compounds) did not fit into these concepts.

Q 6: What is ionic bond? Mention factors for the formation of ionic compounds. OR Explain ionic or electrovalent bond. From the Kossel and Lewis treatment of the formation of an ionic bond, it follows that the formation of ionic compounds would primarily depend upon the ease of formation of the positive and negative ions from the respective neutral atoms. The arrangement of the positive and negative ions in the solid, that is, the lattice of the crystalline compound. The formation of a positive ion involves ionization, i.e., removal of electron(s) from the neutral atom and that of the negative ion involves the addition of electron(s) to the neutral atom. M(g) M+(g) + e Ionization enthalpy X(g) + e X (g) Electron gain enthalpy M+(g) + X(g) MX(s) The electron gain enthalpy, egH, is the enthalpy change, when a gas phase atom in its ground state gains an electron. The electron gain process may be exothermic or endothermic. The ionization, on the other hand, is always endothermic. Electron affinity is the negative of the energy change accompanying electron gain. Obviously ionic bonds will be formed more easily between elements with comparatively low ionization enthalpies and elements with comparatively high negative value of electron gain enthalpy. Most ionic compounds have cations derived from metallic elements and anions from non-metallic elements. The ammonium ion, (made up of two non-metallic elements) is an exception. It forms the cation of a number of ionic compounds. Q 7: What is called crystal structure of ionic solids? Give information about the crystal lattice energy of ionic solid Ionic compounds in the crystalline state consist of orderly three-dimensional arrangements of cations and anions held together by coulombic interaction energies. Such an arrangement is known as crystal structure or crystal configuration. These compounds crystallise in different crystal structures determined by the size of the ions, their packing arrangements and other factors. In ionic solids, the sum of the electron gain enthalpy and the ionization enthalpy may be positive but still the crystal structure gets stabilized due to the energy released in the formation of the crystal lattice. For example : the ionization enthalpy for Na+(g) formation from Na(g) is 495.8 kJ mol1 ; while the electron gain enthalpy for the change Cl(g) + e Cl(g) is, 348.7 kJ mol1 only. The sum of the two, 147.1 kJ mol-1 is more than compensated for by the enthalpy of lattice formation of NaCl (s) (788 kJ mol1).Therefore, the energy released in the processes is more than the energy absorbed. Thus a qualitative measure of the stability of an ionic compound is provided by its enthalpy of lattice formation and not simply by achieving octet of electrons around the ionic species in gaseous state. Thus lattice enthalpy plays a key role in the formation of ionic compounds. The Lattice Enthalpy of an ionic solid is defined as the energy required to completely separating one mole of a solid ionic compound into gaseous constituent ions. For example, the lattice enthalpy of NaCl is 788 kJ mol1. This means that 788 kJ of energy is required to separate one mole of solid NaCl into one mole of Na+(g) and one mole of Cl(g) to an infinite distance.

 This process involves both the attractive forces between ions of opposite charges and the repulsive forces between ions of like charge. The solid crystal being three dimensional; it is not possible to calculate lattice enthalpy directly from the interaction of forces of attraction and repulsion only. Factors associated with the crystal geometry have to be included. Some important points for crystal lattice formation is as follows 1) The greater the crystal lattice energy, more stable is the ionic compound 2) The crystal lattice energy is greater for ions of higher charge and smaller radil. 3) The higher value of crystal lattice energy increases the auto-ionization reaction of ionic compound in aqueous solutions. [Remember ionic compounds become water soluble if their lattice energy is less than their heat of hydration.] Q 9: Explain Covalent Bond Langmuir (1919) refined the Lewis postulations by abandoning the idea of the stationary cubical arrangement of the octet, and by introducing the term covalent bond. When two or more atoms (similar or dissimilar) of any elements attain octet structure by sharing of their valence electrons the bond formed is called covalent bond. The Lewis-Langmuir theory can be understood by considering the formation of the chlorine molecule,Cl2. The Cl atom with electronic configuration, [Ne]3 s2 3p5, is one electron short of the argon configuration. The formation of the Cl2 molecule can be understood in terms of the sharing of a pair of electrons between the two chlorine atoms, each chlorine atom contributing one electron to the shared pair. In the process both chlorine atoms attain the outer shell octet of the nearest noble gas (i.e., argon).
C l + C l C l C l

{The dots represent electrons. Such structures are referred to as Lewis dot structures.} When combining atoms share two electrons each then they form the double bond.
H
O C O or O C O

H C C H C C

H or C H C

H H

H H

When combining atoms share three electrons each then they form the triple bond .
N N o r N N

H or H

Q 10: Write a note on Lewis dot structure and explain it with examples. The Lewis dot structures can be written for other molecules also, in which the combining atoms may be identical or different. The important conditions being that: Each bond is formed as a result of sharing of an electron pair between the atoms. Each combining atom contributes at least one electron to the shared pair. The combining atoms attain the outer shell noble gas configurations as a result of the sharing of electrons. Thus in water and carbon tetrachloride molecules, formation of covalent bonds can be represented as:
Cl Cl C Cl Cl

Thus, when two atoms share one electron pair they are said to be joined by a single covalent bond. In many compounds we have multiple bonds between atoms. The formation of multiple bonds indicates sharing of more than one electron pair between two atoms. If two atoms share two pairs of electrons, the covalent bond between them is called a double bond. For example, in the carbon dioxide molecule, we have two double bonds between the carbon and oxygen atoms. Similarly in ethane molecule the two carbon atoms are joined by a double bond.
H
O C O or O C O

H C C H

H or C H C

H H

 When combining atoms share three electron pairs as in the case of two nitrogen atoms in the N2 molecule and the two carbon atoms in the ethyne molecule, a triple bond is formed.
N N o r N N

H or H

The Lewis dot structures provide a picture of bonding in molecules and ions in terms of the shared pairs of electrons and the octet rule. While such a picture may not explain the bonding and behaviour of a molecule completely, it does help in understanding the formation and properties of a molecule to a large extent. Writing of Lewis dot structures of molecules is, therefore, very useful. Q 11: Explain Born-Haber cycle with example. The formation of ionic bond depends on lattice enthalpy. More the value of lattice enthalpy of the product easier will be the formation of ionic bond. The value of lattice energy will be more only when the attraction force between two atoms (ions) is more. Born-Haber first of all gave value of total enthalpy-lattice enthalpy by studying the enthalpies of different steps involved in the formation of ionic compounds by ionic bonds. Born-Haber Cycle can be explain by taking example of different enthalpy changes involved in the formation of NaCI crystalline compound from its components in standard state. Generally the simple equation for the formation of NaCI crystal can be written as follows: Na(s) + CI2(g) NaCI(s) fH = 411 kjmol1 But different steps of formation of NaCl crystal are as follows (i) First of all, sodium element/atom which is in solid form at room temperature is sublimed and the value of sublimation enthalpy (sH) is 108 klmol1. Na(s) Na(g) sH = + 108 kJmol1 (ii) The value of ionisation enthalpy required to remove electron from one mole Na~g) atom to infinite distance is 496 kjmol1
1 Na(g) ( ) + e .H = + 496 klmol (iii) Gaseous chlorine element exists as diatomic molecule of room temperature. In one mole solid NaCI crystal structure formation only one chlorine atom is required. Hence decomposition of chlorine molecule becomes essential. The enthalpy required for this is called decomposition enthalpy.

