Atomic Structure & Interatomic Bonding 原子結構與原子間的鍵結: Issues To Address..
Atomic Structure & Interatomic Bonding 原子結構與原子間的鍵結: Issues To Address..
Chapter 2 - 1
Atomic Structure (原子結構)
2.2 Fundamental concepts
• atom – electrons 電子 – 9.11 x 10-31 kg
protons 質子
neutrons 中子 }
1.67 x 10-27 kg
• atomic number原子序
= # of protons in nucleus of atom
= # of electrons in neutral species
C 12.011
H 1.008 etc. Chapter 2 - 2
2.2 Fundamental concepts
• Avogadro number 亞彿加厥數
In one mole of a substance, there are 6.0221023
atoms or moleculs. 一莫耳 (mole) 的物質中含有
6.0221023 個 ( 亞佛加厥數 ) 原子或分子。
• atomic mass unit 原子質量單位= amu = 1/12 mass of
C.
amu 是計算原子量的單位。1 amu的定義是:以最常見的
碳同位數 ── 即碳12(12C) 的原子質量 (A = 12.00000)
的 1/12 。
1 amu/atom = 1 g/mol
Chapter 2 - 3
Atomic Structure
Chapter 2 - 4
2.3 Electrons in atoms
• During the latter part of the 19th century, it was found
that many phenomena involving electrons in solids
could not be explained by the classical mechanics (
古典力學).
• Quantum mechanics (量子力學) was established.
Chapter 2 - 5
2.3 Electrons in atoms
• Bohr atomic model 波爾原子模型.
• The energies of the electrons are quantized 電子的能量
呈現量子化.
電子只擁有特定之能量值。一個電子在改變能量時,可以從
原來之能量狀態跳躍到另一特定之高能量 ( 吸收能量 ) 或
低能量 ( 釋放能量 ),跳躍前後之能量差為定值。
電子能量以
能階 (energy
levels)
或狀態 (states) 來
思考
Chapter 2 - 6
2.3 Electrons in atoms
• Bohr atomic model has its limitations
波爾模型出現了許多限制,無法完全說
明電子的所有現象.
• Wave-mechanical model波動 - 力學模
型.
• Electron has both wave-like and
particle-like characteristics.
• Electron no longer moves in a
discrete orbital; its position is
considered to be the probability at
various locations around the nucleus.
電子考慮成圍繞在原子核外面區域中
出現電子機率的位置。
Chapter 2 - 7
Electronic Structure
• Electrons have wavelike and particulate properties.
• Two of the wavelike characteristics are
– electrons are in orbitals defined by a probability.
– each orbital at discrete energy level is determined by
quantum numbers 量子數.
Chapter 2 - 8
Electronic Structure
• Four quantum numbers.
• Shells are specified by a principal quantum number (
主量子數 ), n.
殼層由主量子數 (principal quantum number) n來表
示,n 為由1開始之整數值;這些殼層也可用大寫字母
K,L,M,N,O等來表示,n = 1相當於 K;2相當於 L;3相
當於 M;4相當於 N;5相當於 O 等
– 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
Chapter 2 - 9
Electronic Structure
• Four quantum numbers.
• Shells are specified by a principal quantum number (主量子
數 ), n.
殼層由主量子數 (principal quantum number) n來表示,n 為由
1開始之整數值;這些殼層也可用大寫字母 K,L,M,N,O等來表
示,n = 1相當於 K;2相當於 L;3相當於 M;4相當於 N;5相當
於O等
• Related to the size of an electron’s orbital (average distance
from the nucleus)
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
Chapter 2 - 10
Electronic Structure
• Second quantum number (第二量子數), l, designates the
subshell (副殼層). l=0 to l=n-1.
第二 ( 或稱方位角 ) 量子數 l表示副殼層,l 的值由 n 值所
限制,為自 l = 0 到 l = (n – 1) 範圍的整數值。每一副殼層
對應上述整數值,以小寫字母 ── s,p,d 或 f 來標示。
– 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
Chapter 2 - 11
Electronic Structure
• Second quantum number (第二量子數), l, designates the
subshell (副殼層). l=0 to l=n-1.
• Electron orbital shapes depend on l.
s subshell: spherical and centered on the nucleus.
p subshell: dumbbell shape
Chapter 2 - 12
Electronic Structure
• Third quantum number (第三量子數), ml,
• Also called magnetic quantum number 磁量子數
• Determine the number of electron orbitals for each
subshell.每一副殼層中的電子軌域數目由第三量子數 ml
來決定
• ml : integers between –l and l, including 0. 介於 -l 與 +l
之間包含0之整數。
– 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
Chapter 2 - 13
Electronic Structure
• Fourth quantum number (第四量子數), ms,
• Spin moment 電子自轉動量
• Spin up (自旋向上): 1/2 or Spin down 和(自旋向下):-1/2。
– 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
Chapter 2 - 14
Electronic Structure
Chapter 2 - 15
Electron Energy States
Electrons...
• have discrete energy states
• tend to occupy lowest available energy state.
4d
4p N-shell n = 4
Adapted from Fig. 2.6, Callister &
3d Rethwisch 9e.
