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PHY351

CHAPTER

2
Atomic Structure and Bonding

1
History of atom
17th century:
Robert Boyle asserted that elements are made up of
“simple bodies” which themselves are not ...
Structure of atom
ATOM
Basic Unit of an Element
Diameter : 10 –10 m.
Neutrally Charged
Nucleus
Diameter : 10 –14 m
Account...
Figure 2.2: The relative size of an atom and its nucleus that is made up of protons
and neutrons.

4
Atomic Number and Atomic Mass
Atomic Number
Number of Protons in the nucleus.
Unique to an element
Example : Hydrogen = 1,...
The mass number (A) is the sum of protons and neutrons in
a nucleus of an atom.
Example :
Carbon has 6 Protons and 6 Neutr...
Quantum Numbers of Electrons of
Atoms
Principal Quantum Number
(n)
• Represents main energy levels.
•
•

Range 1 to 7.
Lar...
s, p and d Orbitals

2

2

2

Schematic diagram of s, p and d orbitals
8
Quantum Numbers of Electrons of
Atoms
Magnetic Quantum Number
ml.
• Represents spatial
orientation of single atomic
orbita...
Electron Structure of Multielectron
Atom
Maximum number of electrons in each atomic shell is given by 2n2.
Atomic size (ra...
Multielectron Atoms
Nucleus charge effect: The higher the charge
of the nucleus, the higher is the attraction
force on an ...
The Quantum-Mechanical Model and
the Periodic Table
Elements are classified according to their ground state
electron confi...
Periodic table

Figure 2.3 The updated periodic table showing seven periods, eight main group elements, transition
element...
Metals, Metalloids, and Nonmetals
Reactive metals (or simply metals):
Electro positive materials, have the natural tendenc...
Primary Bonds
Bonding with other atoms, the potential energy of each
bonding atom is lowered resulting in a more stable st...
Ionic bonds :
Strong atomic bonds due to transfer of electrons
Covalent bonds :
Large interactive force due to sharing of ...
Ionic Bond
Ionic bonding is due to electrostatic force of attraction
between cations and anions.
It can form between metal...
Ionic Bond (cont..)
Large difference in electronegativity.
When a metal forms a cation, its radius reduces and when a
nonm...
Ionic Bond (cont..)
Example: Ionic bonding in NaCl

3s1

3p6

Sodium
Atom
Na

Sodium Ion
Na+

I
O
N
I
C

B
O
N
D

Chlorine...
Covalent Bond

In Covalent bonding, outer s and p electrons are shared
between two atoms to obtain noble gas configuration...
Covalent Bond (cont..)

In Hydrogen, a bond is formed between 2 atoms by
sharing their 1s1 electrons

Electron
Pair

H + H...
Covalent Bond (cont..)
In case of F2, O2 and N2, covalent bonding is formed by sharing
p electrons
Example:
- Fluorine gas...
Covalent Bond (cont..)

- Oxygen (Outer orbital - 2s2 2p4) atoms share two p electrons

O + O

O

O

O=O
Bond Energy=28KJ/...
Covalent Bond (cont..)
For a given pair of atoms, with
higher bond order, the bond
length will decrease; as bond
length de...
Metallic Bond
Atoms in metals are closely packed in crystal structure.
Loosely bounded valence electrons are attracted tow...
Metallic Bond (cont..)
Overall energy of individual atoms are lowered by metallic
bonds.
Minimum energy between atoms exis...
Metallic Bond (cont..)
Higher the number of valence electrons involved, higher is the
bonding energy.
Example:-

Ca

Bondi...
Metallic Bond (cont..)

The bond energies and the melting point of metals vary
greatly depending on the number of valence ...
Metallic Bond (cont..)
Pure metals are significantly more malleable than ionic or
covalent networked materials.
Strength o...
Secondary Bonding
Secondary bonds are due to electrostatic attractions of
electric dipoles in atoms or molecules.
Dipoles ...
Fluctuating Dipoles
Weak secondary bonds in noble gasses.
Dipoles are created due to asymmetrical distribution of
electron...
Permanent Dipoles
Dipoles that DO NOT fluctuate with time are called
permanent dipoles.
Example:

CH4

CH3Cl

Symmetrical
...
Hidrogen bond
Hydrogen bonds are Dipole-Dipole interaction between
polar bonds containing hydrogen atom.

