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METALLURGY AND MATERIAL SCIENCE

CHEMICAL BONDS

Dr. Binu C. Yeldose,


Lecturer,
Department of Mechanical Engineering,
Mar Athanasius College of Engineering.
KOTHAMANGALAM
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C.Yeldose
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SURVEY OF ELEMENTS
• Most elements: Electron configuration not stable.

Element Atomic # Electron configuration


Hydrogen 1 1s 1
Helium 2 1s 2 (stable)
Lithium 3 1s 2 2s 1
Beryllium 4 1s 2 2s 2
Boron 5 1s 2 2s 2 2p 1 Adapted from Table 2.2,
1s 2 2s 2 2p 2 Callister 6e.
Carbon 6
... ...
Neon 10 1s 2 2s 2 2p 6 (stable)
Sodium 11 1s 2 2s 2 2p 6 3s 1
Magnesium 12 1s 2 2s 2 2p 6 3s 2
Aluminum 13 1s 2 2s 2 2p 6 3s 2 3p 1
... ...
Argon 18 1s 2 2s 2 2p 6 3s 2 3p 6 (stable)
... ... ...
Krypton 36 1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4 6 (stable)

• Why? Valence (outer) shell usually not filled completely.


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Shell Designation Sub Shell No. of Electrons
K s 2

L s 2
p 6 8

M s 2
p 6
d 10 18

N s 2
p 6
d 10
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f 14
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- Dr. Binu 32
Ionization energy

The ionization energy is the energy required to remove a


single shell (valence) electron from an isolated neutral atom.
The ionization energy is a measure of the ease with which
conduction electrons can be created.

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Electronegativity
Is a measure of the ability of an atom in a molecule
to attract electrons to itself.

Concept proposed by Linus Pauling 1901 -1994


1901-1994

ALLOYING ????
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THE PERIODIC TABLE
• Columns: Similar Valence Structure

inert gases
give up 1e
give up 2e

accept 2e
accept 1e
give up 3e

Metal

Nonmetal
H He
Li Intermediate Ne
Be O F
Na Mg S Cl Ar
K Ca Sc Se Br Kr
Rb Sr Y Te I Xe
Cs Ba Po At Rn
Fr Ra
Adapted
from Fig. 2.6,
Callister 6e.
Electropositive elements: Electronegative elements:
Readily give up electrons Mar Athanasius College of Readily acquire electrons 8
6
Engineering - MECH - Dr. Binu
to become - ions.
to become + ions.
C.Yeldose
Ionization energy vs. atomic number
2500 He
Ionization energy (kJ/mol)

Ne
2000
F Ar
1500
N
H O Cl
1000 Be C P S
B Mg Si
Al Ca
500
Li Na K
0
0 2 4 6 8 10 12 14 16 18 20
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Element
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Atomic radius vs. atomic number
250
K
Atom ic Radius (pm )

200
Na Ca
150 Li Mg
Al Si
100 Be P S Cl
B C N
O F Ar
50 Ne
H He
0
0 2 4 6 8 10 12 14 16 18 20
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Element
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Atomic Radius

• Measures as distance from nucleus to


nucleus and divided by 2.

• Unit commonly used is pm


• picometer= 10-12m

• Example: iodine atomic radius 140pm

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• ATOMIC NUMBER - N – r0

• Strength of material - correlate

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STRENGTH AND ATOMIC RADIUS?
• atomic number is the number of protons in the
nucleus and also the number of electrons around
the nucleus.
• as the atomic number increases, the number of
electrons increases, the number of shells
increases therefore atomic radius increases.
• as a result the valence shell and valence electrons
become away from the nucleus reducing the
attraction between outer shell and nucleus which
in turn reduces the strength.
• thus, as atomic number increases, strength
decreases and as atomic number decreases
strength increases.Mar Athanasius College of 13
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Summary – Atomic Structure
N -atomic number
Atomic radius
Strong/weak attraction
Strength/hardness, M.P. of element/material
correlated to atomic radius
Hardness/strength is inversely proportional to
the chemical bond length.
Cohen in 1985 predicted a new form of carbon (C=6)
nitride (N=7) that exhibits an extremely low
compressibility and super high hardness that
exceeds that of diamond Ref:- B. Bhusan
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Bond Length
• Bond length is the distance between the nuclei of two bonded
atoms. ro = 1-2 Å – primary bonds; 2-5 Å–secondary bonds.
• Bond length increases with increase with atomic number/
radius.

ro

Fmax = F / Cohesive strength of materials

ro Mar Athanasius College of 16


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ro = 1 - 2 Å – primary bonds;
2 - 5 Å – secondary bonds

• 1eV = 100 KJ/mole


• The difference in ro is too small but large
variation in properties.

