States of Matter

Matter and Properties of

Matters
KEY IDEA: Properties of materials depend on their
atoms, and how those atoms are linked together

1. Matter
• Properties of matter
• States of matter

2. Chemical Bonding
• Bonding theory
• Molecular Structure
(VSEPR)
3. Intermolecular Forces

SOLIDS SOLIDS
(fixed volume and shape) (fixed volume and shape)

Glass: Atoms not periodic

Crystal – regular
atomic arrangement

Glass vs. Crystal Structure LIQUIDS

(fixed volume, variable shape)

1
 LIQUIDS GAS
(fixed volume, variable shape) (variable volume and shape)
Liquid Crystals: Molecules line up under an electric field

PLASMA
Properties of Matter
(Gas with free electrons)
• Physical properties
– properties that we can measure and describe, including shape,
color, and texture

• Chemical properties
– chemical properties, such as their flammability

• Macroscopic
– Physical and chemical properties that can be observed with the
eye

• Microscopic
– The underlying structure of a chemical substance, that can be
explored using magnifying devices

chemical element
A substance that contains only one type of atom (each
different element contains its own specific type of atom),
Iron at atomic, miscroscopic cannot be decomposed into other chemical components
and macroscopic levels A chemical compound is a substance
that contains more than one element.
atom
the smallest possible particle
of a substance

molecule
a combination of two or more
atoms held together in a
specific shape by attractive
forces.

2
 Classifications A mixture contains two or more chemical substances.
Unlike pure compounds, mixtures vary in composition because the
poor conductors of electricity and heat proportions of the substances in a mixture can change.
For example, dissolving sucrose and table sugar in water forms a
six elements that are categorized as mixture that contains water molecules and sucrose molecules.
metalloids
dull-appearing, brittle solids are
A sample is homogeneous if it always has the same composition, no matter what
sometimes called semiconductors
part of the sample is examined.
because they conduct electricity
better than nonmetals but not as well
Pure elements and pure chemical compounds are homogeneous.
as metals.
Mixtures can be homogeneous, too; a homogeneous mixture usually is called a
Silicon and germanium are used in
solution.
the manufacture of semiconductor
chips in the electronics industry.
Hydrogen chloride gas is a homogeneous pure substance and always contains
equal numbers of hydrogen atoms and chlorine atoms linked in HCl molecules.
good conductors of heat and electricity and usually
appear shiny. Under other conditions, molecular hydrogen and molecular chlorine do not react
malleable, meaning that they can be hammered into with each other. The two gases form a homogeneous solution whose
thin sheets composition can be changed by adding more of either substance.
ductile meaning that they can be drawn into wires
Except for mercury, which is a liquid, all metals are
solids at room temperature.

Phase of matter
gas
solid liquid

tentukan karakteristik substansi pada dua gambar diatas

meliputi fasa dan jenisnya

SF-Berkeley 104 m
distance

transformation of matter: phase

interstellar 1016 m
(sun-star) football field 102 m
distance

blade of 10-3 m
grass

sun-earth
distance 1011 m
chlorophyll
molecule 10-7 m

diameter
of earth 107 m

H atom 10-10 m

Dimension H nuclei
10-15 m

3
 Measurements in chemistry presisi dan akurasi
Length, area, and volume measure the
precision describes the exactness of a measurement
size of an object. Length refers to one
accuracy describes how close a measurement is to the true value.
dimension, area refers to two dimensions,
and volume refers to three dimensions of
space.

every object possesses a certain

quantity of matter, called its mass
Æ highly accurate mass-measuring
machines, called analytical
balances, work by comparing
forces acting on masses.

cermat dan akurat

The process of determining mass is called weighing. ………………………
Mass and weight are related, but they are not the same property. cermat dan tidak akurat
Mass is a fundamental characteristic of an object, whereas weight results
tidak cermat dan tidak akurat
from gravitational force acting on an object's mass.

Chemical Bonding
significant figures
• Atoms link together by the rearrangement
of their electrons
• Magic numbers (2,10,18,&36) of electrons
form very stable atoms
• Electrons may be transferred or shared to
form stable bonds
extensive and intensive properties • Ionic Bonds
A property that depends on amount is called extensive. • Covalent Bonds
Mass and volume are two examples of extensive properties. • Metallic Bonds
A property that is independent of amount is called intensive.
Density and temperature are intensive properties.