(From K. M. Ralls, T. H. Courtney, and J. Wulff,
Introduction to Materials Science and
4s Engineering, p. 22. Copyright © 1976 by John
Wiley & Sons, New York. Reprinted by
permission of John Wiley & Sons, Inc.)
Energy 3p M-shell n = 3
3s
2p L-shell n = 2
2s
1s K-shell n = 1
Chapter 2 - 16
Table_02_01
Chapter 2 - 17
Electron Configurations 電子組態
• Valence electrons 價電子– those in unfilled
shells 未填滿殼層中的電子,通常為原子最外
層sp能階上的電子數。
• Valence electrons are most available for
bonding and tend to control the chemical
properties 原子內參與鍵結合或化學反應的電子數,
原子的價電子數反映出原子與其他元素起化學反應的
能力,許多固體的物理和化學性質與價電子有密切的關
係。
Chapter 2 - 18
Electron Configurations 電子組態
example: Na (atomic number = 11)
1s22s22p6 3s1
valence electrons
Chapter 2 - 19
Electron Configurations 電子組態
• Filled shells more stable
• H: 1s1
• He: 1s2
• Na: 1s22s22p6 3s1
• 惰性氣體 ( 氦、氖、氬、氪 ) 等元素,它們在最外殼層的
s 和 p 狀態,都被電子完全填滿,故呈現出化學惰性 (
不容易發生化學反應 )。
Chapter 2 - 20
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 2s2
Boron 5 1s 2 2s 2 2p 1 Adapted from Table 2.2,
Callister & Rethwisch 9e.
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)
Chapter 2 - 21
Electronegativity 電負度(陰電性)
• Capability to accept electrons 吸引電子的能力
• Ranges from 0.9 to 4.1,
Large values: tendency to acquire electrons.
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. 2.8,
Callister &
K Ca Sc Se Br Kr
Rethwisch 9e.
Rb Sr Y Te I Xe
Cs Ba Po At Rn
Fr Ra
陰電性 原子獲得電子的趨勢
Electronegativity Tendency of an atom to gain an electron
陽電姓 當陰電性較低時,可用陽電性來表示
Electropositive Elements with low electronegativity i.e.,<2.0
2 - 24
© 2011 Cengage Learning Engineering. All Rights Reserved.
Atomic bonding in solids 原子鍵結
2.5 Bonding forces and
energies
鍵結力與鍵結能
Force
•Attractive force (吸引力, FA)
and Repulsive force (排斥力
FR)
•Net Force (淨力, FN)
FN FA FR
•State of equilibrium 平衡狀態
FA FR 0
•此時兩原子之間保持一定的間
距: equilibrium spacing 平衡間
距, r0
Atomic bonding in solids 原子鍵結
2.5 Bonding forces and
energies
鍵結力與鍵結能
Energy
•Attractive energy (吸引能, EA)
and Repulsive Energy (排斥能
ER)
•Net Energy (淨位能, EN)
E N E A ER
•State of equilibrium 平衡狀態:
EN 曲線最小值處
•此時兩原子之間的能量為E0 :
鍵結能 (bonding energy)
• 鍵結能代表將這兩個緊密結合之原子分
開到無窮遠距離所需之能量。
Atomic bonding in solids 原子鍵結
Figure 2.18
打破鍵結所需之能量
束縛能
Interatomic space
原子的平衡距離,由斥 原子間距
力和吸力平衡造成的。
F=0
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Askland et al. The science and engineering of materials. 6th ed. 2011.
Interatomic bonds 原子鍵結
Chapter 2 - 28
Ionic bond 離子鍵
metal 金屬 + nonmetal 非金屬
donates accepts
electrons electrons
Chapter 2 - 29
Ionic bond – metal + nonmetal
donates accepts
electrons electrons
Dissimilar electronegativities
e.g., NaCl
Chapter 2 - 30
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
庫倫吸引力
Chapter 2 - 31
Ionic Bonding
• Energy – minimum energy most stable
– Energy balance of attractive and repulsive terms
A B
EN = EA + ER = - + n
r r
Repulsive energy ER
Interatomic separation r
Net energy EN
Adapted from Fig.
2.10(b), Callister &
Rethwisch 9e.
Attractive energy EA
Chapter 2 - 32
Ionic Bonding
• Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl
Chapter 2 - 33
Ionic Bonding
• Nondirectional 無方向性: magnitude of the bond is equal
in all direction around an ion. 離子鍵結沒有方向性;也就
是說,一離子周圍所有方向的鍵結大小都相同。
• Bonding energy is relatively large (600~1500 kJ/mol)
high melting temperature 離子鍵之鍵能相當大,因而顯示
出高熔點。
Chapter 2 - 34
Table_02_03
Chapter 2 - 35
Ionic Bonding
• Energy – minimum energy most stable
– Energy balance of attractive and repulsive terms
A B
EN = EA + ER = - + n
r r
Repulsive energy ER
Interatomic separation r
Net energy EN
Adapted from Fig.
2.10(b), Callister &
Rethwisch 9e.
