CHAPTER

2

Atomic Structure
And
Bonding
2-1

Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display

Structure of Atoms
ATOM

Basic Unit of an Element
Diameter : 10 –10 m.
Neutrally Charged

Nucleus

Electron Cloud

Diameter : 10
m
Accounts for almost all mass
Positive Charge
–14

Proton

Mass : 1.673 x 10 –24 g
Charge : 1.602 x 10 –19 C
2-2

Mass : 9.109 x 10 –28 g
Charge : -1.602 x 10 –9 C
Accounts for all volume

Neutron

Mass : 1.675 x 10 –24 g
Neutral Charge

023 x 1023 Carbon Atoms . Example :. Uranium = 92 • Relative atomic mass = Mass in grams of 6.Hydrogen = 1.Copyright © The McGraw-Hill Companies. One Atomic Mass unit is 1/12th of mass of carbon atom. • Example :- One gram Mole of Carbon 2-3 12 Grams Of Carbon 6. • One gram mole = Gram atomic mass of an element.203 x 1023 ( Avagadro Number) Atoms. Inc.Carbon has 6 Protons and 6 Neutrons. Atomic Mass = 12. Permission required for reproduction or display Atomic Number and Atomic Mass • • Atomic Number = Number of Protons in the nucleus Unique to an element Example :.

Inc.. M. and Davis.Copyright © The McGraw-Hill Companies. McGraw-Hill. R. . Permission required for reproduction or display Periodic Table 2-4 Source: Davis. Fundamentals of Chemical Reaction Engineering. 2003.

s c= Speed of light = Wavelength of light . Permission required for reproduction or display Electron Structure of Atoms • Electron rotates at definite energy levels. Energy is emitted during transition to lower level.63 x 10-34 J. • • • Energy is absorbed to move to higher energy level. Inc.Copyright © The McGraw-Hill Companies. Energy change due to transition = E = hc λ h=Planks Constant Absorb Energy (Photon) Emit Energy (Photon) Energy levels Photon = Electromagnetic radiation 2-6 = 6.

p. Permission required for reproduction or display Quantum Numbers of Electrons of Atoms Principal Quantum Number (n) Represents main energy levels.d and f. • Larger the ‘n’ higher the energy. Inc.Copyright © The McGraw-Hill Companies. n=1 n=2 n=3 2-8 n=1 n=2 s orbital (l = 0) p Orbital (l =1) . • Represented by letters s. • Subsidiary Quantum Number l • Represents sub energy levels (orbital). • Range 0…n-1. • Range 1 to 7.

• Atomic size (radius) increases with addition of shells. (Z=26).Copyright © The McGraw-Hill Companies. Permission required for reproduction or display Electron Structure of Multielectron Atom • Maximum number of electrons in each atomic shell is given by 2n2. Inc. of proton 2-10 . Electronic configuration is 1s2 2s2 sp6 3s2 3p6 3d6 4s2 Z = atomic no. • Electron Configuration lists the arrangement of electrons in orbitals. Example :- Orbital letters Number of Electrons 1s2 2s2 2p6 3s2 Principal Quantum Numbers For Iron. = no.

Kr. Ar. Xe. Helium has 1s2 configuration • Electropositive elements give electrons during chemical reactions to form cations. Rn) are chemically very stable All have s2 p6 configuration for outermost shell. Inc. most noble gasses (Ne. Permission required for reproduction or display Electron Structure and Chemical Activity • Except Helium. Cations are indicated by positive oxidation numbers Example:Fe : 1s2 2s2 sp6 3s2 3p6 3d6 4s2 Fe2+ : 1s2 2s2 sp6 3s2 3p6 3d6 Fe3+ : 1s2 2s2 sp6 3s2 3p6 3d5 2-11 .Copyright © The McGraw-Hill Companies.

• Some elements behave as both electronegative and electropositive.1 Electronegativity of Sodium is 1.) • Electronegative elements accept electrons during chemical reaction.Electronegativity of Fluorine is 4.1 Example :. Permission required for reproduction or display Electron Structure and Chemical Activity (Cont. Inc. Te Na Electropositive 0 2-12 K 1 W 2H N Se 3 O Fl 4 Electronegative .Copyright © The McGraw-Hill Companies. • Electronegativity is the degree to which the atom attracts electrons to itself Measured on a scale of 0 to 4..

