Chapter 2 - 1
Properties depend on
- arrangement of atoms
- interactions between atoms
Study Bonding:
• What promotes bonding?
• What types of bonds are there?
• What properties are inferred from bonding?
CHAPTER 2:
BONDING AND PROPERTIES
Chapter 2 - 2
Atomic Structure (Freshman Chem.)
• atom – electrons – 9.11 x 10-31
kg
protons
neutrons
• nucleus of atom: “size of a point on a page” -! ‫فراغ‬
• atomic number = No. of protons in nucleus of atom
= No. of electrons of neutral species
A [=] atomic mass unit = amu = 1/12 mass of 12
C
Atomic wt = wt of 6.023 x 1023
molecules or atoms
Unit 1 amu/atom = 1g/mol
C 12.011
H 1.008 etc.
} 1.67 x 10-27
kg
Chapter 2 - 3
Atomic Structure
• Valence electrons: in the outer-shell
• determine all of the following properties
1) Chemical: reactivity
2) Electrical: conductivity
3) Thermal: conductivity
4) Optical: transmittance
Chapter 2 - 4
Electronic Structure - Review
• Electrons have wavelike and particulate properties.
– This means that electrons are in orbitals defined by a
probability.
– Each orbital at discrete energy level determined by
quantum numbers.
Quantum # Designation
n = principal (energy level-shell) K, L, M, N, O (1, 2, 3, etc.)
l = subsidiary (orbitals) s, p, d, f (0, 1, 2, 3,…, n-1)
ml = magnetic (direction in space) 1, 3, 5, 7 (-l to +l)
ms = spin ½, -½
Chapter 2 - 5
Electron Energy States
1s
2s
2p
K-shell n = 1
L-shell n = 2
3s
3p M-shell n = 3
3d
4s
4p
4d
Energy
N-shell n = 4
• have discrete energy states
• tend to occupy lowest available energy state.
Electrons...
Chapter 2 - 6
• Why? Valence (outer) shell usually not filled completely.
• Most elements: Electron configuration not stable.
SURVEY OF ELEMENTS - Review
Electron configuration
(stable)
...
...
1s22s22p 63s23p 6 (stable)
...
1s22s22p 63s23p 63d 10 4s24p6 (stable)
Atomic #
18
...
36
Element
1s11Hydrogen
1s22Helium
1s22s13Lithium
1s22s24Beryllium
1s22s22p 15Boron
1s22s22p 26Carbon
...
1s22s22p 6 (stable)10Neon
1s22s22p 63s111Sodium
1s22s22p 63s212Magnesium
1s22s22p 63s23p 113Aluminum
...
Argon
...
Krypton
Chapter 2 - 7
Electron Configurations
• Valence electrons – those in unfilled shells
• Filled shells more stable
• Valence electrons are most available for bonding and
tend to control the chemical properties
• Primary Bonding: Ionic, Covalent and Metallic
• example: C (atomic number = 6)
1s2
2s2
2p2
valence electrons
Chapter 2 - 8
Electronic Configurations
ex: Fe - atomic # = 26
valence
electrons
1s
2s
2p
K-shell n = 1
L-shell n = 2
3s
3p M-shell n = 3
3d
4s
4p
4d
Energy
N-shell n = 4
1s2
2s2
2p6
3s2
3p6
3d6
4s2
Chapter 2 - 9
The Periodic Table
• Columns: Similar Valence Structure
Electropositive elements:
Readily give up electrons
to become + ions.
Electronegative elements:
Readily acquire electrons
to become - ions.
giveup1e
giveup2e
giveup3e
inertgases
accept1e
accept2e
O
Se
Te
Po At
I
Br
He
Ne
Ar
Kr
Xe
Rn
F
ClS
Li Be
H
Na Mg
BaCs
RaFr
CaK Sc
SrRb Y
Chapter 2 - 10
• Ranges from 0.7 to 4.0,
Smaller electronegativity Larger electronegativity
• Large values: tendency to acquire electrons.