Sublimation enthalpy

ionization enthalpy

CI2(g) CI(g) D/2 H = + 121 klmol1 (iv) The gaseous atom of chlorine obtained this way accepts one electron and changes to chloride ion. The enthalpy released for this is called electron gain enthalpy (egH)
1 CI(g) + e ( ) egH = - 349 klmol (v) One mole gaseous positive ion (Na+) and one mole gaseous negative ion (Cl) combine with each other and form one mole of solid ionic crystal. The enthalpy released during this is called lattice enthalpy which is expressed as 'U'.

decomposition

Electrongainenthalpy

( )

( )

Latticeenthalpy

NaCI

UH = 787 klmol1

Na(s) + Cl2(g) S H D/2 H+2 Cl(g)

Hf

NaCl(s)

UH

Na(g
)

Cl(g) +e egH

Na+(g)

iH

Q 12: Discuss limitations of the Lewis octet rule The octet rule, though useful, is not universal. It is quite useful for understanding the structures of most of the organic compounds and it applies mainly to the second period elements of the periodic table. There are three types of exceptions to the octet rule. The incomplete octet of the central atom: In some compounds, the number of electrons surrounding the central atom is less than eight. This is especially the case with elements having less than four valence electrons. Examples are LiCl, BeH 2 and BCl3. Li, Be and B have 1,2 and 3 valence electrons only. Some other such compounds are AlCl3 and BF3.

Odd-electron molecules: In molecules with an odd number of electrons like nitric oxide, NO and nitrogen dioxide, NO2, the octet rule is not satisfied for all the atoms
N O
O + N O

The expanded octet: Elements in and beyond the third period of the periodic table have, apart from 3 s and 3p orbitals, 3d orbitals also available for bonding. In a number of compounds of these elements there are more than eight valence electrons around the central atom. This is termed as the expanded octet. Obviously the octet rule does not apply in such cases. Some of the examples of such compounds are: PF 5, SF6, H2SO4 and a number of coordination compounds.
F F P F F F
F S F F F F F

O H O S O O H

Interestingly, sulphur also forms many compounds in which the octet rule is obeyed. In sulphur dichloride, the S atom has an octet of electrons around it. Other drawbacks of the octet theory: It is clear that octet rule is based upon the chemical inertness of noble gases. However, some noble gases (for example xenon and krypton) also combine with oxygen and fluorine to form a number of compounds like XeF2, KrF2, XeOF2 etc., This theory does not account for the shape of molecules. It does not explain the relative stability of the molecules being totally silent about the energy of a molecule. Covalency. (additional point)

 The number of electrons which an atom contributes towards mutual sharing during the formation of a chemical bond is called its covalency in that compound. Thus, the covalency of hydrogen in H2 is one; that of oxygen in O2 is two (O = O, O ::O), and that of nitrogen in N2 is three. Characteristics of a Covalent Bond (additional point) A covalent bond has the following characteristics. (i) Mode of formation. Covalent bonds are formed due to mutual sharing of one or more pairs of electrons. (ii) Directional character. Covalent bonds are directional in nature. This is because in a covalent bond, the shared pair of electrons remains localized in a definite space between the nuclei of the two atoms. This gives a directional character to the covalent bond. Factors Favoring the Formation of a Covalent Bond (additional point). The following factors favour the formation of covalent bonds. (i) High ionization enthalpy (energy). The elements having higher ionisation enthalpy (energy) cannot lose electrons easily. Therefore, they cannot form ionic bonds. Instead, they acquire stability by mutual sharing of electrons, and therefore form covalent bonds. (ii) Nearly equal electron gain enthalpy (or electron affinity). The atoms of the two elements which have equal or nearly equal electron gain enthalpies (or electron affinities) tend to complete their outer shells by mutual sharing of electrons. This is because electron transfer in such cases will not be possible. (iii) Nearly equal electronegativity: Equal or nearly equal electronegativity of the two combining elements does not permit the transfer of electron(s) from one atom to another. Instead, the atoms tend to share the electrons and form a covalent bond. (iv) High nuclear charge and small atomic size: high nuclear charge and smaller atomic size of the combining elements favour covalent bond formation, because the transfer of electrons in such cases will not be possible. The conditions which favour the formation of covalent bonds are summarized below. Formation of a covalent bond is favoured by. (additional point) (i) High ionisation enthalpy (or energy) of the combining elements. (ii) Nearly equal electron gain enthalpies (or electron affinities) and equal electro negativities of the combining elements. (iii) High nuclear charge and small atomic size of the combining elements The Lewis dot structures can be written by adopting the following steps:{additional} The total number of electrons required for writing the structures is obtained by adding the valence electrons of the combining atoms. For example, in the CH4 molecule there are eight valence electrons available for bonding (4 from carbon and 4 from the four hydrogen atoms). For anions, each negative charge would mean addition of one electron. For cations, each positive charge would result in subtraction of one electron from the total number of valence electrons. For example, for the ion, the two negative charges indicate that there are two additional electrons than those provided by the neutral atoms. For ion, one positive charge indicates the loss of one electron from the group of neutral atoms. Knowing the chemical symbols of the combining atoms and having knowledge of the skeletal structure of the compound (known or guessed intelligently), it is easy to distribute the total number of electrons as bonding shared pairs between the atoms in proportion to the total bonds. In general the least electronegative atom occupies the central position in the molecule/ion. For example in the NF3 and nitrogen and carbon are the central atoms where as fluorine and oxygen occupy the terminal positions. After accounting for the shared pairs of electrons for single bonds, the remaining electron pairs are either utilized for multiple bonding or remain as the lone pairs. The basic requirement being that each bonded atom gets an octet of electrons.