Inc.Large interactive force due to sharing of electrons . Permission required for reproduction or display Atomic and Molecular Bonds -Atoms in bonded state are in a more stable energy condition compared to unbonded condition.Copyright © The McGraw-Hill Companies.Very weak electric dipole bonds due to asymmetric distribution of electron densities. . • • • • • 2-12 Ionic bonds :.Weak intermolecular bonds due to attraction between the ends of permanent dipoles. Net decrease of potential energy after bonding.directional Metallic bonds :.Non-directional bonds formed by sharing of electrons Permanent Dipole bonds :.Strong atomic bonds due to transfer of electrons – non-directional Covalent bonds :. Fluctuating Dipole bonds :.

Permission required for reproduction or display Ionic Bonding Ionic bonding is due to electrostatic force of attraction between cations and anions. • Electrons are transferred from electropositive to electronegative atoms • Electropositive Electronegative Electron Element Atom Transfer Electrostatic (coulombic) Attraction Cation Anion +ve charge -ve charge IONIC BOND 2-14 . • It can form between metallic and nonmetallic elements. Inc.Copyright © The McGraw-Hill Companies.

Copyright © The McGraw-Hill Companies.10 . Permission required for reproduction or display Ionic Bonding . Inc.Example To achieve inert gas configuration • Ionic bonding in NaCl Atomic no= 11 3s1 3p7 Sodium Atom Na Sodium Ion Na+ I O N I C B O N D 2-15 Atomic no= 17 Chlorine Atom Cl Chlorine Ion Cl - Figure 2.

11 2-16 .Copyright © The McGraw-Hill Companies. The electron clouds of ion repulse each other when they are sufficiently close. Force versus separation Distance for a pair of oppositely charged ions Figure 2. Inc. Permission required for reproduction or display Ionic Force for Ion Pair • • (Proton + neutron) Nucleus of one ion attracts electron of another ion.

Inc..Z2 = Number of electrons removed or added during ion formation e = Electron Charge a = Interionic seperation distance = Permeability of free space (8.85 x 10-12c2/Nm2) F repulsive =− nb a (n and b are constants) n +1 2 F net = Z Z e − nb (4π ε a ) a 1 2 2 0 2-17 n +1 . Permission required for reproduction or display Ion Force for Ion Pair (Cont.) ( e)(Z e) Z Z e = Z = (4π ε a ) (4π ε a ) 2 F 1 attractive 1 2 2 2 2 0 0 Z1.Copyright © The McGraw-Hill Companies.

76 x 10 1 attraction 2 = +3.60 x 10-19 C .181 nm = 2.Copyright © The McGraw-Hill Companies. Inc. Permission required for reproduction or display Interionic Force . Z2 = -1 for Cle = 1.85 x 10-12 C2/Nm2 a0 = Sum of Radii of Na+ and Cl.ions = 0.76 x 10-10 m Cl- Na+ a0 2 F ( +1)( −1)(1.095 nm + 0.60 × 10 C ) e Z Z = = (4π ε a ) 4π (8. 0 = 8.02 × 10 −9 N 2 2 0 2-18 −19 -12 2 -10 m) .85 x 10 C /Nm2)(2.Example Force of attraction between Na+ and Cl.ions • Z1 = +1 for Na+.

ions pack around central Na+ Ions Ionic packing In NaCl and CsCl Figure 2. fewer anion surround central cation. Example:. six Cl.in NaCl. 2-20 .Copyright © The McGraw-Hill Companies.13 CsCl NaCl • As the ratio of cation to anion radius decreases. Inc. Permission required for reproduction or display Ion Arrangements in Ionic Solids • • Ionic bonds are Non Directional Geometric arrangements are present in solids to maintain electric neutrality.

Permission required for reproduction or display Bonding Energies (Measure of bonding strength) Lattice energies and melting points of ionically bonded solids are high. Inc. • Lattice energy decreases when size of ion increases (because bonding electrons in larger ions are farther away from • the attractive influence of the +ve nucleus).Copyright © The McGraw-Hill Companies. Example :NaCl CsCl BaO 2-21 Lattice energy = 766 KJ/mol Melting point = 801oC Lattice energy = 649 KJ/mol Melting Point = 646oC Lattice energy = 3127 KJ/mol Melting point = 1923oC . • Multiple bonding electrons increase lattice energy.

a bond is formed between 2 atoms by sharing their 1s1 electrons Electron Overlapping Electron Clouds • Pair H + H 2-22 1s1 Electrons H H Hydrogen Molecule H H . Permission required for reproduction or display Covalent Bonding In Covalent bonding. Inc. • In Hydrogen. outer s and p electrons are shared between two atoms to obtain noble gas configuration.Copyright © The McGraw-Hill Companies. • Takes place between elements with small differences in electronegativity and close by in periodic table.