PEMBENTUKAN MOLEKUL GAS HIDROGEN, H2

Mengapa beberapa senyawa padatan meleleh pada
suhu tinggi, sedangkan cairan atau gas pada suhu Energi interaksi antara 2 atom H
kamar? = atom H
0 Jarak antar inti
Mengapa atom-atom unsur yang berbeda
bereaksi? 74 pm

Bagaimana bentuk geometri suatu senyawa? 436 kJ/mol

Ep
IKATAN KIMIA
Gaya tolak Gaya tarik
• menyatakan gaya tarik antar atom bersama membentuk suatu
senyawa • molekul H2 terbentuk dengan Ep=-436 kJ/mol pada jarak antar
• menentukan sifat kimia suatu senyawa dan inti 74 pm
• mengontrol jumlah energi yang dilepas/diserap dalam suatu reaksi
• Menentukan bentuk/geometri suatu senyawa • jarak antar inti yang memberikan energi potensial molekul
paling rendah dapat ditentukan secara eksperimen Æ ikatan
kimia

4
 Teori Lewis STRUKTUR LEWIS

1. Yang berperan dalam ikatan kimia adalah elektron, • Menggunakan nama kimia atom untuk menyatakan inti dan
terutama elektron kulit terluar (elektron valensi) elektron di kulit selain kulit valensi (core electrons) dan titik
untuk menyatakan elektron valensi
2. Elektron valensi umumnya dipindahkan dari atom logam
ke non-logam dan terbentuk kation dan anion. Gaya • Struktur Lewis tidak secara khusus menyatakan cara elektron
elektrostatik antar kation-anion menghasilkan IKATAN berpasangan
IONIK.
• Contoh: Si P
3. Pada ikatan antar atom non-logam, 1 atau lebih Grup 4A Grup 5A
pasangan elektron valensi digunakan bersama oleh atom
yang berikatan membentuk IKATAN KOVALEN.
4. Dalam melepaskan atau menarik atau menggunakan
elektron bersama untuk membentuk ikatan kimia, atom-
atom cenderung mencapai konfigurasi gas mulia (Aturan Tentukan struktur Lewis ion berikut:
oktet/Aturan gas mulia) untuk mencapai stabilitas a. Al3+ b. N3- c. S2-
maksimum.

IKATAN IONIK Ikatan ionik

• Pembentukan ikatan ionik lebih banyak dikontrol oleh energi
potensial pembentukan ion (energi ionisasi dan affinitas • Gaya elektrostatik yang mengikat ion positif
elektron) (kation) dan ion negatif (anion) dalam suatu
• Ikatan ionik yang stabil mempunyai energi total pembentukan
senyawa Æ senyawa ionik
ion-ion penyusun ikatan bersifat EKSOTERMIS: energi
potensial senyawa < energi potensial individu unsur
• Pada atom non-logam:
E untuk melepas e- > Energi untuk menangkap e- ANION • Eg: reaksi antara litium dan flourin
• Pada atom logam: membentuk litium fluorida (serbuk putih
E untuk melepas e- < Energi untuk menangkap e- KATION beracun yang dipakai untuk menurunkan
Contoh: pembentukan NaCl titik leleh solder dan pembuatan keramik)
Na Na+ + e-
Cl + e- Cl -

2Na(padatan) + Cl2(gas) 2NaCl(padatan)

Siklus Born-Haber untuk 1 mol NaCl

PERUBAHAN ENERGI DALAM PEMBENTUKAN Na+(g) + Cl(g) + e-
SENYAWA IONIK
Na(g) Na+(g) + e- EI1=+496 kJ/mol
4 ∆H = -349 kJ
Cl(g) + e- Cl-(g) AE=-349 kJ/mol 3 ∆H3 = +496 kJ 4

Total energi perpindahan 1e- dari atom Na ke atom Cl = Na+(g) + Cl-(g)

Na(g) + Cl(g)
(+496) + (-349) = +147 kJ/mol
reaksi sukar terjadi 2
∆H2 = +122 kJ
∆Ho Na(g) + 1/2Cl2(g)
Na(padatan) + 1/2Cl2(gas) NaCl(padatan) f=-411 kJ ∆H5 = -787 kJ
Reaksi berlangsung 1 ∆H = +107 kJ
1
Perubahan energi pada pembentukan NaCl dapat ditentukan Na(s) + 1/2Cl2(g) 5
menggunakan start
Siklus Born-Haber
∆Hfo NaCl(s) = -411 kJ
Starting point: 1 mol Na(s) dan ½ mol Cl2(g)
End point: 1 mol NaCl(s) NaCl(s)

end

5
Reaksi yang terlibat dalam pembentukan NaCl
1. Konversi atom Na dari fasa padat ke fasa gas Æ ∆H1
2. Disosiasi/peruraian molekul Cl2 menjadi atom-atom Cl Æ
∆H2 (energi disosiasi ikatan)
3. Ionisasi atom Na fasa gas menjadi ion Na+ fasa gas Æ ∆H3
(Energi ionisasi pertama, EI1)
4. Konversi atom Cl fasa gas menjadi ion Cl- fasa gas Æ ∆H4
(Afinitas elektron)
5. Pembentukan sistem kristal dari ion-ion fasa gas Æ ∆H5
(energi kisi)
∆Hfo = ∆H1 + ∆H2 + ∆H3 + ∆H4 + ∆H5 = -411kJ
ENERGI KISI
• Energi yang dibutuhkan untuk memisahkan secara sempurna 1
mol senyawa ionik padatan menjadi ion-ion fasa gasnya.
• ditentukan dari Hk Coulomb: E = k (Q+Q-)/r
• ditentukan secara tidak langsung menggunakan konsep siklus
Born-Haber
Entalpi sublimasi Li +161 kJ/mol dan EI1=+520 kJ/mol.
Energi disosiasi Fluorin +159 kJ/mol F2 dan EA fluorin -328
kJ/mol. Energi kisi LiF -1047 kJ/mol. Tentukan perubahan
energi entalpi total reaksi:
Li(s) + 1/2F2(g) LiF(s) ∆Hof=?

