Intermolecular Attractions and the Properties of

Liquids and Solids

Chapter 1
Kimia Dasar I (CH 1101)
2019-2020
1. Intermolecular Attractions and the Properties of
Liquids and Solids
2. Phase diagram and dynamic equilibrium
3. Vapor Pressure and Solid
4. Boiling Point of solution
5. Energy and Phase Changes
6. Phase Diagram
7. Determine Heat of Vaporization
8. Solid structure
Intermolecular Forces
• Important differences between gases,
solids, and liquids:
• Gases
• Expand to fill their container

• Liquids
• Retain volume, but not shape

• Solids
• Retain volume and shape

Jespersen/Brady/Hyslop Chemistry : The Molecular Nature of Matter , 6th Ed

Inter vs. Intra-Molecular Forces
Intramolecular forces
• Covalent bonds within molecule
• Strong
• Hbond (HCl) = 431 kJ/mol
Intermolecular forces
• Attraction forces between molecules, ions, and atoms
• Weak
• Hvaporization (HCl) = 16 kJ/mol
Covalent Bond (strong) Intermolecular attraction (weak)

Cl H Cl H
Four Types of
Intermolecular Forces
1.Dipole-dipole forces

1.Hydrogen bonds

1.London dispersion forces or Van der Walls

Ion Dipole Forces

Intermolecular Forces :
I. Dipole-Dipole Attractions
• Occur only between polar
molecules
• Molecules need to be close +  + 
together
• Polar molecules tend to align
their partial charges
• As dipole moment  +  +
increases,polarity will
increase and
intermolecular force
increases +  + 
• About 1–4% as strong as a
covalent bond

Jespersen/Brady/Hyslop Chemistry : The Molecular Nature of Matter , 6th Ed

Intermolecular Forces :
II. Hydrogen Bonds
• Special type of dipole-dipole Interaction
• Very strong dipole-dipole attraction
• ~10% of a covalent bond
• Occurs between H (attached to O, N, F) and highly
electronegative atom (O, N, or F) on highly polar bond
• H—F, H—O, and H—N bonds very polar
H O H O H F H O
H H H
H H H

H N H N H O H N

H H H H
Intermolecular Forces :
II. Hydrogen Bonds
• Boiling points of
hydrogen compounds
of elements of Groups
IVA, VA, VIA, and
VIIA.
• Boiling Point of H2O,
HF, and NH3 are higher
than expected because
of hydrogen bonding
Intermolecular Forces :
III. London Dispersion Forces
Electrostatic
attraction
• When atoms near one e e
another, their valence 2+ 2+
e
electrons interact e

• Repulsion causes electron He atom 1 He atom 2

clouds in each to distort and
polarize
• Instantaneous dipoles
result from this distortion    
Intermolecular Forces :
III. London Dispersion Forces
Boiling Point of Halogen and Noble Gases
Larger molecules have stronger London forces and thus
higher boiling points.
Intermolecular Forces :
III. London Dispersion Forces
Number of Atoms in Molecule
• London forces depend on number atoms in
molecule
• Boiling point of hydrocarbons demonstrates this
trend

Formula BP at 1 atm, C Formula BP at 1 atm, C

CH4 –161.5 C5H12 36.1
C2H6 –88.6 C6H14 68.7
C3H8 –42.1 : :
C4H10 –0.5 C22H46 327
Intermolecular Forces :
III. London Dispersion Forces
Molecule Shape Effect and London Forces
• Small area for interaction • Larger area for interaction

More compact – lower BP Less compact – higher BP

Your Turn
List all intermolecular forces for CH3CH2OH.

A. Hydrogen-bonds
B. Hydrogen-bonds, dipole-dipole attractions, London
dispersion forces
C. Dipole-dipole attractions
D. London dispersion forces
E. London dispersion forces, dipole-dipole attractions
Your Turn
In the liquid state, which species has the strongest
intermolecular forces, CH4, Cl2, O2 or HF?
A. CH4
B. Cl2
C. O2
D. HF
Your Turn
What is the strongest type of intermolecular force in
CHCl3?
A. ion-dipole
B. dipole-dipole
C. dispersion
D. Hydrogen bonding
E. None of the above
Intermolecular Forces :
IV. Ion-Dipole Attractions
Attractions between ion and charged end of
polar molecules
Attractions can be quite strong as ions have full
charges

