CHAPTER 2. Atomic Structure And Bonding 2-1
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1 CHAPTER 2 Atomic Structure And Bonding 2-1
2 Structure of Atoms ATOM Basic Unit of an Element Diameter : m. Neutrally Charged Nucleus Diameter : m Accounts for almost all mass Positive Charge Electron Cloud Mass : x g Charge : x 10 9 C Accounts for all volume Proton Mass : x g Charge : x C Neutron Mass : x g Neutral Charge 2-2
3 Atomic Number and Atomic Mass Atomic Number = Number of Protons in the nucleus Unique to an element Example :- Hydrogen = 1, Uranium = 92 Relative atomic mass = Mass in grams of x ( Avagadro Number) Atoms. Example :- Carbon has 6 Protons and 6 Neutrons. Atomic Mass = 12. One Atomic Mass unit is 1/12 th of mass of carbon atom. One gram mole = Gram atomic mass of an element. Example :- One gram Mole of Carbon 12 Grams Of Carbon x Carbon Atoms 2-3
4 Periodic Table 2-4 Source: Davis, M. and Davis, R., Fundamentals of Chemical Reaction Engineering, McGraw-Hill, 2003.
5 Example Problem A 100 gram alloy of nickel and copper consists of 75 wt% Cu and 25 wt% Ni. What are percentage of Cu and Ni Atoms in this alloy? Given:- 75g Cu Atomic Weight g Ni Atomic Weight Number of gram moles of Cu = Number of gram moles of Ni = Atomic Percentage of Cu = Atomic Percentage of Ni = 75 g = mol g/mol 25 g = mol g/mol = 73.5% ( ) ( ) = 25.5% 2-5
6 Electron Structure of Atoms Electron rotates at definite energy levels. Energy is absorbed to move to higher energy level. Energy is emitted during transition to lower level. Energy change due to transition = E = Absorb Energy (Photon) Emit Energy (Photon) hc λ h=planks Constant = 6.63 x J.s c= Speed of light λ = Wavelength of light Energy levels 2-6
7 Energy in Hydrogen Atom Hydrogen atom has one proton and one electron Energy of hydrogen atoms for different energy levels is given by (n=1,2..) principal quantum E = ev n 2 numbers Example:- If an electron undergoes transition from n=3 state to n=2 state, the energy of photon emitted is E = 1. 89ev 3 = 2 2 Energy required to completely remove an electron from hydrogen atom is known as ionization energy 2 2-7
8 Quantum Numbers of Electrons of Atoms Principal Quantum Number (n) Represents main energy levels. Range 1 to 7. Larger the n higher the energy. n=1 n=2 n=3 Subsidiary Quantum Number l Represents sub energy levels (orbital). Range 0 n-1. Represented by letters s,p,d and f. n=1 n=2 s orbital (l=0) p Orbital (l=1) 2-8
9 Quantum Numbers of Electrons of Atoms (Cont..) Magnetic Quantum Number m l. Represents spatial orientation of single atomic orbital. Permissible values are l to +l. Example:- if l=1, m l = -1,0,+1. I.e. 2l+1 allowed values. No effect on energy. Electron spin quantum number m s. Specifies two directions of electron spin. Directions are clockwise or anticlockwise. Values are +1/2 or 1/2. Two electrons on same orbital have opposite spins. No effect on energy. 2-9
10 Electron Structure of Multielectron Atom Maximum number of electrons in each atomic shell is given by 2n 2. Atomic size (radius) increases with addition of shells. Electron Configuration lists the arrangement of electrons in orbitals. Example :- Orbital letters Number of Electrons 1s 2 2s 2 2p 6 3s 2 Principal Quantum Numbers For Iron, (Z=26), Electronic configuration is 1s 2 2s 2 sp 6 3s 2 3p 6 3d 6 4s
11 Electron Structure and Chemical Activity Except Helium, most noble gasses (Ne, Ar, Kr, Xe, Rn) are chemically very stable All have s 2 p 6 configuration for outermost shell. Helium has 1s 2 configuration Electropositive elements give electrons during chemical reactions to form cations. Cations are indicated by positive oxidation numbers Example:- Fe : 1s 2 2s 2 sp 6 3s 2 3p 6 3d 6 4s 2 Fe 2+ : 1s 2 2s 2 sp 6 3s 2 3p 6 3d 6 Fe 3+ : 1s 2 2s 2 sp 6 3s 2 3p 6 3d
