CHAPTER 2:

원자의 구조와 화학결합

Chapter 2 - 1
 Atomic Structure (원자구조)
• atom (원자)
– electrons (전자) 9.11 x 10-31 kg, 양전하 (1.602 x 10-19C)
– protons (양자) 1.67 x 10-27 kg, 음전하 (1.602 x 10-19C)
– neutrons (중성자) 1.67 x 10-27 kg, 전하 없음

• atomic number = # of protons in nucleus of atom

= # of electrons of neutral species
[Number of neutron can vary: isotope]

• atomic mass unit = amu = 1/12 mass of 12C

Atomic wt = wt of 6.022 x 1023 molecules or atoms

1 amu/atom = 1g/mol
2
 Atomic Models
• Bohr Model (old!)
– The “higher” is the orbit is, the bigger is
the energy
– Basic Principles of Quantum mechanics
• Energy is quantized
• Exclusion principle
• Uncertainty principle

3
 Atomic Models
• Wave-mechanical Model
– “Electron cloud”
– Probability

4
 Atomic Structure
• Valence electrons (원자가 전자):
– 최외각에 채워진 전자
• Valence electrons determine all of the following
properties
1) Chemical
2) Electrical
3) Thermal
4) Optical

5
 Electronic Structure
• Electrons have wavelike and particulate
properties.
– This means that electrons are in orbitals defined by a
probability.
– Each orbital at discrete energy level is 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 1, 3, 5, 7 (-l to +l)
ms = spin ½, -½

6
 Electron Energy States
Electrons...
• have discrete energy states
• tend to occupy lowest available energy state.

4d
4p N-shell n = 4

3d
4s

Energy 3p M-shell n = 3
3s
Adapted from Fig. 2.4,
Callister & Rethwisch 3e.
2p L-shell n = 2
2s

1s K-shell n = 1
7
 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,
Callister & Rethwisch 3e.
Carbon 6 1s 2 2s 2 2p 2
... ...
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 4p 6 (stable)

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

Chapter 2 - 8
 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

– example: C (atomic number = 6)

1s2 2s2 2p2

valence electrons

9
 Electronic Configurations
ex: Fe - atomic # = 26 1s2 2s2 2p6 3s2 3p6 3d 6 4s2

4d
4p N-shell n = 4 valence
electrons
3d
4s

3p M-shell n = 3
3s
Adapted from Fig. 2.4,
Callister & Rethwisch 3e.
2p L-shell n = 2
Energy 2s

1s K-shell n = 1

10
 The Periodic Table
• Columns: Similar Valence Structure

inert gases
give up 1e-
give up 2e-

accept 2e-
accept 1e-
give up 3e-
H He
Li Be O F Ne
Adapted from
Na Mg S Cl Ar Fig. 2.6,
Callister &
K Ca Sc Se Br Kr
Rethwisch 3e.
Rb Sr Y Te I Xe
Cs Ba Po At Rn
Fr Ra

Electropositive elements: Electronegative elements:

Readily give up electrons Readily acquire electrons
to become + ions. to become - ions.
11
 Electronegativity
• Ranges from 0.7 to 4.0,
• Large values: tendency to acquire electrons.

Smaller electronegativity Larger electronegativity

Adapted from Fig. 2.7, Callister & Rethwisch 3e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.

12
 Bonding
• Primary Bonding
– Valence band에 있는 전자가 직접 화학결합에 참여
– Ionic bonding, covalent bonding, metallic bonding
• Secondary Bonding
– 원자나 분자내에서 양전하, 음전하가 서로 거리를 두고
분리된경우 생성된 dipole 사이의 coulomb attraction에 의한 결합
– Weaker than primary bonding

13
 Ionic bond – metal + nonmetal

donates accepts
electrons electrons

Dissimilar electronegativities

ex: MgO Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4

(Magnesium Oxide) [Ne] 3s2

Mg2+ 1s2 2s2 2p6 O2- 1s2 2s2 2p6

[Ne] [Ne]

14
 Ionic Bonding
• Occurs between + and - ions.
• Requires electron transfer.
• Large difference in electronegativity required.
• Example: NaCl

Na (metal) Cl (nonmetal)
unstable unstable
electron

Na (cation) + - Cl (anion)
stable Coulombic stable
Attraction

Chapter 2 - 15
 Ionic Bonding
• Energy – minimum energy most stable
– Energy balance of attractive and repulsive terms

A 
B
EN = EA + ER =
r rn
Repulsive energy ER

Interatomic separation r

Net energy EN
Adapted from Fig. 2.8(b),
Callister & Rethwisch 3e.

Attractive energy EA
16
 Examples: Ionic Bonding
• Predominant bonding in Ceramics
NaCl (sodium chloride)
MgO
CaF2 (Calcium Fluoride)
CsCl (Calcium chloride)

Give up electrons Acquire electrons

Adapted from Fig. 2.7, Callister & Rethwisch 3e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.

Chapter 2 - 17
 Covalent Bonding
• similar electronegativity  share electrons
• bonds determined by valence – s & p orbitals
dominate bonding
• Example: CH4
shared electrons
H
C: has 4 valence e-, CH 4
from carbon atom
needs 4 more
H: has 1 valence e-, H C H
needs 1 more
shared electrons
Electronegativities H from hydrogen
are comparable. atoms

Adapted from Fig. 2.10, Callister & Rethwisch 3e.

Chapter 2 - 18
 Ionic-Covalent Mixed Bonding
• 경우에 따라 한 물질내에서 2가지 이상의 결합특성이
존재할 수 있다.
• 대부분의 공유결합은 일부 이온결합특성을 가지고,
전기음성도의 차이가 클 수록 이온결합특성이 커진다.
 (X A X B )2 
  
 x (100%)
% ionic character = 4
1 e
 
 
where XA & XB are Pauling electronegativities
Ex: MgO XMg = 1.3
XO = 3.5
 (3.5 1.3 )2 
  
% ionic character  1  e 4  x (100%)  70.2% ionic
 
 
19
 Primary Bonding
• Metallic Bond -- delocalized as electron cloud

20
 SECONDARY BONDING
Arises from interaction between dipoles
• Fluctuating dipoles
asymmetric electron ex: liquid H 2
clouds H2 H2

+ - + - H H H H
secondary secondary
bonding Adapted from Fig. 2.13,
Callister & Rethwisch 3e. bonding

• Permanent dipoles-molecule induced

secondary
-general case: + - bonding
+ -
Adapted from Fig. 2.14,
Callister & Rethwisch 3e.
secondary
-ex: liquid HCl H Cl bonding H Cl

Chapter 2 - 21
Summary: Bonding
Type Bond Energy
Ionic Large!

Covalent Variable
large-Diamond
small-Bismuth

Metallic Variable
large-Tungsten
small-Mercury
Secondary smallest

Chapter 2 - 22
 Properties From Bonding: Tm
• Bond length, r • Melting Temperature, Tm
Energy
r

• Bond energy, Eo ro
r
Energy smaller Tm

unstretched length
ro larger Tm
r
Eo = Tm is larger if Eo is larger.
“bond energy”

Chapter 2 - 23
 Properties From Bonding : 
• Coefficient of thermal expansion, 
length, L o coeff. thermal expansion
unheated, T1
L L
= (T2 -T1)
heated, T 2 Lo

•  ~ symmetric at ro
Energy
unstretched length
ro
r  is larger if Eo is smaller.

E
smaller 
o
E larger 
o Chapter 2 - 24
 Summary: Primary Bonds
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small 

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate 

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small Tm
small E
large 

Chapter 2 - 25