Chapter 2: Atomic Structure and

Interatomic Bonding

Chapter 2 - 1
 課程大綱
週次 日期 教學進度
1 09.16-09.20 課程介紹、計分方式與注意事項
2 09.23-09.27 Atomic Structure and Interatomic Bonding
3 09.30-10.04 Atomic Structure and Interatomic Bonding
4 10.07-10.11 Atomic Structure and Interatomic Bonding
5 10.14-10.18 The Structure of Crystalline Solids
6 10.21-10.25 The Structure of Crystalline Solids
7 10.28-11.01 The Structure of Crystalline Solids
8 11.04-11.08 Imperfections in Solids
9 11.11-11.15 Imperfections in Solids
10 11.18-11.22 期中考
11 11.25-11.29 Diffusion
12 12.02-12.06 Diffusion
13 12.09-12.13 Mechanical Properties of Metals
14 12.16-12.20 Mechanical Properties of Metals
15 12.23-12.27 Phase Diagrams
16 12.30-01.03 Phase Diagrams
17 01.06-01.10 Phase Diagrams
18 01.13-01.17 期末考
2
Chapter 2 -
2.1 Introduction

ATOMIC STRUCTURE
2.2 Fundamental Concepts
2.3 Electrons in Atoms
2.4 The Periodic Table

ATOMIC BONDING IN SOLIDS

2.5 Bonding Forces and Energies
2.6 Primary Interatomic Bonds
2.7 Secondary Bonding or van der Waals Bonding
2.8 Molecules
Chapter 2 - 3
 2.1 概論(導論 或 簡介)
• 原子的結構
2.2 基本 概念
2.3 原子中的電子
2.4 週期表
• 固體中的原子鍵結
2.5 鍵結力 與 鍵結能
2.6 主要的 原子間 鍵結
2.7 次要鍵結 或 凡得瓦鍵
2.8 分子
 2.1 Introduction

Some of the important properties of solid materials depend on

geometrical atomic arrangements, and also the interactions that
exist among constituent atoms or molecules.

This chapter, by way of preparation for subsequent discussions,

considers several fundamental and important concepts—namely,
atomic structure, electron configurations in atoms and the periodic
table, and the various types of primary and secondary interatomic
bonds that hold together the atoms comprising a solid. These
topics are reviewed briefly, under the assumption that some of the
material is familiar to the reader.

Chapter 2 - 5
 2.1 概論(導論 or 簡介)
• 固態 materials 一些重要的properties 取決於原子的
幾何排列, 以及這些 atoms or molecules 間的相互
作用.

• 此章的重點: atomic structure, 原子的電子組態,

periodic table, solid 中的主要、次要之各類鍵結.
 2.2 Fundamental Concepts

electrons protons neutrons

(negatively charged)
(positively charged)

A Hydrogen Atom

A Helium Atom

A Lithium Atom

Chapter 2 - 7
 2.2 基本概念

electrons 質子 中子
(帶 負電) (帶 正電)

A 氫 atom

A 氦 atom

原子核
A 鋰 atom
電子軌道
 Atomic Number
• atom – electrons – 9.11 x 10-31 kg
protons
neutrons }1.67 x 10 -27 kg

Atomic number (Z) = # of protons in nucleus of atom

= # of electrons of neutral species

Isotopes: an element that differ in the number of

neutrons in the nucleus

Chapter 2 - 9
 Atomic number (Z), 原子序
•每1個化學元素可以由原子核中所含的”質子數目” 或
“原子序 (Z) ”來描述.

•對一電中性或完整的原子而言:
Z= number of protons
= number of electrons
•同位素: 原子核中之中子數(N)不同
(不帶電)
Ex: C 有 15個同位素
符號 8C 9C 10C 11C 12C 13C 14C 15C 16C 17C 18C 19C 20C 21C 22C

Z 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6
N 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
 Atomic Mass (A)
• Atomic mass (A): protons (Z) + neutrons (N)

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

Atomic wt = wt of 6.023 x 1023 molecules or atoms
1 amu/atom = 1g/mol

C 12.011, H 1.008 etc.