IKATAN KOVALEN TEKNIK PENULISAN STRUKTUR LEWIS

Bonding pair 1. Tentukan total jumlah elektron valensi atom-atom yang

Cl Cl Cl Cl berikatan

Lone pair 2. Buat struktur rangka (hubungkan atom yang berikatan

dengan garis)

IKATAN KOVALEN KOORDINASI 3. Tempatkan lone pair elektron di atom terminal (ujung)
untuk mencapai konfigurasi oktet pada atom paling
1 atom menyediakan 2 elektron untuk dipakai bersama ujung (kecuali H)
membentuk ikatan
4. Susun elektron tersisa sebagai lone pair di sekitar atom
Pembentukan H3O+ pusat

5. Jika perlu, pindahkan 1 atau lebih elektron lone pair dari

atom terminal untuk membentuk ikatan rangkap dengan
atom pusat

IKATAN KOVALEN DAN ELEKTRONEGATIVITAS

Elektronegativitas menyatakan kemampuan suatu atom

untuk menarik elektron ikatan saat atom berada sebagai
suatu molekul

• makin besar elektronegativitas atom dalam suatu

molekul, makin kuat atom tersebut menarik elektron
ikatan kovalen

• Dalam satu periode SPU, secara umum elektronegativitas

meningkat dari kiri ke kanan
• Dalam satu golongan SPU, secara umum
elektronegativitas meningkat dari bawah ke atas

6
 increasing ionic character

non polar covalent bond

increasing covalent character

polar covalent bond ionic bond

0 0.5 1.0 1.5 2.0 2.5 3.0

melting point senyawa periode 2 dan 3

What is the trend? What about the distance
Conductivity - high Conductivity - low between the atoms in a bond?
Chlorides of Period 2
compound LiCl BeCl2 BCl3 CCl4 NCl3 OCl2 Cl2 NaCl Na+ Cl- d = 281 pm
melting point 610 415 -107 -23 -40 -121 -102

Chlorides of Period 3 Cl2 Cl-Cl d = 199 pm

compound NaCl MgCl2 AlCl3 SiCl4 PCl3 SCl6 Cl2

melting point 801 714 193 -69 -112 -51 -102 What property can be used to tell
when a bond will ionic or covalent?
high low

Electronegativity Using electronegativities

The electronegativity difference - ∆EN = ENhigher – EN lower to determine bond type

Chlorides of Period 2 ∆EN > 1.7 ionic bond - transfer

compound LiCl BeCl2 BCl3 CCl4 NCl3 OCl2 Cl2

2.2 1.6 1.1 0.6 0 0.6 0

∆EN < 1.7 covalent bond - sharing
∆EN
Chlorides of Period 3
So we have a range of electronegativity difference of
Compound NaCl MgCl2 AlCl3 SiCl4 PCl3 SCl6 Cl2 0 to 1.7 for sharing an electron pair.

∆EN 2.2 1.9 1.6 1.3 1.0 0.6 0

large difference small difference

7
 Is the sharing of electrons
in molecules always equal?

non-polar
bond X Y ∆EN = 0

Which element
is more X Y ∆EN = 0.3

increasing polarity of bond

electronegative?

ENY > ENX X Y ∆EN = 0.6

polar bond X Y ∆EN = 0.9 Nonmetallic element + nonmetallic element Æ Molecular compound

0 < EN < 1.7 Molecular compounds are typically gases, liquids, or low
X Y ∆EN = 1.2 melting point solids and are characteristically poor
Direction of electron migration conductors. Examples are H2O, CH4, NH3.

Space-filled
BF3 – a planar molecule
Metallic compound + nonmetallic compound Æ IONIC
compound F
4.0
B
2.0
Ionic compounds are generally high-melting solids that Ball & stick
are good conductors of heat and electricity in the
molten state.
negative
Examples are NaCl, common salt, and NaF, sodium
fluoride.

top side
positive

Electrostatic potential maps Spartan ‘02

Show the direction of electron

Bond Energy migration ( ) in the following.
Is breaking a bond an endothermic or exothermic process?
C–H
X2 + energy Æ X + X
H–F
C=O
F2 single bond BE = 142 kJ/mole
increasing bond strength

C – Cl

O2 double bond BE = 494 Rank the bond polarity (1-most … 3-least)