Q 13: Discuss Formal Charge :{additional point} Lewis dot structures, in general, do not represent the actual shapes of the molecules. In case of polyatomic ions, the net charge is possessed by the ion as a whole and not by a particular atom. It is, however, feasible to assign a formal charge on each atom. The formal charge of an atom in a polyatomic molecule or ion may be defined as the difference between the number of valence electrons of that atom in an isolated or free state and the number of electrons assigned to that atom in the Lewis structure. It is expressed as : Formal charge (F.C.) on an atom in a Lewis structure = total number of valence electrons in the free atom total number of non bonding (lone pair) electrons ( ) total number of bonding(shared) electrons The counting is based on the assumption that the atom in the molecule owns one electron of each shared pair and both the electrons of a lone pair. Let us consider the ozone molecule (O3). The Lewis structure of O3 may be drawn as :
1 O

O 3

The atoms have been numbered as 1, 2 and 3. The formal charge onthe central O atom marked 1 = 6 2 (6) = +1 The end O atom marked 2 = 6 4 (4) = 0 The end O atom marked 3 = 6 6 (2) = 1 Hence, we represent O3 along with the formal charges as follows:
O

We must understand that formal charges do not indicate real charge separation within the molecule. Indicating the charges on the atoms in the Lewis structure only helps in keeping track of the valence electrons in the molecule. Formal charges help in the selection of the lowest energy structure from a number of possible Lewis structures for a given species. Generally the lowest energy structure is the one with the smallest formal charges on the atoms. The formal charge is a factor based on a pure covalent view of bonding in which electron pairs are shared equally by neighbouring atoms. Q 14: write a note on resonance structures

 It is often observed that a single Lewis structure is inadequate for the representation of a molecule in conformity with its experimentally determined parameters. For example, the ozone, O3 molecule can be equally represented by the structures I and II shown below: In both structures we have a OO single bond and a O=O double bond. The normal OO and O=O bond lengths are 148 pm and 121 pm respectively. Experimentally determined oxygen-oxygen bond lengths in the O3 molecule are same (128 pm). Thus the oxygen-oxygen bonds in the O3 molecule are intermediate between a double and a single bond. Obviously, this cannot be represented by either of the two Lewis structures shown above. The concept of resonance was introduced to deal with the type of difficulty experienced in the depiction of accurate structures of molecules like O 3. According to the concept of resonance, whenever a single Lewis structure cannot describe a molecule accurately, a number of structures with similar energy, positions of nuclei, bonding and non-bonding pairs of electrons are taken as the canonical structures of the hybrid which describes the molecule accurately. Thus for O3, the two structures shown above constitute the canonical structures or resonance structures and their hybrid i.e., the III structure represents the structure of O 3 more accurately. This is also called resonance hybrid. Resonance is represented by a double headed arrow. Some of the other examples of resonance structures are provided by the carbonate ion and the carbon dioxide molecule. Resonance stabilizes the molecule as the energy of the resonance hybrid is less than the energy of any single canonical structure; and, Resonance averages the bond characteristics as a whole. Thus the energy of the O3 resonance hybrid is lower than either of the two canonical forms I and II

Following points are additional but important for competitive exams Many misconceptions are associated with resonance and the same need to be dispelled. The canonical forms have no real existence. The molecule does not exist for a certain fraction of time in one canonical form and for other fractions of time in other canonical forms. There is no such equilibrium between the canonical forms as we have between tautomeric forms ( keto and enol) in tautomerism. The molecule as such has a single structure which is the resonance hybrid of the cannonical forms and which cannot as such be depicted by a single Lewis structure.

Q 15: explain polarity of bonds The existence of a hundred percent ionic or covalent bond represents an ideal situation. In reality no bond or a compound is either completely covalent or ionic. Even in case of covalent bond between two hydrogen atoms, there is some ionic character. When covalent bond is formed between two similar atoms, for example in H 2, O2, Cl2, N2 or F2 the shared pair of electrons is equally attracted by the two atoms. As a result electron pair is situated exactly between the two identical nuclei. The bond so formed is called non polar covalent bond. Contrary to this in case of a heteronuclear molecule like HF, the shared electron pair between the two atoms gets displaced more towards fluorine since the electronegativity of fluorine is far greater than that of hydrogen. The resultant covalent bond is a polar covalent bond. As a result of polarisation, the molecule possesses the dipole moment which can be defined as the product of the magnitude of the charge and the distance between the centres of positive and negative charge. It is usually designated by a Greek letter . Mathematically, it is expressed as follows : Dipole moment () = charge (Q) distance of separation (r)

 Dipole moment is usually expressed in Debye units (D).The conversio n factor is 1 D = 3.33564 1030 C m where C is coulomb and m is meter. Further dipole moment is a vector quantity and is depicted by a small arrow with tail on the positive centre and head pointing towards the negative centre. For example the dipole moment of HF may be represented as :
H F

The shift in electron density is symbolised by crossed arrow ( ) above the Lewis structure to indicate the direction of the shift. In case of polyatomic molecules the dipole moment not only depends upon the individual dipole moments of bonds known as bond dipoles but also on the spatial arrangement of various bonds in the molecule. In such case, the dipole moment of a molecule is the vector sum of the dipole moments of various bonds. For example in H2O molecule, which has a bent structure, the two OH bonds are oriented at an angle of 104.50.
H
H

O H
H

The dipole moment in case of BeF2 is zero. This is because the two equal bond dipoles point in opposite directions and cancel the effect of each other.
Cl Be 1800 Cl + total dipole moment

net dipole

In tetra-atomic molecule, for example in BF3, the dipole moment is zero although the B F bonds are oriented at an angle of 120 to one another, the three bond moments give a net sum of zero as the resultant of any two is equal and opposite to the third.
F F B F
+ total dipole moment = 0

Let us study an interesting case of NH3 and NF3 molecule. Both the molecules have pyramidal shape with a lone pair of electrons on nitrogen atom. Although fluorine is more electronegative than nitrogen, the resultant dipole moment of NH3 ( 4.90 1030 C m) is greater than that of NF3 (0.8 1030 C m). This is because, in case of NH3 the orbital dipole due to lone pair is in the same direction as the resultant dipole moment of the N H bonds, whereas in NF3 the orbital dipole is in the direction opposite to the resultant dipole moment of the three NF bonds. The orbital dipole because of lone pair decreases the effect of the resultant N F bond moments, which results in the low dipole moment of NF3 as represented below.
net dipole

N F F

net dipole F

Q 16: What is VSEPR theory'? Mention factors for the formation of covalent molecules based on this theory. Lewis concept is unable to explain the shapes of molecules. This theory provides a simple procedure to predict the shapes of covalent molecules. Sidgwickand Powell in 1940, proposed a simple theory based on the repulsive interactions of the electron pairs in the valence shell of the atoms. It was further developed and redefined by Nyholm and Gillespie (1957). The main postulates of VSEPR theory are as follows:

 The shape of a molecule depends upon the number of valence shell electron pairs (bonded or nonbonded) around the central atom. Pairs of electrons in the valence shell repel one another since their electron clouds are negatively charged. These pairs of electrons tend to occupy such positions in space that minimise repulsion and thus maximise distance between them. The valence shell is taken as a sphere with the electron pairs localising on the spherical surface at maximum distance from one another. A multiple bond is treated as if it is a single electron pair and the two or three electron pairs of a multiple bond are treated as a single super pair. {additional} Where two or more resonance structures can represent a molecule, the VSEPR model is applicable to any such structure. The repulsive interaction of electron pairs decrease in the order: Lone pair (lp) Lone pair (lp) > Lone pair (lp) Bond pair (bp) > Bond pair (bp) Bond pair (bp) Nyholm and Gillespie (1957) refined the VSEPR model by explaining the important difference between the lone pairs and bonding pairs of electrons. {additional} While the lone pairs are localised on the central atom, each bonded pair is shared between two atoms. As a result, the lone pair electrons in a molecule occupy more space as compared to the bonding pairs of electrons. This results in greater repulsion between lone pairs of electrons as compared to the lone pair - bond pair and bond pair - bond pair repulsions. {additional} These repulsion effects result in deviations from idealised shapes and alterations in bond angles in molecules. For the prediction of geometrical shapes of molecules with the help of VSEPR theory, it is convenient to divide molecules into two categories as (i) molecules in which the central atom has no lone pair and (ii) molecules in which the central atom has one or more lone pairs. The VSEPR Theory is able to predict geometry of a large number of molecules, especially the compounds of p-block elements accurately. It is also quite successful in determining the geometry quite-accurately even when the energy difference between possible structures is very small. The theoretical basis of the VSEPR theory regarding the effects of electron pair repulsions on molecular shapes is not clear and continues to be a subject of doubt and discussion. {additional} Method for Predicting the Shape of Molecules on the Basis of VSEPR Theory. {additional} According to the VSEPR theory, the geometry of a molecule is determined by the number of electron-pairs around the central atom. So, to use this theory for predicting the shapes of molecules just count the number of electron pairs (both, shared and lone pairs). The use of this theory in predicting the shapes of molecules is illustrated below by taking a typical molecule of the type ABn, where A is the central atom, B atoms are bonded to A by single electron pair bonds (single covalent bonds), and n is the number of B atoms bonded to one atom of A. For the sake of easier understanding we have divided molecules into various categories. (1) Molecules without non bonding electron pair (2) Molecules having non bonding electron pair Shapes of the molecules having only the bond (shared) pairs of electrons Note: In following discussion students needs to remember only the example of each case detail explanation is given for better understanding of student. Molecules with two bond pairs. In a molecule having two bond pairs of electrons around its central atom, the bond pairs are located on the opposite sides (at an angle of 180), of the central atom so that the repulsion between them is minimum. Such molecules are therefore linear. For example, in a molecule of the type AB2, in which the central atom A has two electron pairs, the two electron pairs are located on either side of A. Thus, the molecule AB2 takes a linear geometry.

10

Some molecules which show linear geometry are, BeF 2 (beryllium fluoride), BeCl2 (beryllium chloride), BeH2 (beryllium hydride), ZnCl2 (zinc chloride), and HgCl2 (mercuric chloride).
B A 1800 B Cl Be 1800 Cl

Molecules with three bond pairs. . In a molecule having three bond pairs of electrons around its central atom, the electron pairs form an equilateral triangular arrangement around the central atom. Thus, the three bond pairs are at 120C with respect of each other. Therefore, the molecules having three bond pairs around its central atom have trigonal planar (or triangular planar) shape. For example, in a molecule of the type AB3, the three bond pairs of electrons are located around A in a triangular arrangement. Thus, the molecule AB3 has a triangular planar geometry. Some molecules which exhibit triangular planar geometry are BCl 3, BF3 etc.
B 1200
Cl 1200 B

A B B Cl

Cl

Molecules with four bond pairs. In a molecule having four bond pairs of electrons, the four bond pairs are arranged tetrahedrally around the central atom. Thus, the four bond pairs are at an angle of 1090280 with respect to each other. Therefore, the molecule having four bond pairs around its central atom has a tetrahedral shape. For example, in a molecule of the type AB4, the four bond pairs are distributed tetrahedrally around A. Thus, the molecule AB4 has a tetrahedral geometry. Some other molecules which show tetrahedral geometry are CH4, CCl4, SiH4 etc.
B 109 28' A B B

H 109 28'

H H

C H

Molecules with five bond pairs. Five bond pairs orient themselves around the central atom in a trigonal bipyramidal way. Three bond pairs are in a plane (called equatorial plane) and oriented at an angle of 1200 with respect to each other, while the other two bond pairs are opposite to each other, and at right angles to the triangular plane formed by the three bond pairs. Therefore, a molecule having five bond pairs around its central atom has a triangular bipyramidal shape. For example in a molecule of the type AB5, the five bond pairs are distributed in a trigonal bipyramidal around the central atom A. Therefore, the molecules of the type AB5 are trigonal bipyramidal in shape. Some other molecules which show trigonal bipyramidal geometry are; PCl 5, PF5, SbCl5.
B axial bond 900 B B equatorial plane B A 1200 B

Cl

axial bond

900 Cl

Cl equatorial plane

1200 Cl

Cl

11

Molecules with six bond pairs. Six bond pairs in a molecule are distributed octahedral manner around the central atom. Thus, a molecule having six bond pairs around its central atom has an octahedral shape. In a molecule of the type AB6, the six B atoms are placed octahedrally around A. Thus, the molecules of the type AB 6 are octahedral. The molecule SF6 has an octahedral geometry.
B
900

F
900

B A B

F S

Shapes of the molecules having bonding pairs and non bonding pairs of electrons Note: In following discussion students needs to remember only the example of each case detail explanation is given for better understanding of student. Molecules with two bond pairs and one non-bonding pair.(AB2E) Total three electron pairs in a molecule are distributed in trigonal planner shape around the central atom. But as one electron pair is non bonding electron pair molecule have angular shape (bent or V-shape). The molecule have V- shaped and here angle between two bonding pair decreases because of the repulsion created by one non bonding electron pair towards bond pair of electrons. In SO2 bond angle reduce to 119.50 from regular angle of 1200.

O B O B Molecules with three bond pairs and one non-bonding pair.(AB3E) Total four electron pairs in a molecule are distributed in tetra hedral shape around the central atom. But as one electron pair is non bonding electron pair molecule have trigonal pyrimidal. The molecule have trigonal pyramidal shape and here angle between two bonding pair decreases because of the repulsion created by one non bonding electron pair towards three bond pair of electrons. In ammonia molecule bond angle decrease to 107 0 from 1090 28. Other molecule having same phenomenon are NF3, PCl3, H3O+ etc.