(a) Negative ends of water dipoles surround cation

(b) Positive ends of water dipoles surround anion
Your Turn!
Which of the following is the weakest of all
intermolecular forces?
A. Hydrogen-bonds
B. London dispersion forces
C. Dipole-dipole attractions
D. Ion-dipole attractions
E. Ion-Ion attractions
Summary of Intermolecular Attractions
The order of strength (from the
strongest)
1. Ion-Dipole Attractions
2. Hydrogen Bonds
3. Dipole-Dipole Attractions
4. London Forces
Often can predict physical properties (like BP, MP and many
others) by comparing strengths of intermolecular attractions
Boiling Point 
Vapor Pressure ↓
Viscosity 
Changes Of State Involve Equilibria

• Fraction of molecules in condensed state is

higher when intermolecular attractions are
higher
• Intermolecular attractions must be overcome to
separate the particles, while separated particles are
simultaneously attracted to one another

condensed separated
phase phase
Similar Equilibria Reached in Melting
Melting Point (mp)
• Solid begins to change
into liquid as heat added
• Dynamic equilibria exists
between solid and liquid
states
• Melting (red arrows) and
freezing (black arrows)
occur at same rate
• As long as no heat added or
removed from equilibrium
mixture
Energy Changes Accompanying Phase
Changes

• All phase changes are possible under the right

conditions
• Following sequence is endothermic

heat solid  melt  heat liquid  boil  heat gas

• Following sequence is exothermic

cool gas  condense  cool liquid  freeze  cool solid

Phase Changes
Gas

Vaporization Condensation
Energy of System

Sublimation
Deposition
Liquid
Melting
Freezing
or Fusion

Solid
 Exothermic, releases heat
 Endothermic, absorbs heat
Energy Of Phase Changes
Endothermic Phase Changes
1. Must add heat
2. Energy entering system (+)
Sublimation: Hsub > 0
Vaporization: Hvap > 0
Melting or Fusion:Hfus > 0
Exothermic Phase Changes
1. Must give off heat
2. Energy leaving system (–)
Deposition: H < 0 = –Hsub
Condensation: H < 0 = –Hvap
Freezing: H < 0 = –Hfus
Energies of Phase Changes
• Expressed per mole
• Molar heat of fusion (Hfus)
• Heat absorbed by one mole of solid when it melts to give
liquid at constantT and P
• Molar heat of vaporization (Hvap )
• Heat absorbed when one mole of liquid is changed to one
mole of vapor at constant T and P
• Molar heat of sublimation (Hsub )
• Heat absorbed by one mole of solid when it sublimes to
give one mole of vapor at constant T and P
• All of these quantities tend to increase with increasing
intermolecular forces
Heating Curve
Heating Curve of Water at 1 atm

 Horizontal lines
 Phase changes
 Melting point
 Boiling point

 Diagonal lines
 Heating of solid, liquid or gas
Your Turn
How much heat, in J, is required to convert 10.00
g of ice at -10.00 °C to water at
50.00 °C?
Specific heat (J/g °C ): ice, 2.108, water, 4.184
Enthalpy of fusion = 6.010 J/mol
A. 5483 J 10.00 g H 2 O
2.108 J 10 K
 210.8 J
gK 1
B. 5638 J
1 mol 6.010 J
C. 2304 J 10.00 g H 2 O  3335 J
18.02 g H 2 O 1 mole
D. 2364 J 4.184 J 50 K
10.00 g H 2 O  2092 J
E. 62,400 J gK 1
210.8 J + 3335 J + 2092 J = 5638 J
Le Chatelier’s Principle
• Equilibria are often disturbed or upset
• When dynamic equilibrium of system is upset by a
disturbance
• System responds in direction that tends to
counteract disturbance and, if possible, restore
equilibrium
• Position of equilibrium
• Used to refer to relative amounts of substance on each
side of double (equilibrium) arrows
Liquid Vapor Equilibrium
Liquid + Heat  Vapor
• Increasing T
• Increases amount of vapor
• Decreases amount of liquid
• Equilibrium has shifted
• Shifted to the right
• More vapor is produced at expense of liquid
• Temperature-pressure relationships can be
represented using a phase diagram
Vapor Pressure

• Pressure exerted by gas when a liquid or solid

evaporates (pressure exerted by molecules of liquid
or solid in vapor phase).
• Increasing temperature increases vapor pressure
because vaporization is endothermic
• liquid + heat of vaporization ↔ gas
Equilibrium Vapor Pressure
• Vapor Pressure once dynamic equilibrium reached
• Usually referred to as simply vapor pressure
To measure pressures inside vessels, a manometer is
used.
Vapor Pressure Diagram
• Variation of vapor
pressure with T
• Ether
• Volatile
• High vapor pressure
near RT
• Propylene glycol
• Non-volatile
• Low vapor pressure
near RT
RT = 25 C
Effect of Volume on Vapor Pressure
A. Initial V
• Liquid – vapor
equilibrium exists
B. Increase V
• Pressure decreases
• Rate of
condensation
decreases
C. More liquid
evaporates
• New equilibrium
established
Do Solids Have Vapor Pressures?