Electronegativity
Chapter 2 - 11
Ionic bond – metal + nonmetal
donates accepts
electrons electrons
Dissimilar electronegativities
ex: MgO Mg 1s2
2s2
2p6
3s2
O 1s2
2s2
2p4
[Ne] 3s2
Mg2+
1s2
2s2
2p6
O2-
1s2
2s2
2p6
[Ne] [Ne]
1s22s22p 6 (stable)10Neon
Chapter 2 - 12
• Occurs between + and - ions.
• Requires electron transfer.
• Large difference in electronegativity required.
• Example: NaCl
Ionic Bonding
Na (metal)
unstable
Cl (nonmetal)
unstable
electron
+ -
Coulombic
Attraction
Na (cation)
stable
Cl (anion)
stable
Chapter 2 - 13
• Predominant bonding in Ceramics
Examples: Ionic Bonding
Give up electrons Acquire electrons
NaCl
MgO
CaF2
CsCl
Chapter 2 - 14
C: has 4 valence e -
,
needs 4 more
H: has 1 valence e -
,
needs 1 more
Electronegativities
are comparable.
Covalent Bonding
• similar electronegativity ∴ share electrons
• bonds determined by valence – s & p orbitals
dominate bonding
• Example: CH4
shared electrons
from carbon atom
shared electrons
from hydrogen
atoms
H
H
H
H
C
CH4
Chapter 2 - 15
Primary Bonding
• Metallic Bond -- delocalized as electron cloud
• Ionic-Covalent Mixed Bonding
% ionic character =
where XA & XB are Pauling electronegativities
%)100(x1−e
−
(XA−XB)2
4










ionic70.2%(100%)xe1characterionic% 4
)3.15.3( 2
=










−=
−
−
Ex: MgO XMg = 1.3
XO = 3.5
Chapter 2 - 16
Arises from interaction between dipoles
• Permanent dipoles-molecule induced
• Fluctuating dipoles
-general case:
-ex: liquid HCl
-ex: polymer
Adapted from Fig. 2.14,
Callister 7e.
SECONDARY BONDING
asymmetric electron
clouds
+ - + -
secondary
bonding
HH HH
H2 H2
secondary
bonding
ex: liquid H2
H Cl H Cl
secondary
bonding
secondary
bonding
+ - + -
secondary bonding
secondary bonding
Chapter 2 - 17
Type
Ionic
Covalent
Metallic
Secondary
Bond Energy
Large!
Variable
large-Diamond
small-Bismuth
Variable
large-Tungsten
small-Mercury
smallest
Comments
Nondirectional (ceramics)
Directional
(semiconductors, ceramics
polymer chains)
Nondirectional (metals)
Directional
inter-chain (polymer)
inter-molecular
Summary: Bonding
Chapter 2 - 18
Interactions Between Atoms
+
-
+
-
r
+
-
+
-
Spacing (r)
Atomic Radius (R)
Far Atoms: Attraction Close Atoms: Repulsion
Equilibrium spacing = ro
ro = 2 R
+
-
+
-
Dynamic Equilibrium
Chapter 2 - 19
Chapter 2 - 20
Bonding Curve
Chapter 2 - 21
Bonding Curve
• Energy – minimum energy most stable
– Energy balance of attractive and repulsive terms
Attractive energy EA
Net energy EN
Repulsive energy ER
Interatomic separation r
r
A
n
r
B
EN = EA + ER = −−ro
Chapter 2 - 22
Bonding - Estimations
• Estimation of Bonding Energy (Eo) and Equilibrium Spacing (ro)
• Given:
• Bonding occurs at energy minimum
• At minimum: Derivative dE/dr = g(r) = 0
• Solve g(r) = 0 for r ro
• Substitute r=ro in the Energy Eqn:
• Get Eo = E (r=ro)
• Atomic radius R = ro/2
Eo =
“bond energy”
Energy
ro
r
r
A
n
r
B
E = certain f(r) e.g. E = −
For many atoms, ro is approximately 0.3 nm.