A
B B B

N
H
107 0

Molecules with two bond pairs and two non-bonding pair.(AB2E2) Total four electron pairs in a molecule are distributed in tetrahedral shape around the central atom. But as two electron pair is non bonding electron pair molecule have distorted tetra hedral shape or angular shape. The molecule (H2O) have angular shape and here angle between two bonding pair decreases because of the repulsion created by one non bonding electron pair towards three bond pair of electrons. Here lplp > lpbp> bp bp repulsions. Examples include, H2O, H2S, F2O, and SCl2. The H-O-H angle is 104.5 and H-S-H angle is 92. H2O has a structure as shown in Fig.

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A
B

H H B Molecules with four bond pairs and one non-bonding pair.(AB4E) Total five electron pairs in a molecule are distributed in trigonal bi pyramidal shape around the central atom. But as one electron pair is non bonding electron pair molecule have distorted trigonal bi pyramidal shape or see-saw shape. Here there are two possibilities for non bond electron pair to arrange either in axial position or in an equatorial position. If a non bond electron pair arrange in axial position then there are three lp- bp repulsions at 900. If a non bond electron pair arrange in equatorial position then there are two lp- bp repulsions at 900. Thus there will be less repulsion if non bond electron pair arranged in equatorial position hence molecule (SF 4) have see-saw or folded square or distorted tetrahedral shape.
B B
F S F F

F F S F F

A
B B

Molecules with three bond pairs and two non-bonding pair.(AB3E2) Total five electron pairs in a molecule are distributed in trigonal bi pyramidal shape around the central atom. But as two electron pair is non bonding electron pair molecule have distorted trigonal bi pyramidal shape or T shape. Here there are three possibilities for non bond electron pair to arrange either in axial position or in an equatorial position. If both non bonding electron pairs arranged in equatorial position then two lp-bp repulsion is at 1200 and four lp-bp repulsion is at900 while lp-lp repulsion is at 1200. If both non bonding electron pairs arranged in axial position then six lp-bp repulsion is at 900 and while one lp-lp repulsion is at 1800 If one non bonding electron pair arranged in equatorial position and other in axial position then two lp-bp repulsion is at 1200 , two lp-bp repulsion is at 900, one lp-lp repulsion is at 900 and one lp-bp repulsion at 1800. Out of above mention all the three positions least repulsion is posses by the molecule if both non bonding electron pairs arranged in equatorial position hence the molecule have T shape.
B B

F
F Cl F

F F Cl F

A
B

Cl F

Molecules with four bond pairs and two non-bonding pair.(AB4E2) Total six electron pairs in a molecule are distributed in octahedral shape around the central atom. But as two electron pair is non bonding electron pair molecule have distorted octahedral shape or square planner shape. The four bond pairs are distributed in a square planar distribution. The two lone pairs are in a direction at right angles to this plane. Thus, giving a square planar shape to such molecules. Examples include ICl 4, XeF4 .

B B
13

B B

Molecules with five bond pairs and one non-bonding pair.(AB4E2) Total six electron pairs in a molecule are distributed in octahedral shape around the central atom. But as one electron pair is non bonding electron pair molecule has distorted octahedral shape or square pyramidal shape. The four bond pairs are distributed in a square planar distribution. The one bond pair is in a direction at right angles to this plane. While one lone pair is in a direction at right angles to this plane. Hence the molecule has square pyramidal shape. The molecule having such geometry is BrF5 etc. B

B B

B B

Q 17: Three elements have the following Lewis symbols: A (i) Place the elements in the appropriate groups of the periodic table. (ii) Which elements are likely to form ions? What is the expected charge on the ions? (iii) Write the formulae and the Lewis structures of the covalent compounds formed between: (a) A and B, and (b) A and C. Solution. (i) The number of electrons in the outermost shell of the atom of any element gives the number of the group of the periodic table to which the element belongs. Thus,
A having only one valence electron belongs to Group 1 of the Long Form Periodic Table.
B

having 4 valence electrons, belongs to the group 14 of the Long Form Periodic Table.

has seven valence electrons. Thus, it belongs to the group 17 of the Periodic Table. (ii) The elements which have a tendency either to lose or gain one or more electrons are capable of forming ions. Thus,
A

having only one valence electron is likely to form a cation by losing one electron, e.g., Thus,
+

gives a

A + e positively charged ion. A C has seven electrons, it would accept one electron to complete its octet. As a result, C is likely to form a negatively charged ion, (an anion).

(iii) (a) The formation of covalent compound between A and B would require sharing of electrons between the two. Since A has only one electron and B has 4, four atoms of A would unite with one atom of B to give a compound BA 4. This is pictorially shown below.

(b) The formation of covalent compound between A and C would require sharing of electrons between 1 atom each of A and C as shown below.

The compound formed is AC. Q 18 .You are given the electronic configurations of five neutral atoms A, B, C, D and E A - 1s22s22p 63s2 B - 1s22s22p 63s1 C - 1s22s22p 1 D - 1s22s22p5 E - 1s22s22p 6

14

Write the empirical formula for the substances containing: (i) A and D, (ii) B and D, (iii) only D, (iv) only E. Solution. (i) The electronic configurations of A and D are A: 1s2 2s2 2p6 3s2 D: 1s2 2s2 2p5 Thus, the number of electrons in the outermost shell of A are 2, and of D are 7. To complete their octets, A is in a position of losing 2, while D is capable of accepting only one electron. Therefore, for each A there should be two D atoms. Hence the empirical formula of the compound is AD 2. In fact, AD2 is an ionic compound containing A2+ and D-1 . (ii) The electronic configurations of B and D are B: 1s2 2s2 2p6 3s1 D: 1s2 2s2 2p5 B has only one electron in its outermost shell while D has 7. Thus, B can lose one electron and D should accept it to give a compound having a formula of BD. Here, B exists as B+ and D as D-. (iii) The electronic configuration of D is 1s2 2s2 2p5 Thus, there are seven electrons in the outermost shell of D. To form a substance containing only D, each D atom should share a pair of electrons, i.e. D-D D2 Hence, the formula of the substance is D2. It is a covalent compound. (iv) The electronic configuration of E is 1s2 2s2 2p6 Since the octet is complete, hence E shall not show any chemical reactivity. It would exist as E. It is a noble gas. Q 19: Explain: Molecular orbital theory. M.O. theory was proposed by scientists Mulliken and Hund. According to the molecular orbital theory, during the formation of the molecule, atomic orbitals of all the combining atoms get dissolved for the formation of the molecular orbitals. Molecular orbitals are responsible to the molecule as a whole rather than to any individual atom. In other words the same is probability distribution of electron around a group of nuclei (concept of polycentric orbitals). Number of the molecular orbitals formed is equal to the number of atomic orbitals getting dissolved. Half the number of the molecular orbitals are formed are lower in energy compared to the corresponding atomic orbitals getting dissolved. This favours the formation of the bond. Hence they are known as bonding molecular orbital (BMO). Remaining half the numbers of the molecular orbital formed are higher in energy compared to the corresponding atomic orbitals getting dissolved. Hence these resist the formation of the bond and hence are known as Anti bonding molecular orbitals (ABMO). Thus, molecular orbital is constructed by the linear combination of atomic orbitals of combining atoms. Bonding molecular orbitals are formed by the additive combination of the atomic orbitals. Antibonding molecular orbitals are formed by the subtractive combination of atomic orbitals. After the formation of the molecular orbitals, they strictly follow Aufbau's, Pauli's and Hund's rule. For example, when bonding two H-atoms, the acceptable wave function, forms H2 molecule combine linearly in two ways as under and therefore two acceptable molecular wave functions and are formed mo = 1s(1) + 1s(2) * mo = 1s(1) - 1s(2) Q 20:Explain , *, , * type of orbitals. and symbols represent bonding type molecular orbitals while *and * used for anti-bonding molecular orbitals. Probability of electrons in a region between two nuclei is higher, molecular orbital is known as type of bonding molecular orbital (b mo ) while electron probability between two nuclei is lower, molecular orbital oppose formation of bond between two atoms the same is known as anti bonding molecular orbital ( *mo) Rotation of 1800 about bond axis results in change in the signs of wave function electron cloud density is increased indicating molecular orbital known as b mo (i.e. type of bonding molecular orbital). But if electron cloud density is decreased, then this kind of molecular orbital is antibonding molecular orbital (*mo).