As-H N-H P-H

N2 triple bond BE = 942

http://wulfenite.fandm.edu/Data%20/Table_6.html

8
 Comparison of Bonding Types

ionic covalent 100% covalent 100% ionic

Bonding spectrum
ions
molecules
molten salts non- A B A B A+ B-
conductive conductive
valence
transfer of sharing of
electrons electrons
electrons Increasing ∆EN
high mp low mp
Increasing polarity Transfer
∆EN > 1.7 ∆EN < 1.7

melting point senyawa periode 2 dan 3

Here is the electrostatic potential map for H2CO.
What is the trend?
Show the electron Conductivity - high Conductivity - low
migration on this Chlorides of Period 2
planar molecule.
compound LiCl BeCl2 BCl3 CCl4 NCl3 OCl2 Cl2

melting point 610 415 -107 -23 -40 -121 -102

H
C O Chlorides of Period 3
H compound NaCl MgCl2 AlCl3 SiCl4 PCl3 SCl6 Cl2

blue – positive red - negative

melting point 801 714 193 -69 -112 -51 -102

How is this molecule different than BF3?

high low

Electronegativity
What about the distance
The electronegativity difference - ∆EN = ENhigher – EN lower
between the atoms in a bond?
Chlorides of Period 2
NaCl Na+ Cl- d = 281 pm compound LiCl BeCl2 BCl3 CCl4 NCl3 OCl2 Cl2

∆EN 2.2 1.6 1.1 0.6 0 0.6 0

Cl2 Cl-Cl d = 199 pm Chlorides of Period 3
Compound NaCl MgCl2 AlCl3 SiCl4 PCl3 SCl6 Cl2
What property can be used to tell ∆EN 2.2 1.9 1.6 1.3 1.0 0.6 0
when a bond will ionic or covalent?
large difference small difference

9
 Using electronegativities Is the sharing of electrons
to determine bond type in molecules always equal?

non-polar
∆EN > 1.7 ionic bond - transfer bond X Y ∆EN = 0

Which element
∆EN < 1.7 covalent bond - sharing is more X Y ∆EN = 0.3

increasing polarity of bond

electronegative?

So we have a range of electronegativity difference of ENY > ENX X Y ∆EN = 0.6

0 to 1.7 for sharing an electron pair.

polar bond X Y ∆EN = 0.9

0 < EN < 1.7

X Y ∆EN = 1.2
Direction of electron migration

Metallic compound + nonmetallic compound Æ IONIC

compound

Ionic compounds are generally high-melting solids that

are good conductors of heat and electricity in the
molten state.
Examples are NaCl, common salt, and NaF, sodium
fluoride.

Nonmetallic element + nonmetallic element Æ Molecular compound

Molecular compounds are typically gases, liquids, or low

melting point solids and are characteristically poor
conductors. Examples are H2O, CH4, NH3.

Space-filled
BF3 – a planar molecule
Bond Energy
F
4.0 Is breaking a bond an endothermic or exothermic process?
B
2.0
Ball & stick X2 + energy Æ X + X

negative
F2 single bond BE = 142 kJ/mole
increasing bond strength

O2 double bond BE = 494

top side N2 triple bond BE = 942

positive

Electrostatic potential maps Spartan ‘02 http://wulfenite.fandm.edu/Data%20/Table_6.html

10
 Show the direction of electron Comparison of Bonding Types
migration ( ) in the following.
C–H
ionic covalent
H–F ions
molecules
molten salts non-
C=O
conductive conductive
C – Cl valence
transfer of sharing of
electrons electrons
electrons
Rank the bond polarity (1-most … 3-least) high mp low mp

As-H N-H P-H ∆EN > 1.7 ∆EN < 1.7

Here is the electrostatic potential map for H2CO.

100% covalent 100% ionic Show the electron

Bonding spectrum migration on this
planar molecule.
A B A B A+ B-

H
C O
Increasing ∆EN H
Increasing polarity Transfer
blue – positive red - negative

How is this molecule different than BF3?

TEORI IKATAN DAN BENTUK Geometri gugus elektron

MOLEKUL
METODE TOLAKAN PASANGAN ELEKTRON KULIT
VALENSI (VSEPR:valence-shell electron-pair repulsion)
Konsep: pasangan elektron pada kulit valensi atom-atom yang berikatan saling
memberikan tolakan antara yang satu dengan yang lain sedemikian rupa sehingga
menempati ruang sejauh mungkin terhadap pasangan elektron yang lain
2 gugus elektron: linier; 3 gugus elektron: segitiga planar (trigonal
planar); 4 gugus elektron: tetrahedral; 5 gugus elektron: trigonal
bipiramidal; 6 gugus elektron: oktahedral
Jika tidak ada lone-pair electrons (lp), geometri gugus elektron =
geometri molekul
Jika ada lone-pair electrons (lp), geometri molekul ditentukan oleh
geometri gugus elektron

Cara menerapkan VSEPR:

Geometri molekul dengan energi tolakan minimum
1. Gambar struktur Lewis yang stabil
Terms: 2. Tentukan jumlah gugus elektron sekitar atom pusat dan
1. Geometri gugus elektron: orientasi ruang gugus elektron di sekitar atom pusat identifikasikan sebagai gugus elektron ikatan (bonding pair, bp) atau
akibat tolakan antara gugus elektron
Gugus elektron: kelompok elektron valensi yang terlokalisasi di sekitar atom
lone-pair electrons (lp)
pusat 3. Tentukan geometri gugus elektronnya
2. Geometri molekul – bentuk molekul: orientasi ruang atom-atom yang berikatan 4. Deskripsikan geometri molekulnya
di sekitar atom pusat 5. Derajat kuat tolakan: lp-lp > lp-bp > bp- bp

11
 Structure Determination by VSEPR
67
Structure Determination by VSEPR
68

Water, H2O
Ammonia, NH3
••••

H
H O
O H
H The electron pair geometry is tetrahedral.
••••

lone pair of electrons

in tetrahedral position
N
2 bond pairs H H
H
2 lone pairs
The electron pair geometry
is TETRAHEDRAL

The MOLECULAR GEOMETRY — the

The molecular positions of the atoms — is TRIGONAL
geometry is BENT.
BENT. PYRAMID.

CH4

Ukuran relatif pasangan elektron ikatan dan

lone pairs pada molekul CH4, NH3 dan H2O

Molecular Geometry 3

Predict the molecular geometry of IF5.

Lewis structure:
4
Geometri gugus elektron:

Geometri molekul:

12
 4
6

MOLEKUL POLAR DAN MOMEN DIPOL

Molekul yang memiliki pusat muatan positif dan negatif
terpisahkan oleh suatu jarak tertentu.

Kuantifikasi terhadap pemisahan muatan dalam suatu

molekul dinyatakan oleh momen dipol (µ, debye, D), hasil
kali jarak yang memisahkan pusat muatan positif dan
negatif (d, meter) dengan kuantitas muatan (δ, coulomb)
µ= d δ

1 D = 3,34 x 10-30 C m Plat logam Medium non-konduktif

Molekul polar momen dipol ≠ 0
Molekul non-polar momen dipol = 0
Jika molekul polar ditempatkan antara kedua plat logam,
molekul tsb akan mengalami penataan seperti gambar di atas
Molekul polar meningkatkan kapasitas penyimpanan muatan
plat logam sampai pada suatu kuantitas yang sesuai dengan
momen dipol molekul

Bond Polarity
77 78

Molecular Dipole Moments

HCl is POLAR because it has a For polyatomic molecules, the dipole moment is the
positive end and a negative geometric sum of all bond dipole moments.
end. (difference in
electronegativity)
electronegativity)
+ δ -δ
• •
H C• • l ••
Cl has a greater share in
bonding electrons than
does H.
Cl has slight negative charge (-δ) and H has
CO2 - Nonpolar H2O - Polar
slight positive charge (+ δ)

13
 Bond Polarity
79 80
Predict the Polarity of
• This is why oil and water will not mix! Oil is nonpolar,
nonpolar, and Molecules:
water is polar.
• The two will repel each other, and so you can not dissolve
one in the other HCl
• “Like dissolves like”
like” CCl4
NH3
BF3
CH3Cl

Determine the dipol direction

(electron migration)

Molecular Geometry and Directional

Overview
Bonding
• Atoms oriented in very well defined relative positions
• Geometry and Directional Bonding in the molecule.
– Valence-Shell Electron-Pair Repulsion Theory
• Molecular Geometry = general shape of the
– Dipole Moment and Molecular Geometry
molecule as determined by the relative positions of
– Valence Bond Theory the atomic nuclei.
– Description of Multiple Bonding
• Theories Describing the structure and bonding of
• Molecular Orbital Theory molecules are:
– Principles of Molecular Orbital Theory – VSEPR = considers mostly electrostatics in determining the
– Electron Configurations of Diatomic Molecules of the geometry of the molecule.
Second-Period Elements – Valence Bond Theory = considers quantum mechanics and
hybridization of atomic orbitals.
– Molecular Orbitals and Delocalized Bonding
– Molecular Orbital Theory = claims that upon bond formation
8–81 new orbitals that are linear combinations of the atomic 8–82
orbitals are formed.

TEORI IKATAN VALENSI MOLECULAR SHAPES:VALENCE

BOND THEORY (VBT)
Asumsi:
• Valence Bond Theory: a quantum mechanical description of
Elektron suatu molekul menempati orbital bonding that pictures covalent bond formation as the overlap of
two singly occupied atomic orbitals.
atomnya masing-masing • VSEPR effective but ignores the orbital concepts discussed in
quantum mechanics.
• H2 forms due to overlap of two 1s orbitals.
Molekul stabil terbentuk dari atom-atom yang • Electron densities from p-subshell electrons overlap to produce
a bond in F2.
bereaksi jika energi potensialnya minimum • CH4:The 1s orbital of hydrogen must overlap with the 2s and 2p
orbitals of carbon.
Teknik: • Presence of electrons from hydrogen adds new waves that are
in contact with each other and undergo constructive interference
• gambar struktur lewis – new waves result.
• Perkirakan penataan semua pasang-an elektron • The s and p orbitals around an atom such as carbon become
equivalent and the orbitals become a hybrid (sp3) of the original
menggunakan metode VSEPR orbitals. 8–84

• Hybrid orbitals are as far apart as possible.