• Avogadro’s number represents the number of

protons or neutrons necessary to produce a mass
of 1 g.

Chapter 2 - 11
 Atomic mass (A) , 原子質量
• Atomic mass (A): protons (Z) + neutrons (N)
原子質量 (A) : 質子 (Z) + 中子(N)
～
•原子質量 (A)= 原子核中之”質子” 與“中子 ”的質量和.
(不是數量)
(Note: 電子在軌道)
• Atomic weight, 原子量: 自然存在的所有同位素, 其原子質
量的平均值.
• amu, 原子質量單位: 計算原子量的單位 , 以自然界中最常
見的碳 12C 同位素為標準, 1 amu = 1/12 mass of 12C.
• Avogadro’s 常數: 1 mole 有 6.022 x 1023 個原子或分子
• Atomic weight 的表示法 : 1 amu/atom = 1g/mol
Ex 1: C , 12 amu/atom 或 12g/mol
Ex 2: Fe, 55.85 amu/atom or 55.85g/mol
2.3 ELECTRONS IN ATOMS
Bohr Atomic Model

Electrons are assumed to

revolve around the atomic
nucleus in discrete orbitals.

Chapter 2 - 13
 2.3 原子中的電子
• 波爾 原子 模型
軌道 e-

原子核

此模型假設電子位於原子核外之
不連續的軌道上進行公轉
energy levels
or states

Chapter 2 - 15
 以未鍵結電子 或 自由電子 做參考點 (能量為zero, 最不穩定)

以能階或
狀態來思
考 固 不
定 可
能 連
差 續

穩定

波爾 原子模型 波動 力學模型
(氫原子最初的3個電子能態) 氫原子 (氫原子最初的3殼層的電子能態)
全為不連續軌道
Note: 氫原子只有1個電子, 只能填入其一的狀態
Wave-Mechanical Model

Electron is considered to
exhibit both wave-like and
particle-like characteristics.
Position is described by a
probability distribution or
electron cloud.

Chapter 2 - 17
 波動-力學模型
100%

波動-力學模型將電子考慮成既
是波動又是顆粒, 電子不是被看成
在不連續軌道上公轉的顆粒, 而是
圍繞在原子核外之區域中出現的
機率, 也就是說位置被描述成電子
雲分佈的機率.
電子雲 2種模型皆採用

波爾 原子模型 波動 力學模型
 Atomic Structure

• Valence electrons determine all of the

following properties
1) Chemical
2) Electrical
3) Thermal
4) Optical

Chapter 2 - 19
 原子結構
• 價電子 決定所有以下之性質
1. 化學性的
2. 電性的
3. 熱性的
4. 光學性的
 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 determined by quantum
numbers.
– The size, shape, and spatial orientation of an electron’s
probability density are specified by three of these quantum
numbers

Quantum # Designation
n = principal (energy level-shell) K, L, M, N, O (1, 2, 3, etc.)
l = azimuthal (subshell) s, p, d, f (0, 1, 2, 3,…, n -1)
ml = magnetic 1, 3, 5, 7 (-l to +l)
ms = spin ½ , -½

Chapter 2 - 21
 (原子的)電子的結構
• 電子具有波動跟顆粒的性質
– 電子在軌道上的機率
– 每一個能階不同的軌道由量子數(Quantum number, n)決定
– 某一個電子機率密度的大小, 形狀 及 空間方向由3個量子數決定.
與波爾模型相關聯: 電子離原子核的距離與位置有關.
量子數
n =主量子數(能階殼層) K, L, M, N, O (n= 1, 2, 3, etc.)
l = 角量子數(副殼層) s, p, d, f (0, 1, 2, 3,4, (n -1))
ml =磁量子數 1, 3, 5, 7 (-l to +l)
ms =自旋量子數 +½ , -½
電子逆時針自轉.
電子順時針自轉.
is related to the distance The number of energy states
of an electron from the it is related to the for each subshell is
nucleus, or its position shape of the electron determined by the third
subshell quantum number.
Chapter 2 - 23
與電子跟原子核
與副殼層的形狀 副殼層中的能態
間的距離, 或電子 數目由第3個量子
有關
的位置相關 數決定
 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