12 Electron Structure and Chemical Activity (Cont..) Electronegative elements accept electrons during chemical reaction. Some elements behave as both electronegative and electropositive. Electronegativity is the degree to which the atom attracts electrons to itself Measured on a scale of 0 to 4.1 Example :- Electronegativity of Fluorine is 4.1 Electronegativity of Sodium is 1. Na Te N O Fl 0 K 1 W 2H Se 3 4 Electropositive Electronegative 2-12
13 Atomic and Molecular Bonds Ionic bonds :- Strong atomic bonds due to transfer of electrons Covalent bonds :- Large interactive force due to sharing of electrons Metallic bonds :- Non-directional bonds formed by sharing of electrons Permanent Dipole bonds :- Weak intermolecular bonds due to attraction between the ends of permanent dipoles. Fluctuating Dipole bonds :- Very weak electric dipole bonds due to asymmetric distribution of electron densities. 2-12
14 Ionic Bonding Ionic bonding is due to electrostatic force of attraction between cations and anions. It can form between metallic and nonmetallic elements. Electrons are transferred from electropositive to electronegative atoms Electropositive Element Electron Transfer Electronegative Atom Cation +ve charge Electrostatic Attraction Anion -ve charge IONIC BOND 2-14
15 Ionic Bonding - Example Ionic bonding in NaCl Sodium Atom Na 3s 1 3p 6 Chlorine Atom Cl 2-15 Sodium Ion Na + I O N I C B O N D Chlorine Ion Cl - Figure 2.10
16 Ionic Force for Ion Pair Nucleus of one ion attracts electron of another ion. 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
17 Ion Force for Ion Pair (Cont..) F ( Z )( Z ) Z e e = = attractive ( 4 ) ( ) 2 2 π ε a 4π ε 0 0a Z1,Z2 = Number of electrons removed or added during ion formation e = Electron Charge a = Interionic seperation distance ε = Permeability of free space (8.85 x c 2 /Nm 2 ) F F net repulsive = Z 1 = Z e nb a n+1 nb ( ) 2 4 0a a π ε 2 2 n+ 1 Z e 2 (n and b are constants) 2-17
18 Interionic Force - Example Force of attraction between Na+ and Cl - ions Z 1 = +1 for Na +, Z 2 = -1 for Cl - e = 1.60 x C, ε 0 = 8.85 x C 2 /Nm 2 a 0 = Sum of Radii of Na + and Cl - ions = nm nm = 2.76 x m Na + Cla 0 F attraction = Z 1 Z 2e 0a 2 2 ( 4 ) π ε = 4π (8.85 x 10 ( + 1)( 1)( C 2 19 C) /Nm2)(2.76 x m) = N 2-18
19 Interionic Energies for Ion Pairs Net potential energy for a pair of oppositely charged ions = E net = Z 1 Z 2 e + b ( ) 2 4π ε 0a a 2 Attraction Repulsion Energy Energy n Energy Released Energy Absorbed E net is minimum when ions are at equilibrium seperation distance a
20 Ion Arrangements in Ionic Solids Ionic bonds are Non Directional Geometric arrangements are present in solids to maintain electric neutrality. Example:- in NaCl, six Cl- ions pack around central Na+ Ions Ionic packing In NaCl and CsCl Figure 2.13 CsCl NaCl As the ratio of cation to anion radius decreases, fewer anion surround central cation. 2-20
21 Bonding Energies Lattice energies and melting points of ionically bonded solids are high. Lattice energy decreases when size of ion increases. Multiple bonding electrons increase lattice energy. Example :- NaCl Lattice energy = 766 KJ/mol Melting point = 801 o C CsCl Lattice energy = 649 KJ/mol Melting Point = 646 o C BaO Lattice energy = 3127 KJ/mol Melting point = 1923 o C 2-21
22 Covalent Bonding In Covalent bonding, outer s and p electrons are shared between two atoms to obtain noble gas configuration. Takes place between elements with small differences in electronegativity and close by in periodic table. In Hydrogen, a bond is formed between 2 atoms by sharing their 1s 1 electrons H + H H H Electron Pair Overlapping Electron Clouds H H s 1 Electrons Hydrogen Molecule