15

There is a nodal plane between two nuclei in A.B.M.O. Electron cloud density in nodal plane is zero. The linear combination of atomic orbitals to form molecular orbitals obey the following conditions The combining atomic orbitals must have same energy and similar symmetry. The combining atomic orbitals must come closer so that proper overlapping of orbitals takes place.
+ 2pz(1) + 2pz(1)
+
+

2pz(2)
+

MO( )
+

2pz(2)
+

*MO( *)

+
2px(1) 2px(2)

MO( )

+ +

+
2px(1) 2px(2)

*MO( *)

Q 21:How molecular orbitals are formed? Molecular orbitals are formed by linear combination of atomic orbitals. Q 22:Give M.O. diagram for H2 molecule. How bonding molecular orbitals and antibonding molecular orbitals are formed? Calculate bond order. Linear combination of atomic orbitals results in to molecular orbitals. Additive combination of a wave function corresponding to 1s orbital of each hydrogen atom results in to formation of ls orbital i.e. BMO. For e.g mo = 1s(1) + 1s(2) Subtractive combination of wave function corresponding to 1s orbital of each hydrogen atom results into formation of *1s orbital. * mo = 1s(1) - 1s(2) Bond order = [Nb Na] = (2 0) = 1 No. of unpaired electron = 0 Magnetic property : diamagnetic.
* 1s
H-atom
1s

H2 molecule

H-atom

Q 23:What information are available from bond order. Zero and negative values of bond order indicate instability of a molecule. Positive values of bond order indicate that the molecules are stable. The dissociation energy of molecules having bond order 2 or higher is greater than dissociation energy of molecules having bond order 1.5. The integral values of bond order indicate the number of bonds described as a single bond, double bond and atriple bond. Bond order and bond length are inversely related. If bond order is higher, bond length is low. Eg.: bond length in H 2 molecule is shorter than in H2+.

16

 If all the electrons present in molecules are paired, then molecule is diamagnetic. But if unpaired electron is present in molecule, it exhibits paramagnetism. Q 24:Write a note on bond order. Bond order is defined as the number of covalent bond between two atoms. The order of bond formed in a diatomic molecule is given by the following equation. Bond order = (no. of electrons in BMO - no. of electrons in ABMO) Significance: If bond order of molecule comes out zero or negative means the molecule is unstable while only those molecules, which have value of bond order positive, are stable. The bond order is directly related with dissociation energy. Higher the bond order, higher is the dissociation energy of molecules. Integral value of bond order indicates the number of bonds viz. single, double or triple bond. Bond order is inversely proportional to bond length. Increase in bond order results in decrease in bond length. e.g. bond length in N2 molecule (bond order = 3) is 110 nm while bond length in O 2 molecule (bond order = 2) is 121 nm. Q 25:Explain: Concept of hybridisation :{additional} Hybridisation is a process in which different energetic atomic orbitals first gets mixed and then gets redistributed in such a way that newly formed hybrid orbitals are quite identical to each other with respect to shape, size and energy. Of course, mixing of orbitals is conceptual rather than reality. Or Hybridisation is a process of producing a set of equivalent wave functions by linear combination of acceptable solutions of wave functions of different types. Q 26:Define Hybridisation energy. :{additional} The difference between energy of atom in ground state and the energy of hypothetical structure at the moment of bond formation is known as hybridisation energy. C2H2, BeCl2, BF3, NO3-, CH4, NH4+, Ni(CN)4-2, Fe(CO)5, PCI5, PF5, [Co(NH3)6]+3, SF6 Q 27:Define hydrogen bond and explain with suitable illustrations. Hydrogen bond is defined as : "electrostatic attractive forces developed between covalently bonded and partially positively charged hydrogen atom with partially negatively charged atom possessing non bonding electrons pair". Hydrogen bond is much weaker than covalent bond since its bond energy is 40 KJ/mole. Hydrogen bond arises due to following facts when a H-atom is bonded to a highly electronegative atom by a covalent bond, the bonding electron pair is displaced towards electronegative atom like Nitrogen, Oxygen, Chlorine etc. this makes hydrogen atom considerably partially positively charged. Thus, hydrogen nucleus exerts strong electrostatic attraction on the electronegative atom of the adjacent molecule. Conditions for hydrogen bonding: A hydrogen atom should be bonded to a highly electronegative atom like fluorine, oxygen, nitrogen. Larger the electro negativity of the other atom, greater is the strength of hydrogen bond. Eg. : Electro negativity of F, 0, N decreases as F > 0 > N. Strength of hydrogen bond decreases as F - H > 0 - H > N - H The size of electronegative atom should be very small. Hydrogen bond is shown by dotted line (. . . ..) . Strong hydrogen bond is seen in the case of liquid states ofNH3, H2O and HF. Due to strong hydrogen bonding hydrides of first elements of group number 15, 16 and 17 i.e. NH 3, H2O and HF have high boiling temperature. NH3, H2O and HF in their liquid states possess strong hydrogen bond. Hence their boiling points and melting points are very high in expectation to those of hydrides of other elements of the same group viz. the higher melting points and boiling points of hydrides of first elements of group 15, 16 and 17 (NH 3, H2O, HF) support presence of hydrogen bond in them.