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Periodic Trends in Lattice Energy
Coulomb’s Law
charge A X charge B
electrostatic force α
distance2

energy = force X distance therefore

charge A X charge B
electrostatic energy α
distance

cation charge X anion charge


electrostatic energy α α ∆H0lattice
cation radius + anion radius

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A B
• Net bonding force F (r ) ≡ r M − rN For N>M

r – centre to centre spacing


A an B – Material constants –type of bonds
M =2 PRIMARY BOND
=7 Van der Waals bonds
N = 7 to 10 Metallic bonds
= 9 to 12 Covalent bonds
= 10 to 12 Ionic bonds

First term and second terms of right hand side represents


the attractive and repulsive forces
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Fmax = F / Cohesive strength of materials/Theoretical strength
of material.

Fmax per unit cross-sectional area A, reaches to the value of


materials Young's modulus E. F max
σ max = =E
A
Structural steel E = 200 GPa. Therefore Fmax = 200 GPa.

But practically it is much lower value = 0.6 GPa?

Presence of Imperfections
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Cohesive strength

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courtesy: Callister
C.Yeldose
Charge and Attractive Force Control on
Effective Ionic Radii

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Solid

Liquid Gas

E0
ro

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CHEMICAL BONDS

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Marriage

Forming
of a bond
The
is like
breaking
marriage
of a bond
•More stable/ relates to
a divorce.
equilibrium
•exothermic
Divorce

•Less stable/
want of electrons to
fill outer shell
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•Endothermic
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Types of Chemical Bonding

1. Metal with nonmetal:

electron transfer and ionic bonding

2. Nonmetal with nonmetal:

electron sharing and covalent bonding

3. Metal with metal:

electron pooling and metallic bonding

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Classification of Chemical bonds
(a) Primary bonds (Strong Bonds:-100 - 1500 kJ/mole
/ 1-15 eV/bond - ro = 1 - 2 Å )

• Ionic bond (NON METAL+ METAL)


• Covalent bond (NON METAL+ NON METAL)
• Metallic bond (METAL+ METAL)

(b) Secondary bonds (Weak Bonds:- 1- 50 kJ/mole


/ 0.01- 0.5 eV/bond - ro = 2 - 5 Å )

Inter molecular, gases and liquids - feeble and less stable.


• Di-pole bond
• Hydrogen bond
• Van der Waals bond
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Bonding Overview
All bonding forces are due to electrostatic charge.
Opposite charges attract, Like charges repel.
This diagram shows the attraction and repulsion
between atoms: The outer ring (e-) is the electron
cloud. The inner red ring is the nucleus.

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Dog - Bone
Bonds

• the natural attraction


between dogs and
bones is like the
attraction between
opposite charges
and atomic bonds.

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Ionic Bonding

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Types of Chemical Bonding

1. Metal with nonmetal:

electron transfer and ionic bonding


2. Nonmetal with nonmetal:

electron sharing and covalent bonding

3. Metal with metal:

electron pooling and metallic bonding

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Characteristics Ionic Bonding
Metal+ non metal

Transfer of electrons - easily exchange/ transfer electrons so as


to stabilize their outer shells (i.e. become more inert gas-like)

NON DIRECTIONAL – over lapping of electrons orbitals are


spherically symmetric.
magnitude of the bond equal in all directions around an ion
OR BOND POSSES EQUAL STRENGTH IN ALL DIRECTIONS.

Bond energies : 600 – 1500 kJ/mol (6-15 eV / atom)


High melting temperature, hard, brittle, electrically and
thermally insulative.
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Density???????????- highEngineering - MECH - Dr. Binu
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• Both ionically and covalent bonded
materials are poor conductors, because
electrons are not to leave their host atoms.