O2 and N2. covalent bonding is formed by sharing p electrons • Fluorine gas (Outer orbital – 2s2 2p5) share one p electron to attain noble gas configuration.Copyright © The McGraw-Hill Companies.Examples • In case of F2. F + F • H F F F F Bond Energy=160KJ/mol Oxygen (Outer orbital . Inc.2s2 2p4) atoms share two p electrons O + O O O O=O Bond Energy=28KJ/mol • Nitrogen (Outer orbital . Permission required for reproduction or display Covalent Bonding .2s2 2p3) atoms share three p electrons HH 2-23 N + N N N N N Bond Energy=54KJ/mol .

Result four sp3 orbitals. Permission required for reproduction or display Covalent Bonding in Carbon • Carbon has electronic configuration 1s2 2s2 2p2 Ground State arrangement 1s 2s 2p Two ½ filed 2p orbitals • Hybridization causes one of the 2s orbitals promoted to 2p orbital.Copyright © The McGraw-Hill Companies. Inc. 1s 2-24 Indicates carbon Forms two Covalent bonds 2p Four ½ filled sp3 orbitals Indicates four covalent bonds are formed .

Single and double bonds alternate between the atoms. The Carbon atoms are arranged in hexagonal ring. H H H C C C C C C H H H Structure of Benzene 2-27 Figure 2. Permission required for reproduction or display Covalent Bonding in Benzene • • • Chemical composition of Benzene is C6H6. Inc.Copyright © The McGraw-Hill Companies.23 Simplified Notations .

Permission required for reproduction or display Metallic Bonding • • • • • Atoms in metals are closely packed in crystal structure. metallic bonds are Non-directional *a mechanical property used to describe the extent to which materials can be deformed plastically without fracture 2-28 Valence electron charge cloud . Loosely bounded valence electrons are attracted towards nucleus of other atoms.Copyright © The McGraw-Hill Companies. Electrons spread out among atoms forming electron clouds. Positive Ion These free electrons are reason for electric conductivity and ductility* Since outer electrons are shared by many atoms. Inc.

• Minimum energy between atoms exist at equilibrium distance a0 • Fewer the number of valence electrons involved.Na Bonding energy 108KJ/mol.Copyright © The McGraw-Hill Companies. Melting temperature 851oC 2-29 . valence electrons are freer to move). Example:..e. more metallic the bond is (i.e. from unstable atoms to stable bonding).) Overall energy of individual atoms are lowered by metallic bonds (i. • Melting temperature 97. Permission required for reproduction or display Metallic Bonds (Cont.7oC • Higher the number of valence electrons involved.Ca Bonding energy 177KJ/mol. higher is the bonding energy. Example:. Inc.

Inc.Copyright © The McGraw-Hill Companies. Permission required for reproduction or display Secondary Bonding Secondary bonds are due to attractions of electric dipoles in atoms or molecules. • Dipoles are created when positive and negative charge centers exist. 2-30 =q. • nucleus Dipole moment= -q +q q= Electric charge d = separation distance d • There two types of bonds fluctuating.d permanent and .

Dipoles are created due to asymmetrical distribution of electron charges. • Electron cloud charge changes with time. • • nucleus + Symmetrical distribution of electron charge 2-31 _ Figure 2.Copyright © The McGraw-Hill Companies.27 Asymmetrical Distribution (Changes with time) . Permission required for reproduction or display Fluctuating Dipoles They have complete outervalence-electron shells Weak secondary bonds in noble gasses. Inc.

Inc. Examples:- CH4 (Methane) CH3Cl (Chloromethane) 2-32 Symmetrical Arrangement Of 4 C-H bonds Asymmetrical Tetrahedral arrangement No Dipole moment Creates Dipole .Copyright © The McGraw-Hill Companies. Permission required for reproduction or display Permanent Dipoles • Dipoles that do not fluctuate with time are called Permanent dipoles (weak bonding forces among covalently bonded molecules can be created if molecules contain permanent dipoles) .

Inc. Attraction between positive oxygen pole and negative hydrogen pole. Example :In water. Permission required for reproduction or display Hydrogen Bonds (special case of permanent dipole-dipole interaction betw. H O 105 0 Figure 2. polar molecules) • Hydrogen bonds are Dipole-Dipole interaction between polar bonds containing hydrogen atom. dipole is created due to asymmetrical arrangement of hydrogen atoms.28 H 2-33 Hydrogen Bond .Copyright © The McGraw-Hill Companies.