Example :- In wa...
Van der Waals bond
The main characteristic: A week bond formed due to the
attraction between the positive nucleas at the c...
Mixed Bond
Chemical bonding of atoms or ions can involve more than one
type of primary bond and also can involve secondary...
References
 A.G. Guy (1972) Introduction to Material Science, McGraw
Hill.
 J.F. Shackelford (2000). Introduction to Mat...
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  1. 1. PHY351 CHAPTER 2 Atomic Structure and Bonding 1
  2. 2. History of atom 17th century: Robert Boyle asserted that elements are made up of “simple bodies” which themselves are not made up of any other bodies. 19th century: - John Dalton stated that matter is made up of small particles called atoms. - Henri Becquerel and Marie and Pierre Curie in France, introduced the concept of radioactivity. - Joseph J. Thompson found electrons. In 1910 Ernest Rutherford found protons. In 1932 James Chadwick found neutrons. 2
  3. 3. Structure of atom ATOM Basic Unit of an Element Diameter : 10 –10 m. Neutrally Charged Nucleus Diameter : 10 –14 m Accounts for almost all mass Positive Charge Proton Mass : 1.673 x 10 –24 g Charge : 1.602 x 10 –19 C Electron Cloud 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 3
  4. 4. Figure 2.2: The relative size of an atom and its nucleus that is made up of protons and neutrons. 4
  5. 5. 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 6.203 x 1023 (Avagadro Number) Atoms. 5
  6. 6. The mass number (A) is the sum of protons and neutrons in a nucleus of an atom. Example : Carbon has 6 Protons and 6 Neutrons. Therefore; A= 12. One Atomic Mass unit is 1/12th of mass of carbon atom. One gram mole = Gram atomic mass of an element. Isotope: Variations of element with same atomic number but different mass number. One gram Mole of Carbon 12 Grams Of Carbon 6.023 x 1023 Carbon Atoms 6
  7. 7. Quantum Numbers of Electrons of Atoms Principal Quantum Number (n) • Represents main energy levels. • • Range 1 to 7. Larger the ‘n’ higher the energy. 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 n=3 n=1 n=2 s orbital (l=0) p Orbital (l=1) 7
  8. 8. s, p and d Orbitals 2 2 2 Schematic diagram of s, p and d orbitals 8
  9. 9. Quantum Numbers of Electrons of Atoms Magnetic Quantum Number ml. • Represents spatial orientation of single atomic orbital. • Permissible values are –l to +l. • Example:- if l=1, ml = -1,0,+1. I.e. 2l+1 allowed values. • No effect on energy. • • • • • Electron spin quantum number ms. 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. 9
  10. 10. Electron Structure of Multielectron Atom Maximum number of electrons in each atomic shell is given by 2n2. Atomic size (radius) increases with addition of shells. Electron Configuration lists the arrangement of electrons in orbital.  Example :- Orbital letters Number of Electrons 1s2 2s2 2p6 3s2 Principal Quantum Numbers  For Iron, (Z=26), Electronic configuration is 1s2 2s2 sp6 3s2 3p6 3d6 4s2 10
  11. 11. Multielectron Atoms Nucleus charge effect: The higher the charge of the nucleus, the higher is the attraction force on an electron and the lower the energy of the electron. Shielding effect: Electrons shield each other from the full force of the nucleus. The inner electrons shield the outer electrons and do so more effectively. In a given principal shell, n, the lower the value of l, the lower will be the energy of the subshell; s < p < d <f. Figure 2.9 The energy level for all subenergy levels up to n = 7. The orbitals will fill in the 11 same exact order,
  12. 12. The Quantum-Mechanical Model and the Periodic Table Elements are classified according to their ground state electron configuration. Table 2.4 Allowed values for the quantum numbers and electrons 12
  13. 13. Periodic table Figure 2.3 The updated periodic table showing seven periods, eight main group elements, transition element and inner transition elements. Note that the majority of the elements are classified as metals 13 or metalloids.
  14. 14. Metals, Metalloids, and Nonmetals Reactive metals (or simply metals): Electro positive materials, have the natural tendency of losing electrons and in the process form cations. Reactive nonmetals (or simply nonmetals): Electronegative, they have the natural tendency of accepting electrons and in the process form anions. Metalloids: Can behave either in a metallic or a nonmetallic manner. Examples: – In group 4A, the carbon and the next two members, silicon and germanium, are metalloids while tin and lead, are metals. – In group 5A, nitrogen and phosphorous are nonmetals, arsenic and antimony are metalloids, and finally bismuth is a metal. 14