2p L-shell n = 2
2s

1s K-shell n = 1
Chapter 2 - 25
 電子 的能態
電子...
• 具有分散的 能階狀態
• 頃向占據最低能階.
4d
4p N-shell n = 4

3d
4s

Energy 3p M-shell n = 3
3s

2p L-shell n = 2
2s

1s K-shell n = 1
26
First, the smaller the principal quantum number, the lower the energy level;
for example, the energy of a 1s state is less than that of a 2s state, which in
turn is lower than the 3s. Second, within each shell, the energy of a subshell
level increases with the value of the l quantum number. For example, the
energy of a 3d state is greater than a 3p, which is larger than 3s. Finally,
there may be overlap in energy of a state in one shell with states in an
adjacent shell, which is especially true of d and f states; for example, the
energy of a 3d state is greater than that for a 4s. Chapter 2 - 27
1. 最小的 主量子數(principal quantum number), 為最低能階(energy
level); For example, 能量: 1s state < 2s state < 3s state.
2. 在每一殼層內, 副殼層的能量隨著 l 量子數(的數值) 而增加.
For example, the energy of a 3d state > 3p > 3s.
3. 某一殼層內狀態的能量有可能與鄰近殼層狀態的能量重疊(overlap),
在 d and f states 最常見; for example, the energy of a 3d state > 4s.
28
Sequence with which the Orbitals
Fill with Electrons

Chapter 2 - 29
電子填入軌道的順序

30
 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 1: Filled, Stable, He (atomic number = 2)

1s2 , Valence electrode = 0

– Example 2: Unfilled, C (atomic number =6)

– 1s2 2s2 2p2 , Valence electrodes = 4
– Example 2: Unfilled, Al (atomic number = 13)
1s2 2s2 2p6 3s2 3p1 , Valence electrodes = 3

unfilled shells Chapter 2 - 31

Electron Configurations(組態,配置)
• 價電子數–存在於未填滿殼層中之電子
• 被填滿的殼層比較穩定
• 價電子參與了原子間的鍵結 , 控制化學性質

電子結構偏差:
Ex: Fe, atomic number = 26

預期之電子結構為 1s22s22p63s23p63d8
真實的電子結構為 1s22s22p63s23p63d64s2
未填滿的3d 能階造成鐵的磁性行為
 Electronic Configurations
ex: Fe - atomic # = 26 1s2 2s2 2p6 3s2 3p6 3d 6 4s2

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

Energy 3p M-shell n = 3
3s

2p L-shell n = 2
2s

1s K-shell n = 1

Chapter 2 - 33
 Electronic Configurations
ex: Fe - atomic # = 26 , 1s2 2s2 2p6 3s2 3p6 3d 6 4s2

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

Energy 3p M-shell n = 3
3s

2p L-shell n = 2
2s

1s K-shell n = 1

34
 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
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.

Useful web site: http://www.ptable.com/?lang=zh-tw Chapter 2 - 35
 元素調查
• 絕大部分的元素: 電子組態非穩態.
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
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.
Useful web site: http://www.ptable.com/?lang=zh-tw
Chapter 2 - 36
 2.4 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
Na Mg S Cl Ar
K Ca Sc Se Br Kr
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.
Chapter 2 - 37
 2.4 The Periodic Table
捨 • 同一列: 具有類似的 價電 結構
棄捨 接接
1 棄 受受 惰
個 2捨 課本 P23, 表 2.1 2 1 性
電 個棄 個個 氣
子電
3 1s 電電 體

(
子個 2s
2 子子 s2 p6
H He
電 2p

)
10
Li Be
子 3s
O F Ne 殼
Na Mg 3p
18 S Cl Ar 層
K Ca Sc
3d Se Br Kr 完
Rb Sr Y
4s
Te I Xe
全
4p
36 填
Cs Ba 4d Po At Rn
4f 滿
Fr Ra

正電性 元素: 陰電性 元素:

容易捨棄 價電子 而成為帶正 容易接受 價電子 而成為
電的離子. 帶負電的離子. Chapter 2 - 38
 Electronegativity
• Ranges from 0.7 to 4.0,
• Large values: tendency to acquire electrons.