• Tentukan hibridisasi atom pusat dengan cara
memadankan pasangan e- dengan orbital hibrida

14
 Other Kinds of Hybrid Orbitals
• Hybridization varies from sp, sp2, up to sp3d2 depending upon
the number of orbitals involved in the bonding.
• Each of these has a characteristic shape see table in book.
• Hybridization determined by using VSEPR to establish the
geometry, i.e., the number of electron clouds around the central
atom. The number of electron clouds = the number of hybrid
orbitals.
E.g.: Determine the hybridization of B in BF3.
• The σ bond formed between an s orbital and a p orbital or even
between two p orbitals.
• E.g. CH3CH2OH, has all σ bonds - even though there are C-C
bonds and C-O bonds which each involve the interaction of sp3
orbitals to form the σ bonds.
• SF6: sp3d2.
VBT: Multiple bonds
• C2H4 planar with a trigonal geometry = sp2
hybridization for each of the carbon atoms and
they form σ bonds with hydrogen.
• Each carbon has 4 orbitals in its valence shell.
This means one of the p-orbitals for each C is not
hybridized.
• Proximity to each other results in overlap to give
a charge distribution resembling a cloud which is
above and below the plane of the molecule and
called a π –bond .
• Overlap above and below makes rotation of
carbon atoms difficult.
• E.g. C2H2: sp (linear) hybridized. Leads to the
existence of a σ bond as well as two π bonds.
• Summarizing a
• single bond is a σ bond,
double bond is a σ bond and a π bond,
•
• triple bond is a σ bond and 2 π bonds.
E.g. Dinitrogen difluoride exists as cis and trans
isomers( a compound having the same formula
with a different arrangement of atoms).
8–85
Investigate the bonding.
8–86

Hybrid Orbitals
Untuk atom O dalam H2O
Hybrid Geometric Arrangements Number of Example
Orbitals Orbitals
sp Linear 2 Be in BeF2
2p
sp2 Trigonal planar 3 B in BF3 sp3 sp3
sp3 Tetrahedral 4 C in CH4 lone O-H
2s pairs bonds
Energy

sp3d Trigonal bipyramidal 5 P in PCl5

sp3d2 Octahedral 6 S in SF6

1s 1s 1s
8–87

O atom O atom O atom

(ground state) (hybridized state) (in H2O)

Pembentukan orbital hibrida sp3 Pembentukan orbital hibrida sp

15
 Pembentukan orbital hibrida sp2
Multiple Bonding
• According to valence bond theory, one
hybrid orbital is needed for each bond
(whether a single or multiple) and for each
lone pair.
– For example, consider the molecule ethene.

Multiple Bonding (unhybridized)

2p 2p
• Each carbon atom is bonded to three other
atoms and no lone pairs, which indicates sp2
the need for three hybrid orbitals. 2s
Energy

– This implies sp2 hybridization.

– The third 2p orbital is left unhybridized and lies
perpendicular to the plane of the trigonal sp2 1s 1s
hybrids.
– The following slide represents the sp2 C atom (ground state) C atom (hybridized)
hybridization of the carbon atoms.

Figure 10.25

Multiple Bonding
• To describe the multiple bonding in
ethene, we must first distinguish between
two kinds of bonds.
– A σ (sigma) bond is a “head-to-head” overlap of
orbitals with a cylindrical shape about the bond
axis. This occurs when two “s” orbitals overlap or
“p” orbitals overlap along their axis.
– A π (pi) bond is a “side-to-side” overlap of parallel
“p” orbitals, creating an electron distribution above
and below the bond axis.

16
 Multiple Bonding Bonding in Ethylene
• The remaining “unhybridized” 2p orbitals
on each of the carbon atoms overlap side-
to-side forming a π bond.

– You therefore describe the carbon-carbon double

bond as one σ bond and one π bond.

Pembentukan orbital hibrida pada molekul

berikatan rangkap C2H2
asetilen
C2H4
etilen

MO Theory of Bonding
H atom H2 molecule H atom
• Molecular Orbital Theory extends quantum theory and states
that electrons spread throughout the molecule in molecular
orbitals = region in a molecule in which an electron is likely to
be which is similar to the concept discussed in quantum theory.
Molecular orbitals are considered to be the result of the
combination of atomic orbitals.
σ1s*
• Hydrogen: when two atomic orbitals from hydrogen approach
each other they form 2 molecular orbitals, σ and σ*, bonding
orbital and antibonding orbital respectively.
– The energy of the bonding orbital is lower than the original atomic 1s 1s
orbital.
– The energy of the antibonding orbital is higher than the original
atomic orbitals and thus destabilizes the molecule.
*
• The electron distribution of H2 would be: σ1s ↑↓ , σ1s . An
excited state of this molecule would be σ1s ↑ , * ↓ .
σ 2s 8–101 8–102

σ1s
Because the energy of the two electrons is lower than the energy of the
individual atoms, the molecule is stable.