Chapter 2 - 23
• Bond length, r
• Bond energy, Eo
• Melting Temperature, Tm
Tm is larger if Eo is larger.
Properties From Bonding: Tm
ro
r
Energy
r
larger Tm
smaller Tm
Eo =
“bond energy”
Energy
ro
r
unstretched length
Chapter 2 - 24
• Coefficient of thermal expansion, α
• α ~ symmetry at ro
α is larger if Eo is smaller.
Properties From Bonding : α
= α (T2-T1)
∆L
Lo
Coefficient of thermal expansion
∆L
length, Lo
unheated, T1
heated, T2
ro
r
Smaller α
Larger α
Energy
unstretched length
Eo
Eo
Chapter 2 - 25
Ceramics
(Ionic & covalent bonding):
Metals
(Metallic bonding):
Polymers
(Covalent & Secondary):
Large bond energy
large Tm
large E
small α
Variable bond energy
moderate Tm
moderate E
moderate α
Directional Properties
Secondary bonding dominates
small Tm
small E
large α
Summary: Primary Bonds
secondary bonding
Bonding in Solids > Liquids > Gases
Chapter 2 - 26
Reading: Focus on Atomic Bonding in Solids
Core Problems:
2.7, 2.8, 2.12, 2.13,
2.17, 2.19, 2.21 (Callister 3rd
Addition)
Quiz: Next Class
ANNOUNCEMENTS
Chapter 2 - 27
Quiz
Energy
Atomic Spacing rA
B
c
Rank materials A, B and C according to
1. Increasing melting temperature > >
2. Decreasing bonding energy > >
3. Increasing Atomic Radius > >
4. Increasing coefficient of thermal expansion > >
Chapter 2 - 28
Quiz
Energy
Atomic Spacing r
A
B
c
Rank materials A, B and C according to
1. Increasing melting temperature > >
2. Decreasing bonding energy > >
3. Increasing Atomic Radius > >
4. Increasing coefficient of thermal expansion > >

Ch02 m

  • 1.
    Chapter 2 -1 Properties depend on - arrangement of atoms - interactions between atoms Study Bonding: • What promotes bonding? • What types of bonds are there? • What properties are inferred from bonding? CHAPTER 2: BONDING AND PROPERTIES
  • 2.
    Chapter 2 -2 Atomic Structure (Freshman Chem.) • atom – electrons – 9.11 x 10-31 kg protons neutrons • nucleus of atom: “size of a point on a page” -! ‫فراغ‬ • atomic number = No. of protons in nucleus of atom = No. of electrons of neutral species A [=] atomic mass unit = amu = 1/12 mass of 12 C Atomic wt = wt of 6.023 x 1023 molecules or atoms Unit 1 amu/atom = 1g/mol C 12.011 H 1.008 etc. } 1.67 x 10-27 kg
  • 3.
    Chapter 2 -3 Atomic Structure • Valence electrons: in the outer-shell • determine all of the following properties 1) Chemical: reactivity 2) Electrical: conductivity 3) Thermal: conductivity 4) Optical: transmittance
  • 4.
    Chapter 2 -4 Electronic Structure - Review • Electrons have wavelike and particulate properties. – This means that electrons are in orbitals defined by a probability. – Each orbital at discrete energy level determined by quantum numbers. Quantum # Designation n = principal (energy level-shell) K, L, M, N, O (1, 2, 3, etc.) l = subsidiary (orbitals) s, p, d, f (0, 1, 2, 3,…, n-1) ml = magnetic (direction in space) 1, 3, 5, 7 (-l to +l) ms = spin ½, -½
  • 5.