• The delocalized electrons of metals move


easily along a potential gradient. Therefore
metallic boned materils are good
conductors

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Ionic bonds:
One big greedy thief dog
• Ionic bonding is like one
big greedy dog steeling the
other dog's bone.
• The bone represents the
electron that is up for
grabs.
• When the big dog gains an
electron he becomes
negatively charged and the
little dog who lost the
electron becomes
positively charged.
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Properties of Ionic Compounds

• Crystalline structure.
• A regular repeating arrangement of ions in
the solid.
• Ions are strongly bonded.
• Structure is rigid.
• High melting points- because of strong
forces between ions.

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Conductivity
• Conducting electricity is allowing charges
to move.
• In a solid, the ions are locked in place.
• Ionic solids are insulators.
• When melted, the ions can move around.
• Melted ionic compounds conduct.
• Dissolved in water they conduct.

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EXAMPLES: IONIC BONDING
• Predominant bonding in Ceramics
NaCl
MgO
H He
2.1 CaF 2 -
Li Be O F Ne
1.0 1.5 Cs Cl 3.5 4.0 -
Na Mg Cl Ar
0.9 1.2 3.0 -
K Ca Ti Cr Fe Ni Zn As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 2.0 2.8 -
Rb Sr I Xe
0.8 1.0 2.5 -
Cs Ba At Rn
0.7 0.9 2.2 -
Fr Ra
0.7 0.9

Give up electrons Acquire electrons


Adapted from Fig. 2.7, Callister 6e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the Chemical Bond, 3rd edition,
Copyright 1939 and 1940, 3rd edition. Copyright Mar 1960Athanasius
by Cornell College of 38
University. 9
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Covalent Bond

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Types of Chemical Bonding

1. Metal with nonmetal:

electron transfer and ionic bonding

2. Nonmetal with nonmetal:

electron sharing and covalent bonding


3. Metal with metal:

electron pooling and metallic bonding

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Covalent Bond

covalent bond- a bond formed when atoms share


electrons equally

Two atoms share one or more pairs of outer-shell electrons.

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Characteristics Covalent Bonding

Non Metal+ Non metal


Sharing of electrons
strongest of all chemical bonds
Sharing – net decrease in P.E - good overlap of orbital- bring
shared electrons close both the nuclei-Overlapping orbitals
are directionally oriented and not spherically symmetric.
DIRECTIONAL – magnitude of the bond is not equal in all
directions .
Bond energies : 100 – 1000 kJ/mol (1-10 eV / atom)
High melting temperature, hard, brittle, electrically and
thermally insulative
Density???????????- low
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Covalent Bonds:
Dogs of equal strength
Think of two or more
dogs with equal
attraction to the bones.

The dogs (atoms) are


identical, so the dogs
share the pairs of
available bones evenly.

Since one dog does not


have more of the bone
than the other dog, the
charge is evenly
distributed.
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Oxygen O 8 1s22s22p4

Oxygen Atom Oxygen Atom

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Oxygen Molecule (O2)
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EXAMPLES: COVALENT BONDING

H2 O

column IVA
H2 F2
C(diamond)
H He
2.1
Si C - Cl 2
Li Be C O F Ne
1.0 1.5 2.5 2.0 4.0 -
Na Mg Si Cl Ar
0.9 1.2 1.8 3.0 -
K Ca Ti Cr Fe Ni Zn Ga Ge As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 1.6 1.8 2.0 2.8 -
Rb Sr Sn I Xe
0.8 1.0 1.8 2.5 -
Cs Ba Pb At Rn
0.7 0.9 1.8 2.2 -
Fr Ra
0.7 0.9
Adapted from Fig. 2.7, Callister 6e. (Fig. 2.7 is GaAs
adapted from Linus Pauling, The Nature of the Chemical Bond, 3rd edition, Copyright 1939 and
1940, 3rd edition. Copyright 1960 by Cornell University.

