CH 3

강의자료 저작권 관련 유의사항 안내
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용도로 사용할 수 없으며, 다른 사람들과 공유할 수
없습니다. 위반에 따른 법적 책임은 행위자 본인에게
있습니다.”
나. 금지되는 행위
(1) 위와 같이 내려 받은 강의자료를 수강생 본인 외 제3자에게 배포(출력물의 경우), 전송(파일
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저작물이 포함되어 있을 수 있고, 그것이 외국에서 접근가능한 상태가 되기 때문입니다. 따라서,
강의자료를 타인과 공유하거나 전송 및 공개하는 행위를 하여서는 안 됩니다.
Materials Inorganic Chemistry
Chapter 3. Simple Bonding Theory

3.1 Lewis Electron-Dot Diagrams
- Valence bond theory: Bonds between two atoms exist when they share
one or more pairs of electrons. O
....
O C O
....
H H
- Some molecules have nonbonding pairs, i.e. lone pair.
- Most Lewis structures follow the octet rule. Hydrogen keeps duet rule.
Resonance
: There is more than one possible way in which the valence electrons are
placed in a Lewis structure.
- Higher electron counts

: octet expansion, expanded shell or expanded electron count
- Hypervalent: central atoms that have electron counts greater than the
atom’s usual requirement. (use of d & f orbitals)
: SF6, IF7 (14e-), [TaF8]3- (16e-), [XeF8]2- (18e-)
Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry: INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/46p
3.1 Lewis Electron-Dot Diagrams
- Only valence electrons participate in chemical bonding.
- Dashed lines: bonded electron pairs ..
. ..
P H F
..
..
- Dots: nonbonded electrons
- Hydrogen: duet, Other elements: octet O C O
Useful guidelines for Lewis structure

1. MXn, M is usually centrally located.
2. Hydrogen and the halogens generally form one bond. Group 16
elements often form two bonds. Group 15 elements form three bonds.
Group 14 elements form four bonds.
3. Group 2 and Group 13 elements are often electron-deficient (Be, B).
4. Expanded shell or expanded electron count:
The elements beyond P are
hypervalent (expands octet) due to
the participation of d orbitals.
5. Small bond distances are necessary for effective p-type overlap
(C, N, O, P, S elements for strong p bonds and multiple bonds).
6. No of bonds = [(Total e- needed) – (Valence e- available)]/2.
3.1.3 Formal Charge
- Formal charge is the apparent electronic charge of each atom in a
molecule, based on the electron-dot structure.
- The formal charge is only a tool for assessing Lewis structure.
- Guides for evaluating resonance

structure
1. Minimize nonzero and high
formal charge
2. Avoid nonzero formal charge
on adjacent atoms
3. Place negative charge on atoms
with high c.
Gary L. Miessler, Paul J. Fischer, Donald A. Tarr./Inorganic chemistry: INTERNATIONAL EDITION /PESRSON/FIFTH EDITION/2013/47,48p
3.1.3 Formal Charge
Most important
3.1.3 Formal Charge
Most important
None of these structures are satisfactory!
- Some molecules have satisfactory electron-dot structures with octets but

have better structures with expanded electron counts when formal
charges are considered.
3.1.3 Formal Charge
3.1.4 Multiple Bonds in Be & B Compounds
- The lack of sufficient valence electrons in Be and B elements.
- Structure minimizing formal charges for these molecules have only four electrons in
the valence shell of Be and six electrons in that of B.
- The alternative, requiring eight electrons
on the central atom, predicts multiple bonds.
- In the solid, a complex network is
formed with coordination number 4.
- The BF3 combines readily with other
molecules that can contribute a lone
pair of electrons.
3.2 Valence Shell Electron-Pair
Repulsion (VSEPR) Theory
- A method for predicting the shape
of molecules based on the
electron-pair electrostatic
repulsion.
- Steric Number (SN = m + n) is
the number of positions occupied
by atoms or lone pairs around a
central atom.
- The structures for 2, 3, 4, 6
electron pairs are completely
regular with all bond angles and
distances same.
- The structures for 5, 7 electron
pairs have different bond angles
and distances.
Repulsion Theory
3.2.1 Lone-Pair Repulsion
- Lone pairs, single bonds, double bonds, and triple bonds can all be
treated similarly when predicting molecular shape.
- But there is difference in electrostatic repulsion forces among them.
- Decrease of adjacent bond angles for lone pair
- Lone pair prefers the

equatorial positions with
two 90o interactions.
- Three lone pairs tend to occupy the equatorial positions
with two 90o interactions.
- Seesaw (SF4)
- Distorted T (BrF3)
- Linear (XeF2)
- Square planar - trans
form (XeF4)
- If a single LP is present,
in some cases the LP
causes distortion. In
other cases, the structure
is octahedra.
3.2.2 Multiple Bonds
- Double and triple bonds to have slightly greater repulsive effects than
single bonds because of the repulsive effect of p electrons.
- Multiple bonds tend to occupy more space than single bonds and to
cause structural distortions.
Repulsion Theory
Hybrid Combinations for Molecular Geometry
Hybrid orbitals
sp, pd
sp2, sd2
sp3, sd3
dsp3, sp3d
d2sp3, sp3d2
3.2.3 Electronegativity & Atomic Size Effect
Electronegativity (c)
: the power of an atom in a molecule to attract electrons to itself
- Electronegativity plays an important role in determining the
arrangement of outer atoms around a central atom and influencing
bond angles.
- The effect of electronegativity and atomic size frequently parallel
each other.
- Fluorine has the highest electronegativity.
- The electronegativity decreases toward the lower left corner of the
periodic table.
- The noble gases have higher electronegativity than halogen due to a
greater effective nuclear charge.
1. For the orbitals of a given atom, electronegativity decreases as 1s >