23 Covalent Bonding - Examples In case of F 2, O 2 and N 2, covalent bonding is formed by sharing p electrons Fluorine gas (Outer orbital 2s 2 2p 5 ) share one p electron to attain noble gas configuration. F + F H F F F F Bond Energy=160KJ/mol Oxygen (Outer orbital - 2s 2 2p 4 ) atoms share two p electrons O + O O O O = O Bond Energy=28KJ/mol 2-23 Nitrogen (Outer orbital - 2s 2 2p 3 ) atoms share three p electrons H H N + N N N N N Bond Energy=54KJ/mol
24 Covalent Bonding in Carbon Carbon has electronic configuration 1s 2 2s 2 2p 2 Ground State arrangement 1s 2s 2p Two ½ filed 2p orbitals Indicates carbon Forms two Covalent bonds 2-24 Hybridization causes one of the 2s orbitals promoted to 2p orbital. Result four sp3 orbitals. 1s 2p Four ½ filled sp 3 orbitals Indicates four covalent bonds are formed
25 Structure of Diamond Four sp 3 orbitals are directed symmetrically toward corners of regular tetrahedron. This structure gives high hardness, high bonding strength (711KJ/mol) and high melting temperature (3550 o C). Carbon Atom Figure 2.18 Tetrahedral arrangement in diamond Figure
26 Carbon Containing Molecules In Methane, Carbon forms four covalent bonds with Hydrogen. Molecules are very weekly bonded together resulting in low melting temperature (-183 o C). Carbon also forms bonds with itself. Molecules with multiple carbon bonds are more reactive. Examples:- H C H C H H Ethylene H C C Acetylene H Methane molecule Figure
27 Covalent Bonding in Benzene Chemical composition of Benzene is C 6 H 6. The Carbon atoms are arranged in hexagonal ring. Single and double bonds alternate between the atoms. H H C C C H H C C C H H Structure of Benzene Figure 2.23 Simplified Notations 2-27
28 Metallic Bonding 2-28 Atoms in metals are closely packed in crystal structure. Loosely bounded valence electrons are attracted towards nucleus of other atoms. 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, metallic bonds are Non-directional Valence electron charge cloud Figure 2.24
29 Metallic Bonds (Cont..) Overall energy of individual atoms are lowered by metallic bonds Minimum energy between atoms exist at equilibrium distance a 0 Fewer the number of valence electrons involved, more metallic the bond is. Example:- Na Bonding energy 108KJ/mol, Melting temperature 97.7 o C Higher the number of valence electrons involved, higher is the bonding energy. Example:- Ca Bonding energy 177KJ/mol, Melting temperature 851 o C 2-29
30 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. +q -q Dipole moment=µ =q.d q= Electric charge d = separation distance Figure 2.26 d There two types of bonds permanent and fluctuating. 2-30
31 Fluctuating Dipoles Weak secondary bonds in noble gasses. Dipoles are created due to asymmetrical distribution of electron charges. Electron cloud charge changes with time. Symmetrical distribution of electron charge Figure 2.27 Asymmetrical Distribution (Changes with time) 2-31
32 Permanent Dipoles Dipoles that do not fluctuate with time are called Permanent dipoles. Examples:- CH 4 Symmetrical Arrangement Of 4 C-H bonds No Dipole moment CH 3 Cl Asymmetrical Tetrahedral arrangement Creates Dipole 2-32
33 Hydrogen Bonds Hydrogen bonds are Dipole-Dipole interaction between polar bonds containing hydrogen atom. Example :- In water, dipole is created due to asymmetrical arrangement of hydrogen atoms. Attraction between positive oxygen pole and negative hydrogen pole. H O H Figure 2.28 Hydrogen Bond 2-33
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