17
 Molecular Orbital Theory of Other
Bond Order
Diatomic Molecules
• The term bond order refers to the number of bonds •
bonding).
( )2
He2: (σ1s )2 σ1*s ⇒ no net stabilization (or

that exist between two atoms. •

2
( )
2 * 1
He + (σ1s ) σ1s ⇒ a net of one bonding electron.
• Bond order: BO = 1/2(nb − na) where nb is the
number of bonding electrons and na is the number
of antibonding electrons.
E.g. For He2 BO(He2) = 1/2(2 −2) = 0.
E.g.2 H2 on the other hand would have a BO(H2) =
– The bond order of a diatomic molecule is defined as 1/2(2 − 0) = 1 or there is a single bond between
the two atoms.
one-half the difference between the number of • Li2:
( )
(σ1s )2 σ1*s (σ2s )2 ⇒ BO=1/2(4 − 2) = 1.
1

electrons in bonding orbitals, nb, and the number of

( ) ( ) ( )
• Molecule of lithium should2be stable.
O2: (σ1s )2 σ1*s (σ2s )2 σ*2s (π2p )4 (σ2p )2 π*2p ;
2 2
electrons in antibonding orbitals, na. •

bond order = 1
2 (n b - na) BO= 1/2(10 − 6) = 2. Last two filled orbitals are
antibonding ⇒ one elctron in each orbital (Hund’s Fig. 10.34 MO Diagram of
8–103 rule) or two unpaired electrons ⇒ O2 a 8–104
paramagnetic molecule. N2

Delocalized Bonding
MO Levels of 2nd Row Elements
• Molecular orbital theory handles delocalization quite nicely since molecular
Large 2s-2p interaction Small 2s-2p interaction orbitals can be said to be spread over the entire.
• Metals and energy bands formed by them.
B2 C2 N2 O2 F2 Ne2 • Solidification of metal atoms forms large “molecules” with extensive
delocalization of electrons.
σ*2p ↑↓ • Molecular orbitals for all metals are very similar and a continuous band is formed.
• They can conduct electricity when the atoms are excited so that an electron
π*2p ↑ ↑ ↑↓↑↓ ↑↓↑↓ occupies an excited state. The energy separation between the occupied and
unoccupied orbitals is small so that little energy is required to cause this.
σ2p ↑↓ ↑↓ ↑↓ ↑↓
π2p
↑ ↑ ↑↓↑↓ ↑↓↑↓ ↑↓↑↓ ↑↓↑↓ ↑↓↑↓
σ*2s ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
σ2s ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
Bond Order 1 2 3 2 1 0 8–105 8–106
Magnetic behavior P D D P D

P = Paramagnetic; D = Diamagnetic

INTERMOLECULAR FORCES

8–107 8–108

Fig. 10.34 MO Diagram of N2

18
 A Molecular Comparison of A Molecular Comparison of
Gases, Liquids and Solids Gases, Liquids and Solids
• Physical properties of substances understood in terms of
kinetic molecular theory:
– Gases are highly compressible, assumes shape and volume of
container:
• Gas molecules are far apart and do not interact much with each
other.
– Liquids are almost incompressible, assume the shape but not
the volume of container:
• Liquids molecules are held closer together than gas molecules, but
not so rigidly that the molecules cannot slide past each other.
– Solids are incompressible and have a definite shape and
volume:
• Solid molecules are packed closely together. The molecules are so
rigidly packed that they cannot easily slide past each other.

A Molecular Comparison of Gases, Intermolecular Forces

Liquids and Solids
• The covalent bond holding a molecule together is an
• Converting a gas into a liquid or solid requires the intramolecular force.
molecules to get closer to each other: • The attraction between molecules is an intermolecular
– cool or compress. force.
• Converting a solid into a liquid or gas requires the • Intermolecular forces are much weaker than
molecules to move further apart: intramolecular forces (e.g. 16 kJ/mol vs. 431 kJ/mol for
– heat or reduce pressure. HCl).
• The forces holding solids and liquids together are • When a substance melts or boils the intermolecular
forces are broken (not the covalent bonds).
called intermolecular forces.
• When a substance condenses intermolecular forces are
formed.

Intermolecular Forces in Solutions

19
 Intermolecular Forces Intermolecular Forces
Ion-Dipole Forces
• Interaction between an ion (e.g. Na+) and a dipole
(e.g. water).
• Strongest of all intermolecular forces:
QQ
F =k 1 2
d2
– Since Q1 is a full charge and Q2 is a partial charge, F is
comparatively large.
• F increases as Q increases and as d decreases:
– the larger the charge and smaller the ion, the larger the
ion-dipole attraction.

Intermolecular Forces Intermolecular Forces

Dipole-Dipole Forces
• Dipole-dipole forces exist between neutral polar
molecules.
• Polar molecules need to be close together.
• Weaker than ion-dipole forces:
QQ
F =k 1 2
d2
– Q1 and Q2 are partial charges.