Attractive energy EA
Chapter 2 - 36
Examples: Ionic Bonding
• Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl
Chapter 2 - 37
Covalent Bonding 共價鍵
• similar electronegativity相近的電負度 share electrons電
子共用
• bonds determined by valence – s & p orbitals dominate
bonding
• Example: H2 H2
Chapter 2 - 38
共價鍵 Covalent bonds
兩個或兩個以上的原子,彼此間共用價電子而產生的鍵結
Electronegativities of C and H
are comparable so electrons Fig. 2.15, Callister & Rethwisch 9e.
are shared in covalent bonds. (Adapted from J.E. Brady and F. Senese, Chemistry:
Matter and Its Changes, 4th edition. Reprinted with
permission of John Wiley and Sons, Inc.)
Chapter 2 - 42
Metallic bond 金屬鍵
• Metallic Bond -- delocalized as electron cloud 價電
子生成電子海
• 價電子並非固定被固體中某個原子綁住,而是在金屬整
體中自由漂移。這些電子形成一”電子海”或”電子雲”,屬
於整體金屬所有。
Chapter 2 - 43
Metallic bonds
陽電性的金屬元素付出它的
價電子,而形成一個圍繞著
原子(核心)的電子海。
這種原子的陰電性≤3
e.g. Al付出3個價電子,留
下帶3價正電的原子核及內層
電子所組成的核心。帶負電
的價電子成為游離價電子
(non-localized valence
electron),不再附屬於特定
的原子,可在電子海內自由
運動,且可同時附屬於好幾
個核心。帶正電的核心與電
子吸引而成為一體,產生金
屬鍵。
Metallic Bonds
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2.8 Mixed Bonding 混鍵
Chapter 2 - 45
混合的鍵結 Mixed bonding
大部分的材料中,原子的鍵結是兩種或兩種以上鍵結的合成。
e.g. Fe的鍵結為金屬鍵和共價鍵的組合。
由兩種或多種金屬形成的化合物 (金屬間化合物 intermetallic
compounds) ,可能會有混合的金屬鍵和離子鍵產生;尤其是
元素間存在著大的陰電性差異時。
在陶瓷與半導體中,材料的組成多為金屬和非金屬的結合,原
子間的鍵結為共價鍵(covalent)和離子鍵(ionic)的混合鍵結。
在週期表中的IIIA、IVA和VA族元素 ( 如硼、矽、鍺、砷、
銻、碲、釙和砈 ) 也會發生另一種混鍵。這些元素在原子
之間的混鍵屬於金屬與共價的混合,如圖所示為擬金屬
(metalloids) 或半金屬 (semi-metals)。
Chapter 2 - 49
Fluctuating induced dipole bonds
擾動感應偶極鍵
Fig_02_21b
Chapter 2 - 50
Polar-molecule-induced dipole bonds
極性分子-感應偶極鍵
Chapter 2 - 51
Permanent dipole bonds
永久電偶極
Chapter 2 - 52
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. 2.20,
Callister & Rethwisch 9e. bonding
Chapter 2 - 53
Secondary bonding
Chapter 2 - 54
Chapter 2: Atomic Structure
• 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 - 56
Chapter 2: Atomic Structure
原子間距 原子的平衡距離,由斥力和吸力平衡造成的。固態
Interatomic spacing 金屬之原子平衡距離為原子直徑。
The interatomic spacing in a solid metal is
approximately equal to the atomic diameter,
or twice the atomic radius r.
束縛能 打破鍵結所需之能量 Minimum energy required
Binding energy to break the bond
Figure 2.18
打破鍵結所需之能量
束縛能
Interatomic space
原子的平衡距離,由斥 原子間距
力和吸力平衡造成的。
F=0
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Askland et al. The science and engineering of materials. 6th ed. 2011.
Chapter 2: Atomic Structure
彈性模數
高熔點
Energy
低熔點
ro r
smaller Tm
Figure 2.19 larger Tm
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2 - 59
Reserved.
Askland et al. The science and engineering of materials. 6th ed. 2011.
Properties From Bonding: α
• Coefficient of thermal expansion, α
length, L o coeff. thermal expansion
unheated, T1
ΔL ΔL
= α (T2 -T1)
heated, T 2 Lo
• α ~ symmetric at ro
Energy
unstretched length
ro
r α is larger if Eo is smaller.
E
larger α
o
E smaller α
o Chapter 2 - 60
Chapter 2: Atomic Structure
(Interatomic energy)
鍵結較弱→加熱後位移較大→熱膨
脹係數較高
鍵結較強→加熱後位移較小→熱膨
脹係數較低
© 2011 Cengage Learning
Figure 2.20 Engineering. All Rights Reserved. Chapter 2 - 2
Askland et al. The science and engineering of materials. 6th ed. 2011.
Chapter 2: Atomic Structure
四種鍵結之束縛能比較
Askland et al. The science and engineering of materials. 6th ed. 2011.
Metallic Variable
large-Tungsten Nondirectional (metals)
small-Mercury
Secondary smallest Directional
inter-chain (polymer)
inter-molecular
Chapter 2 - 63
Summary: Primary Bonds
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small α
Chapter 2 - 64