• Molecules with nonmetals


• Molecules with metals and nonmetals
• Elemental solids (RHS of Periodic Table)
• Compound solids (about column
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College of
11
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Density???????????- high –
ionic bond

Density???????????- low-
covalent bond
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Metallic Bonding

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Types of Chemical Bonding

1. Metal with nonmetal:

electron transfer and ionic bonding

2. Nonmetal with nonmetal:

electron sharing and covalent bonding

3. Metal with metal:

electron pooling and metallic bonding

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Characteristics Metallic Bonding
Metal+ metal
Delocalized electrons /electron cloud/sea of electrons

NON DIRECTIONAL – over lapping of electrons orbitals


are spherically symmetric.
magnitude of the bond equal in all directions around an
ion OR BOND POSSES EQUAL STRENGTH IN ALL
DIRECTIONS
Bonding energy: wide range: -
E (Hg) = 0.7eV/atom, E (W) = 8.8.eV/atom

Metals are lustrous


Ductile, electrically and thermally conductive
Density???????????- high
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• The free electron theory of metals, which
started with Drude (1902) and Lorentz
(1916).

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Metallic Bonds
Mellow dogs with plenty of bones to go around

• Think of a room full of puppies who have plenty of bones


to go around and are not possessive of any one particular
bone. This allows the electrons to move through the
substance with little restriction. The
Mar Athanasius College of model is often 51
described as the "kernels
Engineeringof atoms
- MECH in a sea of electrons."
- Dr. Binu
C.Yeldose
Metallic Bond
Metallic Bonding
Bonding between atoms with
low electronegativity. ie 1,2
or 3 valence electrons,
therefore there are many
vacancies in valence shell.

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Sea of Electrons

• Electrons are free to move through the


solid.
• Metals conduct electricity.

+ + + +
+ + + +
+ + + +

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• Metals have low ionization energies,
energies thus they do not have a
tight hold on their valence electrons.

• These outer electrons easily move around, as they do not


"belong" to any one atom, but are part of the whole metal crystal.

• Metals are good conductors of heat and electricity. This is


directly due to the mobility of the electrons.

-Metals are malleable (can be flattened) and ductile (can be


drawn into wires) because of the way the metal cations and
electrons can "flow" around each other, without breaking the
crystal structure.

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- Metals are lustrous. This is due to the uniform way that the
valence electrons of the metal absorb and re-emit light energy.

• The free electrons oscillate in the alternating electric field of


the incident light beam, absorbing energy at all wavelengths
and so making the metal opaque.

• In turn the oscillating electrons emit waves and in this way


produce the reflected beam.

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PROPERTIES FROM BONDING

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r5
Shallow well

r4

r0 Deep well

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Mean inter atomic distance

r5

Bond energy
r4

r0

Shallow well Deep well


Weakly bonded solid Strongly bonded solid

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Shallow well

Deep well

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Young’s modulus is a numerical constant, named for the

18th century English physician and physicist Thomas Young,

that describes the elastic properties of a solid

undergoing tension or compression in only one direction.

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Elastic Modulus - Metal Cutting

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TABLE 2.2 Mechanical Properties of Various Materials at Room Temperature
Elongation
in 50 mm
Metals (Wrought) E (GPa) Y (MPa) UTS (MPa) (%)
Aluminum and its alloys 69–79 35–550 90–600 45–4
Copper and its alloys 105–150 76–1100 140–1310 65–3
Lead and its alloys 14 14 20–55 50–9
Magnesium and its alloys 41–45 130–305 240–380 21–5
Molybdenum and its alloys 330–360 80–2070 90–2340 40–30
Nickel and its alloys 180–214 105–1200 345–1450 60–5
Steels 190–200 205–1725 415–1750 65–2
Titanium and its alloys 80–130 344–1380 415–1450 25–7
Tungsten and its alloys 350–400 550–690 620–760 0
Nonmetallic materials
Ceramics 70–1000 — 140–2600 0
Diamond 820–1050 — — —
Glass and porcelain 70-80 — 140 —
Rubbers 0.01–0.1 — — —
Thermoplastics 1.4–3.4 — 7–80 1000–5
Thermoplastics, reinforced 2–50 — 20–120 10–1
Thermosets 3.5–17 — 35–170 0
Boron fibers 380 — 3500 0
Carbon fibers 275–415 — 2000–3000 0
Glass fibers 73–85 — 3500–4600 0
Kevlar fibers 62–117 — 2800 0
Note: In the upper table the lowest values for E, Y, and UTS and the highest values for elongation are for pure metals.
Multiply gigapascals (GPa) by 145,000 to obtain pounds per square in.College
Mar Athanasius (psi), megapascals
of (MPa) by 145 to obtain psi. 63
Engineering - MECH - Dr. Binu
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Problems in machining Titanium
Compared to high strength steels, titanium, due to its
unique physical and chemical properties, poses the
following problems:

• Lower thermal conductivity of Ti hinders quick


dissipation of the heat caused by machining, leading to
increased wear of cutting tools.