Smaller electronegativity Larger electronegativity

Chapter 2 - 39
 (Electronegativity)電負度 因
• Range from 0.7 to 4.0, 為
• Large values: 頃向獲得電子.(比較會搶電子) 殼
課本 P24, 層
圖 2.4 數
少
,
能
(2s,次低的s)
階
低.
(1s,最低的s)

Larger electronegativity

Smaller electronegativity
因為外殼層逐漸被填滿, 對
於電子的吸引力越來越強.
Chapter 2 - 40
2.5 Bonding Forces and Energies

F N = FA + FR = 0

The bonding energy for these

two atoms, E0, corresponds to
the energy at this minimum
point; it represents the energy
that would be required to
separate these two atoms to
an infinite separation.
Chapter 2 - 41
 2.5 Bonding Forces(力) and Energies(能)
吸引力 (FA)
吸引
作用力(F)

原子間距
排斥

排斥力 (FR)
淨力 (FN)
F N = FA + FR = 0 。
平衡間距 2原子間的平衡間距 (r0), 3A
排斥能 (ER)
排斥
位能(E)

2原子間的鍵結能, E0,
原子間距 會對應於能量的最低點;
吸引

此鍵結能的大小代表能
將2個原子分離到無限
吸引能 (EA) 遠的距離所需的能量
Binding Energy (鍵結能) Chapter 2 - 42
 Bond
Three different types of primary or chemical bond are found
in solids—ionic, covalent, and metallic. For each type, the
bonding necessarily involves the valence electrons;
furthermore, the nature of the bond depends on the electron
structures of the constituent atoms. In general, each of these
three types of bonding arises from the tendency of the atoms
to assume stable electron structures, like those of the inert
gases, by completely filling the outermost electron shell.

Secondary or physical forces and energies are also found in

many solid materials; they are weaker than the primary ones,
but nonetheless influence the physical properties of some
materials. The sections that follow explain the several kinds
of primary and secondary interatomic bonds.
Chapter 2 - 43
 強鍵結 鍵結
dF/dr
弱鍵結 1. 固態中之3種主要鍵結
(或稱 化學鍵)
力 距離
• 離子鍵、共價鍵、金屬鍵
彈性系數:
2. 每一種主要鍵結均與價電
強鍵結>弱鍵結
子相關
r1 3. 任一種鍵結均倾向穩定的
r2
電子結構(如鈍氣族), 以
熱膨脹系數:
使最外電子殼層完全填滿.
弱 強鍵結<弱鍵結
能 距離 次要鍵 (or稱 物理鍵結) 亦在
△E
許多固體中發現, 但比主要鍵
結弱許多,可是仍然能影響材
強 料的物理性質.
△E Chapter 2 -
2.6 Primary Interatomic Bonds
Ionic Bonding

Chapter 2 - 45
 2.6 Primary Interatomic Bonds
Ionic (離子) Bonding

•外層電子多, 陰電性高, 接受電子

•外層電子少, 陰電性低, 給出電子
Chapter 2 - 46
Ionic Bonding in NaCl

Chapter 2 - 47
 Ionic Bonding in NaCl

庫倫鍵結力 NaCl 離子鍵之概略圖

離子鍵: 庫倫吸引力, 正、負離子藉由它們的淨電荷來

相互吸引. Chapter 2 - 48
 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 7e.

Attractive energy EA
Chapter 2 - 49
 A, B 為常數, 視
Ionic Bonding 材料而定, n約為8
• Energy – 越低越穩定
– Energy balance of attractive and repulsive terms
A B
EN = EA + ER = - +
r rn
排斥能 ER
排斥
位能(E)

原子間分開的距離 r
淨能 EN
吸引

Adapted from Fig. 2.8(b),

Callister 7e.