    Chapter 2 -5 Electron Energy States 1s 2s 2p K-shell n = 1 L-shell n = 2 3s 3p M-shell n = 3 3d 4s 4p 4d Energy N-shell n = 4 • have discrete energy states • tend to occupy lowest available energy state. Electrons...
  • 6.
    Chapter 2 -6 • Why? Valence (outer) shell usually not filled completely. • Most elements: Electron configuration not stable. SURVEY OF ELEMENTS - Review Electron configuration (stable) ... ... 1s22s22p 63s23p 6 (stable) ... 1s22s22p 63s23p 63d 10 4s24p6 (stable) Atomic # 18 ... 36 Element 1s11Hydrogen 1s22Helium 1s22s13Lithium 1s22s24Beryllium 1s22s22p 15Boron 1s22s22p 26Carbon ... 1s22s22p 6 (stable)10Neon 1s22s22p 63s111Sodium 1s22s22p 63s212Magnesium 1s22s22p 63s23p 113Aluminum ... Argon ... Krypton
  • 7.
    Chapter 2 -7 Electron Configurations • Valence electrons – those in unfilled shells • Filled shells more stable • Valence electrons are most available for bonding and tend to control the chemical properties • Primary Bonding: Ionic, Covalent and Metallic • example: C (atomic number = 6) 1s2 2s2 2p2 valence electrons
  • 8.
    Chapter 2 -8 Electronic Configurations ex: Fe - atomic # = 26 valence electrons 1s 2s 2p K-shell n = 1 L-shell n = 2 3s 3p M-shell n = 3 3d 4s 4p 4d Energy N-shell n = 4 1s2 2s2 2p6 3s2 3p6 3d6 4s2
  • 9.
    Chapter 2 -9 The Periodic Table • Columns: Similar Valence Structure Electropositive elements: Readily give up electrons to become + ions. Electronegative elements: Readily acquire electrons to become - ions. giveup1e giveup2e giveup3e inertgases accept1e accept2e O Se Te Po At I Br He Ne Ar Kr Xe Rn F ClS Li Be H Na Mg BaCs RaFr CaK Sc SrRb Y
  • 10.
    Chapter 2 -10 • Ranges from 0.7 to 4.0, Smaller electronegativity Larger electronegativity • Large values: tendency to acquire electrons. Electronegativity
  • 11.
    Chapter 2 -11 Ionic bond – metal + nonmetal donates accepts electrons electrons Dissimilar electronegativities ex: MgO Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4 [Ne] 3s2 Mg2+ 1s2 2s2 2p6 O2- 1s2 2s2 2p6 [Ne] [Ne] 1s22s22p 6 (stable)10Neon
  • 12.
    Chapter 2 -12 • Occurs between + and - ions. • Requires electron transfer. • Large difference in electronegativity required. • Example: NaCl Ionic Bonding Na (metal) unstable Cl (nonmetal) unstable electron + - Coulombic Attraction Na (cation) stable Cl (anion) stable
  • 13.
    Chapter 2 -13 • Predominant bonding in Ceramics Examples: Ionic Bonding Give up electrons Acquire electrons NaCl MgO CaF2 CsCl
  • 14.
    Chapter 2 -14 C: has 4 valence e - , needs 4 more H: has 1 valence e - , needs 1 more Electronegativities are comparable. Covalent Bonding • similar electronegativity ∴ share electrons • bonds determined by valence – s & p orbitals dominate bonding • Example: CH4 shared electrons from carbon atom shared electrons from hydrogen atoms H H H H C CH4
  • 15.
    Chapter 2 -15 Primary Bonding • Metallic Bond -- delocalized as electron cloud • Ionic-Covalent Mixed Bonding % ionic character = where XA & XB are Pauling electronegativities %)100(x1−e − (XA−XB)2 4           ionic70.2%(100%)xe1characterionic% 4 )3.15.3( 2 =           −= − − Ex: MgO XMg = 1.3 XO = 3.5
  • 16.