• Lower modulus of elasticity leads to high spring back,


causing Ti parts to move away from the cutting tool.

• Lower hardness and high chemical reactivity of Ti lead


to galling with the cutting tool.
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M.T.
Bond substance kJ/mol eV/atom
(oC)

NaCl 640 3.3 801


Ionic
MgO 1000 5.2 2800
Si 450 4.7 1410
Covalent
C (Diam.) 713 7.4 > 3550
Hg 68 0.7 - 39
Al 324 3.4 660
Metallic
Fe 406 4.2 1538
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W 849
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M.T.
Bond substance kJ/mol eV/atom
(oC)

Van der Ar 7.7 0.08 - 189


Waals Cl2 31 0.32 - 101

NH3 35 0.36 - 78
Hydrogen
H2O 51 0.52 0

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BOND ENERGIES AND BOND LENGTHS
Bond energy Bond length
Bond
kJ/mol nm
C-C 370 0.154
C=C 680 0.13
C ≡C 890 0.12
C-H 435 0.11
C-N 305 0.15
C-O 360 0.14
C=O 535 0.18
C-F 450 0.14
C-Cl 340
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• Single bond: one pair of electrons are shared between two atoms

• Double bond: two pairs of electrons are shared between two atoms

• Triple bond: three pairs of electrons are shared between two atoms

Bond energy: the amount of energy required to break a bond holding two atoms
together.

triple bond > double bond > single bond

Bond length: the distance separating the nuclei

single bond > double bond > triple bond

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SUMMARY-BONDING -PROPERTIES

• HARDNESS/STRENGTH –Atomic radius


• Tensile Vs Compressive force - more required?
• MP
• DIRECTIONAL / NON-DIRECTIONAL
• DENSITY
• CONDUCTIVITY
• E- Young's modulus, MP, CTE.
• α – CTE
• DUCTILITY/BRITTLE ??
• Metals are lustrous and opaque

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REVIEW QUESTIONS
1. Correlate the strength of an element with atomic radius.
2. Explain the maximum number of electrons permitted in K, L, M, N shells.
3. Correlate the bond length with coefficient of thermal expansion.
4. Correlate the bond length with young's modulus of a material.
5. Correlate the bond length with melting point of a material.
6. What is the significance of cohesive strength of a material.
7. To separate two atoms, tensile or compressive force more required? Explain why?
8. Why ionic and covalent bonded material exhibit bad conductors of heat and
electricity ?
9. Why metallic bonds are opaque?
10. Why metallic bonded material are ductile?
11. Why ionic and covalent bonded material are hard and brittle?
12. What is directional and non-directional bonds?
13. Why covalent bonded material are less denser than metallic and ionic bonded
material?
14. What kind of bonding you expect in the following materials: NaCl, Cadmium
telluride, Bronze, SO2, RbI, FeC, C6H6, InAs, UH3, CaS, BN, GdO, GdTe.
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15. Explain the need of highly pressurized injection
Engineering - MECH of diesel into the cylinder.
- Dr. Binu
C.Yeldose
Secondary Bonds

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- +
+
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Vander Waals Forces

• Random electron movements creates


dipoles.
• Dipoles induces dipoles.
• Process is repeated.
• Oppositely charged dipoles attract.

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Dipole-dipole attraction
. More electronegative atom in a covalent
bond.
. Permanent dipoles.
. Attraction between dipoles.