吸引能 EA
Chapter 2 - 50
 Examples: Ionic Bonding
• Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

Chapter 2 - 51
 Examples: Ionic Bonding
• 最主要發生在 Ceramics
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

Chapter 2 - 52
 Ionic Bonding
• Ionic bond – metal + nonmetal
Donates electrons accepts electrons
• 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 - 53
 Ionic Bonding
• Ionic bond : ( 金屬 + 非金屬)
捐獻 electrons 接受 electrons
• 發生在 + 及 – 離子.
• 需要電子轉換(轉讓).
• 需要很大的陰電性差異.
• Example: NaCl
Na (metal) Cl (非metal)
unstable unstable
electron

Na (陽離子) + - Cl (陰離子)
stable stable
Coulombic
Attraction Chapter 2 - 54
 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

Chapter 2 - 55
 共價鍵
• 類似的陰電性  分享 electrons
• 鑑結取決於價電子 – s & p 軌道支配鍵結

•Example: CH4
H 從C原子分享出的電子
CH 4
C: has 4 valence e-,
needs 4 more
H C H
H: has 1 valence e-,
needs 1 more 從氫原子分享出的電子
H

Electronegativities are 相當.

Chapter 2 - 56
 Primary Bonding
• Metallic Bond -- delocalized as electron cloud

• Ionic-Covalent Mixed Bonding

 (X A -X B )2 
 - 
x (100 %)
4
% ionic character =
1- e
 
 
where XA & XB are Pauling electronegativities
Ex: MgO XMg = 1.3
XO = 3.5

 (3.5 -1.3 )2 
 - 
% ionic character  1 - e 4  x (100%)  70.2% ionic
 
 
Chapter 2 - 57
• 事實上, 很少有純的”離子鍵”及”共價鍵”, 多數為2者之
混合鍵
• Ionic-Covalent Mixed Bonding

 -
( X A - X B )2 
% 離子特性 = 1 - e 4 x ( 100%)
 
 
其中, XA & XB 為 A、 B元素之電負度(陰電性)
Ex: MgO; X Mg = 1.3 , X O= 3.5
  -
( 3.5 -1.3) 2
 1 - e  x (100%)4
% 離子特性 =
 
 
 70.2% ionic Chapter 2 - 58
 electronegativities

 electronegativities: the ability of an atom to attract electrons to itself.

Chapter 2 - 59
 電負度(陰電性)

 電負度(陰電性): 一個原子吸引電子的能力
Chapter 2 - 60
 Comparison
The ionic bond is nondirectional, the covalent bond is
highly directional.

Chapter 2 - 61
 比較
• ionic bond 是 ”非方向性”,
• covalent bond 是 ”高度方向性”.

分享電子 轉換電子

接受電子

分子 正離子 負離子
covalent bond ionic bond Chapter 2 - 62
 Metallic Bond
Metallic bonding: bonds formed by electrostatic attraction
between delocalized electrons called conduction electrons, and the metallic ions
within metals.
Inner shell electrons (strongly bonded to nuclear)

Becomes free electrons (conduction electrons)

electron cloud or electron gas

Electron in outer-shell (easy removed from orbital)

Chapter 2 - 63
 金屬鍵
金屬鍵: 鍵結的形成是經由 稱為”傳導電子” 之位移電
子間 的 靜電吸引 而形成, 金屬鍵存在於金屬中.
內殼層電子 (對於原子核有很強的鍵結)
變成自由電子(傳導電子)

+
電子雲(海)
外殼層電子 (非常容易離開軌跡)

Chapter 2 - 64
 Energy well in metallic bonds

E a

ao = 2R, pair of metal atoms, equilibrium atomic

ao separation ao is reached when net potential energy is
Emin a minimium (Emin)
R
R
Chapter 2 - 65
 金屬鍵的能井

E a
ao = 2R, 一對金屬原子, 平衡時之原
ao 子間距 (ao ) 為淨能 (net potential
R Emin energy) 為最小時 (Emin)
R
Chapter 2 - 66
 2.7 SECONDARY BONDING OR
VAN DER WAALS BONDING
Arises from interaction between dipoles
• Fluctuating dipoles
asymmetric electron ex: liquid H 2
clouds H2 H2