Intermolecular Forces

Dipole-Dipole Forces
• There is a mix of attractive and
repulsive dipole-dipole forces as
the molecules tumble.
• If two molecules have about the
same mass and size, then dipole-
dipole forces increase with
increasing polarity.

20

Intermolecular Forces
• Ion-Induced Dipole:
– An ion induces a dipole moment in an adjacent
molecule or atom.
• Interaction between an ion (e.g. Na+) and a
dipole (e.g. water).
Intermolecular Forces
London Dispersion Forces
• One instantaneous dipole can induce another
instantaneous dipole in an adjacent molecule (or
atom).
• The forces between instantaneous dipoles are
called London dispersion forces.
• Polarizability is the ease with which an electron
cloud can be deformed.
• The larger the molecule (the greater the number of
electrons) the more polarizable.
Intermolecular Forces
London Dispersion Forces
• Weakest of all intermolecular forces.
• It is possible for two adjacent neutral molecules to
affect each other.
• The nucleus of one molecule (or atom) attracts the
electrons of the adjacent molecule (or atom).
• For an instant, the electron clouds become
distorted.
• In that instant a dipole is formed (called an
instantaneous dipole).
Intermolecular Forces
London Dispersion Forces
Intermolecular Forces
Polarizability & Periodic Table
• Polarizability increases down a group of atoms or
ions because size increases & larger electron
clouds are more easily distorted
• Polarizability decreases from left to right across
a period because the effective nuclear charge
holds the electrons more tightly
• Cations are less polarizable than parent atom
because they are smaller, whereas anions are
more polarizable because they are larger
21
 Intermolecular Forces
London Dispersion Forces
Intermolecular Forces
London Dispersion Forces
• London dispersion forces increase as molecular weight
increases.
• London dispersion forces exist between all molecules.
• London dispersion forces depend on the shape of the
molecule.
• The greater the surface area available for contact, the
greater the dispersion forces.
• London dispersion forces between spherical molecules
are lower than between sausage-like molecules.
Intermolecular Forces
Hydrogen Bonding
• Special case of dipole-dipole forces.
• By experiments: boiling points of compounds with H-
F, H-O, and H-N bonds are abnormally high.
• Intermolecular forces are abnormally strong.
• H-bonding requires H bonded to an electronegative
element (most important for compounds of F, O, and
N).
– Electrons in the H-X (X = electronegative element) lie much
closer to X than H.
– H has only one electron, so in the H-X bond, the δ+ H
presents an almost bare proton to the δ- X.
– Therefore, H-bonds are strong.
Intermolecular Forces
Hydrogen Bonding
22
 Intermolecular Forces
Hydrogen Bonding
• Hydrogen bonds are responsible for:
– Ice Floating
• Solids are usually more closely packed than liquids;
• therefore, solids are more dense than liquids.
• Ice is ordered with an open structure to optimize H-bonding.
• Therefore, ice is less dense than water.
• In water the H-O bond length is 1.0 Å.
• The O…H hydrogen bond length is 1.8 Å.
• Ice has waters arranged in an open, regular hexagon.
• Each δ+ H points towards a lone pair on O.
• Ice floats, so it forms an insulating layer on top of lakes,
rivers, etc. Therefore, aquatic life can survive in winter.

Intermolecular Forces
Hydrogen Bonding
• Hydrogen bonds are responsible for:
– Protein Structure
• Protein folding is a consequence of H-bonding.
• DNA Transport of Genetic Information

Intermolecular Forces
Comparing Intermolecular Forces

23
 Intermolecular Forces in Solutions
Ion-Dipole (40-600 kJ/mol)
H bond (10-40 kJ/mol)
Dipole-Dipole (5-25 kJ/mol)
Ion-Induced dipole (3-15 kJ/mol)
Dipole-Induced Dipole (2-10 kJ/mol)
Dispersion (0.05-40 kJ/mol)
The Uniqueness of Water
• Water has many unusual properties when
compared with properties that periodic trends
would otherwise predict:
Strongest – Higher boiling point
– Higher specific heat capacity
to
– Higher surface tension, capillarity
– Higher heat of vaporization
Weakest
– Lower vapor pressure
– Higher viscosity
– Dissolves many substances
– Liquid state at room T & P
– Solid form floats on liquid –less dense

The electrons forming each bond between

hydrogen and oxygen are drawn strongly toward
the oxygen atom

This results in two very polar bonds

The 104.5° bond angle makes a strong dipole

Water molecules also form hydrogen bonds

Comparison of Ice and Water

Issues: H-bonds and Motion
• Ice: 4 H-bonds per water molecule
• Water: 2.3 H-bonds per water molecule
• Ice: H-bond lifetime - about 10 microsec
• Water: H-bond lifetime - about 10 psec
• (10 psec = 0.00000000001 sec)
• Thats "one times ten to the minus eleven
second"!

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