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Dipole-dipole attraction-Factors
• More the number of electronegative
atoms, higher attraction
• More electronegative atoms, higher
attraction

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Why ice float on water

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Hydrogen Bond
. Hydrogen in a covalent bond with nitrogen,
oxygen or fluorine.
. Permanent dipoles.
. Attraction between dipoles.
. Strongest intermolecular force.
. Intermolecular forces much weaker than normal
covalent bonds

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HYDROGEN BOND
(Water)
Each hydrogen has 1 valence electron

H Each hydrogen wants 1 more

The oxygen has 6 valence electrons

O The oxygen wants 2 more


They share to make each other happy

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Water
• Put the pieces together
• The first hydrogen is happy
• The oxygen still wants one more

HO
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Water

• The second hydrogen attaches


• Every atom has full energy levels

HO
H
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Hydrogen Bonding

Tetrahedron

H2O molecule

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H H

Hydrogen bonding
O

Ice structure

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Ice, like all solids, has a well-defined structure; each water
molecule is surrounded by four neighboring H2Os. two of
these are hydrogen-bonded to the oxygen atom on the
central H2O molecule, and each of the two hydrogen atoms is
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similarly bonded to another neighboring
Engineering - MECH - Dr. Binu H2O.
C.Yeldose
When ice melts to form liquid water, the uniform three-
dimensional tetrahedral organization of the solid breaks
down as thermal motions disrupt, distort, and occasionally
break hydrogen bonds. The methods used to determine the positions of
molecules in a solid do not work with liquids, so there is no unambiguous way
of determining the detailed structure of water. The illustration here is probably
typical of the arrangement of neighbors around any particular H2O molecule,
but very little is known about the
Marextent to which
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propagated to more distant molecules C.Yeldose
Hydrogen Bonds (H-bonds)

Hydrogen bonds of water


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Recent work from Richard SayKally's
laboratory
This computer-generated
shows that the hydrogen bonds in liquid
water break and re-form so rapidly
nanoscale view of liquid water is
(often in distorted configurations) that from the lab of Gene Stanley of
the liquid can be regarded as a Boston University .The oxygen
continuous network of hydrogen-bonded atoms are red, the hydrogen atoms
molecules. white.

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Ice floats because it is about 9% less dense than liquid water

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• Ice floats because it is about 9% less dense
than liquid water.

• lakes and rivers freeze from top to bottom, allowing


fish to survive even when the surface of a lake has
frozen over. If ice sank, the water would be displaced
to the top and exposed to the colder temperature,
forcing rivers and lakes to fill with ice and freeze solid
= Acts as a insulator (eg. Igloo).

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WHY WATER HAS HIGH
SPECIFIC HEAT

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• Low molecular mass - so more moles per kg

• It is higher than most other liquids or high heat


carrying away capacity or J/Kg

• This is mainly because a given mass of water


contains more molecules (and therefore more
degrees of freedom in which to store energy)
than the same mass of other liquids.

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• molecular weight, weight of a molecule of a
substance expressed in atomic mass units
(amu). The molecular weight may be
calculated from the molecular formula of
the substance; it is the sum of the atomic
weights of the atoms making up the
molecule.

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Elemental composition of H2O:

Atomic Number of
Symbol Element Mass percent
weight atoms

H Hydrogen 1.007947 2 11.1899 %

O Oxygen 15.99943 1 88.8101 %

The molecular weight of water is thus

(2 × 1.008)+(1×15.999) = 2.016+15.999 = 18.015 amu. or g/mol


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Elemental composition of NH3:

Symbol Element Atomic weight Number of atoms Mass percent


N Nitrogen 14.00672 1 82.2446 %
H Hydrogen 1.007947 3 17.7554 %

Molar mass (molecular weight) of NH3 is 17.0306 g/mol

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SUMMARY: BONDING

Type Bond Energy Comments

Nondirectional (ceramics)
Ionic Large!

Variable Directional
(semiconductors,
Covalent large-Diamond ceramics, polymer chains)
small-Bismuth

Variable
large-Tungsten Nondirectional
Metallic
small-Mercury (metals)

Directional
Secondary smallest
inter-chain (polymer),
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Strong forces within molecules and weak
forces between them.
Strong covalent bonding forces within molecules

ATOMIZATION ?? Weak intermolecular forces between molecules

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Elastic properties determined by binding between
atoms. HOW?

Plastic properties determined by microstructure.

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microstructure

Resistance to crack propagation


WHY?

Binding of atoms

Resistance to plastic deformation


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Resistance to elastic deformation – STIFFNESS
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ENGINEERING STRESS

TRUE STRESS

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