+ - + - H H H H
secondary secondary
bonding bonding

• Permanent dipoles-molecule induced

secondary
-general case: + - bonding
+ -

secondary
-ex: liquid HCl H Cl bonding H Cl

-ex: polymer secondary bonding

Chapter 2 - 67
 2.7 SECONDARY BONDING OR
VAN DER WAALS BONDING
由偶(雙)極所引起的交互反應
• 擾動感應偶極(dipoles)
不對稱之電子雲 ex: liquid H 2
H2 H2

+ - + - H H H H
次要鍵結 secondary
(只是吸引, 沒有電子轉換) bonding
• Permanent dipole (永久偶極) -molecule induced
secondary
-general case: + - bonding
+ -

secondary
-ex: liquid HCl H Cl bonding H Cl

-ex: polymer secondary bonding

Chapter 2 - 68
Chapter 2 - 69
分子間之正、負電性相互吸引所造成

Chapter 2 - 70
2.8 Molecules

Chapter 2 - 71
 2.8 Molecules(分子)

•很多常見的分子是由原子經主要鍵結組合而
成, 如雙原子分子(Ex: O2, H2), 和化合物(Ex:
H2O, CO2).
•凝態(液、 固態)時, 分子間的鍵結為很弱的
次要鍵, 因此分子材料的熔點跟沸點很低.
•現代的高分子材料(聚合物), 由於具有很大的
分子(長鍊), 所以次要鍵結(凡得瓦爾鍵 and
氫鍵)的重要性就相對增加,因而影響其材料性
質(如熔點).
Chapter 2 - 72
 Summary: Bonding
Type Bond Energy Comments
Ionic Large! Nondirectional (ceramics)

Covalent Variable Directional

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

Metallic Variable
large-Tungsten Nondirectional (metals)
small-Mercury
Secondary smallest Directional
inter-chain (polymer)
inter-molecular
Chapter 2 - 73
 Summary(總結): Bonding
Type Bond Energy Comments (註解)
Ionic Large! Nondirectional (ceramics)
(硬, 高熔點)
Covalent Variable Directional
large-Diamond (semiconductors, ceramics
small-Bismuth polymer chains)

Metallic (硬, 高熔點)

Variable
large-Tungsten Nondirectional (metals)
small-Mercury
Secondary smallest Directional
inter-chain (polymer)
inter-molecular
Chapter 2 - 74
Chapter 2 - 75
熔點高, 代表鍵結能強, 通常硬度也很大
Chapter 2 - 76
Chapter 2 - 77
 (主)

(主) (次)

(主)

Chapter 2 - 78
 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 - 79
 Properties From Bonding: Tm (熔點)
• 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 - 80
 Properties From Bonding : a
• Coefficient of thermal expansion, a
length, L o coeff. thermal expansion
unheated, T 1
DL DL
= a(T2 -T1 )
heated, T 2 Lo

• a ~ symmetry at ro
Energy
unstretched length
ro
r a is larger if Eo is smaller.

Eo
Eo
Chapter 2 - 81
 Properties From Bonding : a
• Coefficient of thermal expansion (熱膨脹系數), a
length, L o
unheated, T 1 coeff. thermal expansion
DL
heated, T 2 DL
= a ( T2 -T 1)
Lo
• a ~ symmetry at ro
Energy
unstretched length
ro
r a is larger if Eo is smaller.

Eo
Eo
Chapter 2 - 82
 Summary: Primary Bonds
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small a

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate a

Polymers Directional Properties

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

Chapter 2 - 83
 Summary: Primary Bonds
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm (熔點)
large E (能)
small a(熱澎脹系數)
Variable bond energy
Metals
moderate Tm
(Metallic bonding):
moderate E
moderate a
Directional Properties
Polymers
Secondary bonding dominates
(Covalent & Secondary):
small Tm
small E
large a Chapter 2 - 84