17

 The energy of hydrogen bond is about 40 kj mol-1, which is higher than the van der Waals' forces. The density of water is maximum at 277 K. In the temperature interval of 273 K to 277 K the density of water being more than that of ice, ice floats on water. Ice is a solid crystal of water having hydrogen bond. The magnitude of hydrogen bond is maximum in solid state of a substance and is minimum in gaseous state of a substance. The effect of hydrogen bond is observed on the structures and the properties of the compounds. Q 28:Write a note on types of Hydrogen Bonds and describe its effect on physical properties of substance Hydrogen bond is mainly of two types (i) Intramolecular Hydrogen Bond (ii) Intermolecular Hydrogen Bond If hydrogen bond is formed between atoms of same molecule, then that type of hydrogen bond is called intramolecular hydrogen bond. e.g. o-nitro phenol & o-chloro phenol
OH N O O
OH Cl

As the intermolecular hydrogen bond is formed with more than one molecules of the same compound, the number of such hydrogen bonds is more. As a result, the melting points and boiling points of such compounds are comparatively higher. The intramolecular hydrogen bond is formed internally between atoms of the same molecule. As a result, the number of such hydrogen bonds is limited. Hence, the melting points and boiling points of the compounds having intramolecular hydrogen bond are relatively lower. E.g. The boiling point of p-chlorophenol is higher than that of o-chlorophenol because intramolecular hydrogen bond is present in o-chlorophenol and intermolecular hydrogen bond is present in p-chlorophenol.
OH OH OH

Cl

Cl P-chloro phenol

Cl

Q 29:Give importance of hydrogen bond. Evaporation of water is low at ordinary temperature because of H-bonds in water. This results in abundance of water preserved on earth. Collection of water in animal and plant cells is due to H-bond. Water molecule forms H-bonds with clay inside the earth so moisture in earth is retained. Hydrogen bonds are formed in protein molecules of living animals due to - CONH group present in proteins. This is the reason for the muscular function due to H-bond formation. Some medicines show faster effects and rapid results due to H-bond formations. H-bond play important role in biochemical molecules present in living cells like nucleic acids, DNA, RNA etc. Cotton fabrics do not dry faster than synthetic fabrics as water molecules form stronger H bonds with cotton fabrics. Q 30:Why ice floats on water? It has been confirmed by X-ray studies that in ice the oxygen atoms of H neighbouring water molecules tetrahedrally surround each water molecule. Between the two oxygen atoms of neighbouring water molecules there is a hydrogen atom, which is linked to one oxygen through a covalent bond and to the other oxygen atom through a hydrogen bond.

18

 The tetrahedral arrangement of H2O molecules in ice is not packed closely but there are some vacant spaces in the crystalline structure giving open cage structure to ice. Ice has a relatively large volume than the given mass of liquid water; consequently density of ice is less than water. Hence, it floats over water. When ice is melted the hydrogen bonds start breaking the molecules of water closer by moving in the vacant space. This increases density of water than that of ice. The density of water keeps on increasing till 4C temperature. This is called uneven expansion of water. Beyond 4C temperature the density of water starts decreasing due to usual thermal expansion. Q 31:Give properties of metals. Following are the important properties of metals. Metals are good conductor of heat and electricity. Metals show malleability and ductility. Usually metals exist in hard and crystalline nature of course metals like alkali metals are soft. Metals show luster. Metals are opaque. Metals have low ionisation energy values. A metallic crystal consists of 8 to 12 atoms arranged around the metal atom. All metals except mercury and gallium are solid. Q 32:Explain the metallic bond and electron Sea model. Following two are important characteristics of metallic atoms. Metallic atoms have less number of electrons in valence shell compared to valence orbitals. Metallic atoms have low ionisation energy. Thus metal atom has less attraction for the valence electrons and valence electrons of metal atom are insufficient for the formation of valence bond. As a result there is no covalent bond form between two metal atoms and such bond does not have directional properties. The valence electrons of metal atoms are equivalent for the whole crystal and such electrons are called delocalised electrons. These delocalised electrons can change their position in the metal very easily. In this metal-crystal the positively charged atomic kernel (positive part of atom excluding valence electrons) can be described as a positively charged sphere embedded in delocalised electron cloud. According to static electricity, the atomic kernels being positively charged, must be repelling each other and yet attraction between very close atomic kernels and mobile electrons keep the kernel bound together. The positively charged kernels and electrons arranged around it having attractive force is called Metallic Bond. The atomic kernel remains in space as close as possible and keeps equal distance between them. The metallic bond can be explained by the following theories: (1) Electron sea model (2) energy gap model Q 33:Electron Sea Model According to this model, a metal is assumed to consist of a lattice of positive ions (or kernels) embedded is a sea of delocalised valence electrons. They remain near each other. Among such positively charged atomic kernels, there is a presence of delocalised electrons and they by strong attractive forces keep the kernels tightly close. Such attractive force is called Metallic Bond. All electrons of metal are not delocalised but those which exert strong attraction for kernels. Figure 1.10 shown electron sea model of metallic bond. Metallic bond can, be specifically defined as "The forces that hold the atoms together in a metal as a result of the attraction between positive ions and surrounding delocalised electrons are known as Metallic Bonds."

19

Kernel

+ + + +

+ + + +

+ + + +

+ + + +

+ + + +

Q 34:Explain ductility and malleability of metal. :{additional} When a stress is applied on the surface of a metal, the layer of atomic kernels on the surface of the metal get displaced. At the same time, the delocalised electron clouds surrounding it, also move. Thus, by applying stress, there is no relative difference in the atom-electron state (lattice). As a result metal shows property of malleability and ductility. Q 35:How metals conduct electricity? :{additional} Electrical conductivity of metal is due to presence of free and mobile electrons i.e. delocalized electrons. In metal crystals the electrons are flowing in all directions but when potential difference is applied to metal, there will be directed flow of electrons towards the positive electrode i.e. as potential difference is established between two points the total negative charge of atomic kernel and delocalized electrons increases. Due to increase in total energy of metal, delocalized electrons move towards positive side of conductor. When one electron is moving with charge from its position the other electron must also move. With the entrance of electrons from negative side, one electron from metal moves towards positive end and the total number of electrons remain constant. Thus, metal exhibit electrical conductivity. Q 36:How metals allow flow of heat? :{additional} When one end of a metal is at higher temperature than the other end, heat flows from hot end towards the cold one. The average kinetic energy of the atomic kernels of hot end is higher than that of the cold end. As the kinetic energy of kernels increases, its vibrational energy also increases so that there is an increase in kinetic energy of delocalized electrons. The delocalized electrons with this increased energy move in the metal crystal lattice and impart its energy to the kernels far away from it, resulting into increase in temperature. After sometime metal become uniformly hot. Q 37:Why metals have lusterous surface? :{additional} When visible radiation fall on metal surface the surface delocalized electron cloud gets excited to reach at higher energy level. When these electrons return back to their original position (energy level) they release the same amount of energy. Thus, momentary exchange of visible radiation causes luster on metal surface. Valence bond theory As we know that Lewis approach helps in writing the structure of 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.