    Chapter 2 -16 Arises from interaction between dipoles • Permanent dipoles-molecule induced • Fluctuating dipoles -general case: -ex: liquid HCl -ex: polymer Adapted from Fig. 2.14, Callister 7e. SECONDARY BONDING asymmetric electron clouds + - + - secondary bonding HH HH H2 H2 secondary bonding ex: liquid H2 H Cl H Cl secondary bonding secondary bonding + - + - secondary bonding secondary bonding
  • 17.
    Chapter 2 -17 Type Ionic Covalent Metallic Secondary Bond Energy Large! Variable large-Diamond small-Bismuth Variable large-Tungsten small-Mercury smallest Comments Nondirectional (ceramics) Directional (semiconductors, ceramics polymer chains) Nondirectional (metals) Directional inter-chain (polymer) inter-molecular Summary: Bonding
  • 18.
    Chapter 2 -18 Interactions Between Atoms + - + - r + - + - Spacing (r) Atomic Radius (R) Far Atoms: Attraction Close Atoms: Repulsion Equilibrium spacing = ro ro = 2 R + - + - Dynamic Equilibrium
  • 19.
  • 20.
    Chapter 2 -20 Bonding Curve
  • 21.
    Chapter 2 -21 Bonding Curve • Energy – minimum energy most stable – Energy balance of attractive and repulsive terms Attractive energy EA Net energy EN Repulsive energy ER Interatomic separation r r A n r B EN = EA + ER = −−ro
  • 22.
    Chapter 2 -22 Bonding - Estimations • Estimation of Bonding Energy (Eo) and Equilibrium Spacing (ro) • Given: • Bonding occurs at energy minimum • At minimum: Derivative dE/dr = g(r) = 0 • Solve g(r) = 0 for r ro • Substitute r=ro in the Energy Eqn: • Get Eo = E (r=ro) • Atomic radius R = ro/2 Eo = “bond energy” Energy ro r r A n r B E = certain f(r) e.g. E = − For many atoms, ro is approximately 0.3 nm.
  • 23.
    Chapter 2 -23 • Bond length, r • Bond energy, Eo • Melting Temperature, Tm Tm is larger if Eo is larger. Properties From Bonding: Tm ro r Energy r larger Tm smaller Tm Eo = “bond energy” Energy ro r unstretched length
  • 24.
    Chapter 2 -24 • Coefficient of thermal expansion, α • α ~ symmetry at ro α is larger if Eo is smaller. Properties From Bonding : α = α (T2-T1) ∆L Lo Coefficient of thermal expansion ∆L length, Lo unheated, T1 heated, T2 ro r Smaller α Larger α Energy unstretched length Eo Eo
  • 25.
    Chapter 2 -25 Ceramics (Ionic & covalent bonding): Metals (Metallic bonding): Polymers (Covalent & Secondary): Large bond energy large Tm large E small α Variable bond energy moderate Tm moderate E moderate α Directional Properties Secondary bonding dominates small Tm small E large α Summary: Primary Bonds secondary bonding Bonding in Solids > Liquids > Gases
  • 26.
    Chapter 2 -26 Reading: Focus on Atomic Bonding in Solids Core Problems: 2.7, 2.8, 2.12, 2.13, 2.17, 2.19, 2.21 (Callister 3rd Addition) Quiz: Next Class ANNOUNCEMENTS
  • 27.
    Chapter 2 -27 Quiz Energy Atomic Spacing rA B c Rank materials A, B and C according to 1. Increasing melting temperature > > 2. Decreasing bonding energy > > 3. Increasing Atomic Radius > > 4. Increasing coefficient of thermal expansion > >
  • 28.
    Chapter 2 -28 Quiz Energy Atomic Spacing r A B c Rank materials A, B and C according to 1. Increasing melting temperature > > 2. Decreasing bonding energy > > 3. Increasing Atomic Radius > > 4. Increasing coefficient of thermal expansion > >