  15. 15. Primary Bonds Bonding with other atoms, the potential energy of each bonding atom is lowered resulting in a more stable state. Three primary bonding combinations : metal-nonmetal nonmetal-nonmetal metal-metal 15
  16. 16. 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 16
  17. 17. Ionic Bond 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 Electronegative Electron Element Atom Transfer Cation +ve charge Electrostatic Attraction Anion -ve charge IONIC BOND 17
  18. 18. Ionic Bond (cont..) Large difference in electronegativity. When a metal forms a cation, its radius reduces and when a nonmetal forms an anion, its radius increases. The electronegativity variations 18
  19. 19. Ionic Bond (cont..) Example: Ionic bonding in NaCl 3s1 3p6 Sodium Atom Na Sodium Ion Na+ I O N I C B O N D Chlorine Atom Cl Chlorine Ion Cl - 19
  20. 20. Covalent Bond 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. Overlapping Electron Clouds 20
  21. 21. Covalent Bond (cont..) In Hydrogen, a bond is formed between 2 atoms by sharing their 1s1 electrons Electron Pair H + H H H 21
  22. 22. Covalent Bond (cont..) In case of F2, O2 and N2, covalent bonding is formed by sharing p electrons Example: - Fluorine gas (Outer orbital – 2s2 2p5) share one p electron to attain noble gas configuration. F + F H F F F F Bond Energy=160KJ/mol 22
  23. 23. Covalent Bond (cont..) - Oxygen (Outer orbital - 2s2 2p4) atoms share two p electrons O + O O O O=O Bond Energy=28KJ/mol - Nitrogen (Outer orbital - 2s2 2p3) atoms share three p electrons N + N N N N N Bond Energy=54KJ/mol 23
  24. 24. Covalent Bond (cont..) For a given pair of atoms, with higher bond order, the bond length will decrease; as bond length decreases, bond energy will increase (H2, F2, N2). Nonpolar bonds: sharing of the bonding electrons is equal between the atoms and the bonds. Polar covalent bond: Sharing of the bonding electrons is unequal (HF, NaF). 24
  25. 25. Metallic Bond 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 25
  26. 26. Metallic Bond (cont..) Overall energy of individual atoms are lowered by metallic bonds. Minimum energy between atoms exist at equilibrium distance a0. Fewer the number of valence electrons involved, more metallic the bond is. Example:- Na Bonding energy 108KJ/mol Melting temperature 97.7oC 26
  27. 27. Metallic Bond (cont..) Higher the number of valence electrons involved, higher is the bonding energy. Example:- Ca Bonding energy 177KJ/mol Melting temperature 851oC 27
  28. 28. Metallic Bond (cont..) The bond energies and the melting point of metals vary greatly depending on the number of valence electrons and the percent metallic bonding. 28
  29. 29. Metallic Bond (cont..) Pure metals are significantly more malleable than ionic or covalent networked materials. Strength of a pure metal can be significantly increased through alloying. Pure metals are excellent conductors of heat and electricity. 29
  30. 30. Secondary Bonding Secondary bonds are due to electrostatic attractions of electric dipoles in atoms or molecules. Dipoles are created when positive and negative charge centers exist. There two types of bonds: permanent fluctuating 30
  31. 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 Asymmetrical Distribution (Changes with time) 31
  32. 32. Permanent Dipoles Dipoles that DO NOT fluctuate with time are called permanent dipoles. Example: CH4 CH3Cl Symmetrical Arrangement Of 4 C-H bonds Asymmetrical Tetrahedral arrangement No Dipole moment Creates Dipole 32
  33. 33. Hidrogen bond 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 105 0 O H Hydrogen Bond 33
  34. 34. Van der Waals bond The main characteristic: A week bond formed due to the attraction between the positive nucleas at the center and the electron outside. Example: H2O 34
  35. 35. Mixed Bond Chemical bonding of atoms or ions can involve more than one type of primary bond and also can involve secondary dipole bonds. For primary bonding, there can be the following combination: Ionic-covalent (Example: GaAs, ZnSe) Metallic-covalent (Example: group 4A in Si or Ge) Metallic-ionic (Example: Al9CO3, Fe5Zn21) Ionic-covalent-metallic 35
  36. 36. References  A.G. Guy (1972) Introduction to Material Science, McGraw Hill.  J.F. Shackelford (2000). Introduction to Material Science for Engineers, (5th Edition), Prentice Hall.  W.F. Smith (1996). Priciple to Material Science and Engineering, (3rd Edition), McGraw Hill.  W.D. Callister Jr. (1997) Material Science and Engineering: An Introduction, (4th Edition) John Wiley. 36
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