20

 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 basedon quantum mechanical principles are introduced. These are valence bond (VB) theory and molecular orbital (MO) theory. Q 38:Explain formation of H2 molecule in the context of energy changes with the help of valence bond 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 overlap criteria of atomic orbitals, the hybridization of atomic orbitals and the principles of variation and superposition. 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 NB and electrons present in them are represented by eA and eB. When the two atoms are at large distance from each other, there is no interaction between them. As these two atoms approach each other, new attractive and repulsive forces begin to operate. old force of attraction new force of attraction

potential energy

eA
0

HA

HB

eA

bond energy
HA repulsive forces HB

internucleus distance
eB

eB

bond length
74pm

Attractive forces arise between: (i) nucleus of one atom and its own electron that is NA eA and NB eB. (ii) nucleus of one atom and electron of other atom i.e., NA eB, NB eA. Similarly repulsive forces arise between (i) electrons of two atoms like eA eB, (ii) nuclei of two atoms NA NB. 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 isolated hydrogen atoms. The energy so released is called as bond enthalpy, which is corresponding to minimum in the curve depicted in the graph. Conversely, 435.8 kJ of energy is required to dissociate one mole of H2 molecule. H2(g) + 435.8 kJ mol1 H(g) + H(g) Q 39:Mention the assumptions of Valence Bond Theory : According to valence bond theory, the half filled atomic orbitals (having same energy and symmetry) overlap with each other and form covalent bond. As a result there is pairing of electrons in valence orbitals.

21

 The strength of covalent bond is directly proportional to the magnitude of over lapping of orbitals or if the overlapping of valence orbitals of atom is more, then stronger will be the covalent bond The assumptions of valence bond theory can be given as follows : (i) Generally there must not be much difference in energies of overlapping atomic orbitals. (ii) The overlapping orbitals must be half filled and the spin of the electrons in them must be in opposite direction to each other. (iii) There must be overlapping of atomic orbitals to proper extent, so that chemical bond formation can take place. Q 40: Explain Orbital Overlap Concept In the formation of hydrogen molecule, there is a minimum energy state when two hydrogen atoms are so near that their atomic orbitals undergo partial interpenetration. This partial merging of atomic orbitals is called overlapping of atomic orbitals which results in the pairing of electrons. The extent of overlap decides the strength of a covalent bond. In general, greater the overlap the stronger is the bond formed between two atoms. Therefore, according to orbital overlap concept, the formation of a covalent bond between two atoms results by pairing of electrons present in the valence shell having opposite spins. Directional Properties of Bonds:{additional} As we have already seen the formation of covalent bond depends on the overlapping of atomic orbitals. The molecule of hydrogen is formed due to the overlap of 1 s-orbitals of two H atoms, when they combine with each other. In case of polyatomic molecules like CH4, NH3 and H2O, the geometry of the molecules is also important in addition to the bond formation. For example why is it so that CH 4 molecule has tetrahedral shape and HCH bond angles are 109.5? Why is the shape of NH3 molecule pyramidal ? The valence bond theory explains the formation and directional properties of bonds in polyatomic molecules like CH4, NH3 andH2O, etc. in terms of overlap and hybridisation of atomic orbitals. Q 41:Describe overlapping of Atomic Orbitals When two atoms come close to each other, there is overlapping of atomic orbitals. This overlap may be positive, negative or zero depending upon the properties of overlapping of atomic orbitals. The various arrangements of s and p orbitals resulting in positive, negative and zero overlap are depicted in following figure. Positive overlapping negative over lapping

pz
+

pz

+ -

pz

pz

+ +
z

+
z

+ z
z

- px px

py p y

- +
+
z

py p y

pz

px px

+
+
+
z

pz

Pz

Py

Zero over lapping

Pz

22

 The criterion of overlap, as the main factor for the formation of covalent bonds applies uniformly to the homonuclear or heteronuclear diatomic molecules and polyatomic molecules. In the case of polyatomic molecules like CH4, NH3 and H2O, the VB theory has to account for their characteristic shapes as well. The shapes CH4, NH3, and H2O molecules are tetrahedral, pyramidal and bent respectively. It would be therefore interesting to find out if these geometrical shapes can be explained in terms of the orbital overlaps. Let us first consider the CH4 (methane) molecule. The electronic configuration of carbon in its ground state is [He]2 s2 2p2 which in the excited state becomes [He] 2 s1 2px1 2py1 2pz1. The energy required for this excitation is compensated by the release of energy due to overlap between the orbitals of carbon and the hydrogen. The four atomic orbitals of carbon, each with an unpaired electron can overlap with the 1 s orbitals of the four H atoms which are also singly occupied. This will result in the formation of four C-H bonds. As the three p orbitals of carbon are at 90 to one another, hence the HCH angle in methane should be at 90. Thus three C-H bonds will be oriented at 90 to one another. The 2s orbital of carbon and the 1s orbital of H are spherically symmetrical and they can overlap in any direction. Therefore the direction of the fourth C-H bond cannot be ascertained. Above description does not fit in with the tetrahedral HCH angles of 109.5. It indicates that simple atomic orbital overlap does not account for the directional characteristics of bonds in CH 4. Using similar procedure and arguments, it can be seen that in the case of NH 3 and H2O molecules, the HNH and HOH angles should be 90. This is in disagreement with the actual bond angles of 107 and 104.5 in the NH 3 and H2O molecules respectively. Q 42:Explain types of Overlapping and Nature of Covalent Bonds
The covalent bond may be classified into two types depending upon the types of overlapping: (i) Sigma() bond, and (ii) bond (i) Sigma() bond : This type of covalent bond is formed by the end to end (hand-on) overlap of bonding orbitals along the internuclear axis. This is called as head on overlap or axial overlap. This can be formed by any one of the following types of combinations of atomic orbitals. s-s overlapping : In this case, there is overlap of two half filled s-orbitals along the internuclear axis as shown below .

s-p overlapping: This type of overlap occurs between half filled s-orbitals of one atom and half filled p-orbitals of another atom.

pp overlapping : This type of overlap takes place between half filled p-orbitals of the two approaching atoms.

(ii) pi() bond : In the formation of p bond the atomic orbitals overlap in such a way that their axes remain parallel to each other and perpendicular to the internuclear axis. The orbitals formed due to sidewise overlapping consists of two saucer type charged clouds above and below the plane of the participating atoms.

Strength of Sigma and pi Bonds Basically the strength of a bond depends upon the extent of overlapping. In case of sigma bond, the overlapping of orbitals takes place to a larger extent. Hence, it is stronger as compared to the pi bond where the extent of overlapping occurs to a smaller extent. Further, it is important to note that pi bond between two atoms is formed in addition to a sigma bond. It is always present in the molecules containing multiple bond (double or triple bonds)

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