2s > 3s > 4s > 5s …
2. For a given element, electronegativity decreases with the number of
electrons. M2+ > M+ > M0 > M- > M2- …
3.2.3 Electronegativity & Atomic Size Effect
Various concepts of electronegativity
1. Pauling concept: stabilization of bond by polarity, c(F) =4.0
2. Allred-Rochow: effective nuclear charge and size
Total Energy (E)

3. Mulliken: electronegativity of orbitals rather than atoms
c = (IE1 + EA1)/2, c = a + 2bq (c = dE/dq, E = aq + bq2)
(a = electronegativity at neutral state, b = charge coefficient,
q = charge) -1 -0.5 0 +0.2
- As b decreases, the change of charge has less influence on c. Charge (q)
Electronegativity & Bond Angles
- As the electronegativity of halogen increases, the halogen exerts a
stronger pull on electron pairs it shares with the central atom. This
effect reduces the concentration of electrons near the central atom,
allowing the lone pair to spread out and reducing bond angles.
- If the central atom remains the same, molecules that have a larger
difference in electronegativity values between their central and outer
atoms have smaller bond angles.
- As the central atom becomes more electronegative, it pulls electrons in

bonding pairs more strongly toward itself, increasing the concentration
of electrons near the central atom.
- The net effect is that an increase in bonding pair-bonding pair repulsion
near the central atom increases the bond angles.
Electronegativity & Electron Affinity
옆의 그래프는 전하에 따른 원자의 에너지 변화에

대한 것입니다. 전자친화도는 q=1인 음이온 상태와
q=0인 중성상태의 에너지 차이에 해당합니다.
그림에서 볼수 있듯이 F가 음전하가 커짐에 따라
빨리 안정화되다가 전자간 반발때문에 q=-1
근처에서 오히려 불안정해져서 결과적으로 Cl보다
에너지가 높아지는 것을 볼수 있습니다. 이 결과로
중성상태와의 에너지차이가 Cl보다 작아져서
전자친화도가 작아지는 것이지요.
다음주에 배우겠지만 이 그래프에서 중성에서의
전기음성도는 q=0에서의 접선의 기울기입니다. F가
Cl보다 기울기가 가파르다는 것을 볼 수 있고 이것은
F의 전기음성도가 Cl 보다 크다는 것을 의미합니다.
- More electronegative CF3 groups lead to wider bond angles, indicating
the more important role of atomic size.
- The axial bonds are longer than

the equatorial bonds, indicating
the greater repulsion of lone and
bonding pairs in axial positions.
- There is a tendency for less
electronegative groups to occupy
equatorial positions, similar to
lone pairs and multiple bonded
atoms.
- The effects on bond angles by
less electronegative atoms are
however typically less than lone
pairs and multiple bonds.
3.3 Molecular Polarity
- The greater the difference in electronegativity, the more polar the bond.
- The polarity of molecules is measured indirectly by measuring the
dielectric constant.
- The dipole moment for the molecule
- The dipole moments of NH3, H2O, and NF3 reveal the dramatic effect of
lone pairs.
- London forces or dispersion forces: attractive forces between nonpolar
molecules.
3.4 Hydrogen Bonding
- Hydrogen bonding: unusually strong intermolecular forces for hydrogen
bonded to oxygen, fluorine, and nitrogen.
- Dipole interaction between electropositive hydrogen and negative elements
- There is a significant orbital overlap between hydrogen and F,O,N.
- The molecules having hydrogen bonding show exceptionally high boiling
points.
3.4 Hydrogen Bonding
- The hydrogen bonding between water molecules induces the decrease
of density when they freeze.
- The hydrogen bonding causes coiling of

protein and polynucleic acid molecules.
- A combination of hydrogen bonding with
other dipolar forces imposes
considerable secondary structure on
these large molecules.
- Clathrates: molecules trapped in holes

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강의자료 저작권 관련 유의사항 안내

“본 강의자료는 연세대학교 학생들을 위해

Chapter 3. Simple Bonding Theory

- Higher electron counts

Useful guidelines for Lewis structure

- Guides for evaluating resonance

None of these structures are satisfactory!

- Some molecules have satisfactory electron-dot structures with octets but

- Decrease of adjacent bond angles for lone pair

- Lone pair prefers the

1. For the orbitals of a given atom, electronegativity decreases as 1s >

Total Energy (E)

- As the central atom becomes more electronegative, it pulls electrons in

옆의 그래프는 전하에 따른 원자의 에너지 변화에

- The axial bonds are longer than

- The hydrogen bonding causes coiling of

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