• Yes
• At given temperature
• Some solid particles have enough KE to escape into
vapor phase
• When vapor particles collide with surface
• They can be captured
• Equilibrium vapor pressure of solid
• Pressure of vapor in equilibrium with solid
Boiling Point (bp)

• T at which vapor pressure of liquid = atmospheric

pressure.
• Bp increases as strength of intermolecular forces
increase

Normal Boiling Point

• T at which vapor pressure of liquid = 1 atm
Your Turn!
Which of the following will affect the boiling point of
a substance?
A. Polarizability
B. Intermolecular attractions
C. The external pressure on the material
D. All of these
E. None of these
Your Turn!
Which of the following substances will have the
highest boiling point?
A. LiCl
B. Cl2
C. HCl
D. CO2
E. Not enough information to tell
Your Turn!
Which of the following substances will have the
highest boiling point?
A) F2
B) Cl2
C) I2
D) Br2
E) Not enough information to tell
Phase Diagram
• Show the effects of both pressure and temperature
on phase changes
• Boundaries between phases indicate equilibrium
• Triple point:
• The temperature and pressure at which s, l, and g are all
at equilibrium
• Critical point:
• The temperature and pressure at which a gas can no
longer be condensed
• TC = temperature at critical point
• PC = pressure at critical point
Phase Diagram
Phase Diagram of Water
Supercritical Fluid
• Substance with temperature above its critical
temperature (TC) and density near its liquid density
• Have unique properties that make them excellent
solvents
• Values of TC tend to increase with increased
intermolecular attractions between particles
Your Turn
At 89 °C and 760 mmHg,
what physical state is
present?
A. Solid
B. Liquid
C. Gas
D. Supercritical fluid
E. Not enough information is
given
Types of Solids
• Crystalline Solids
• Solids with highly regular arrangements of components
• Amorphous Solids
• Solids with considerable disorder in their structures
Crystalline Solids

• Unit Cell
• Smallest segment
that repeats
regularly
• Smallest repeating
unit of lattice
• 2-Dimensional Unit
Cells
Crystal Structures Have Regular
Patterns
• Lattice
• Many repeats of unit cell
• Regular, highly
symmetrical system
• Three (3) dimensional system of
points designating positions of
components
• Atoms
• Ions
• Molecules
Three Types Of 3-D Unit Cells

• Simple cubic
• Has one host atom at each corner
• Edge length a = 2r
• where r is radius of atom or ion
• Body-centered cubic (BCC)
• Has one atom at each corner and one in
center
4r
• Edge length a 
3
• Face-centered cubic (FCC)
• Has one atom centered in each face, and
one at each corner
• Edge length a  2 2 r
The theoretical density
• Theoretical density calculation from crystal
structure.

• = number of atoms in the unit cell “atoms”

• = Molar Mass (atomic weight) “g/mol”
• = volume of unit cell
• = Avogadro’s number (6.023 x 1023 atoms/mol)
Example: FCC Metal Al
 lattice parameter, a = 4.05 Å, n = 4. Atomic
weight of Al is 26.98 g/mol

26.98
atoms/mol
g/cm3
Example: BCC Metal Tantalum

330.6 pm; 16.69 g/cm3.

1. Determine the mass of a tantalum atom.
2. Determine the atomic weight of tantalum in
g/mol.
Solution: BCC Ta (1)
1. The edge length a = 330.6 pm x 1 cm/1010 pm
= 330.6 x 10-10 cm = 3.306 x 10-8 cm.
The volume of the unit cell
(3.306 x 10-8 cm)3 = 3.6133 x 10-23 cm3
Mass of the 2 tantalum atoms in the BCC:
16.69 g/cm3 x 3.6133 x 10-23 cm3
= 6.0307 x 10-22 g.
The mass of one atom of Ta:
6.0307 x 10-22 g / 2 = 3.015 x 10-22 g
Solution: BCC Ta (2)

2. The atomic weight of Ta in g/mol:

3.015 x 10-22 g times 6.022 x 1023 /mol
= 181.6 g/mol
Example: BCC Metal Cr
 128 pm. Calculate the density of solid
crystalline chromium (51.9 g/mol) in gram/cm3.
Solution:
r=(128 pm) (1 cm / 1010 pm) = 1.28 x 10-8 cm
4r
a
3
2.956 x 10-8 cm)3 = 2.4 x 10-23 cm3
Mass of two atoms in BCC:
51.9 g/mol x 2 = 103.8 g/mol
Example: BCC Metal Cr

the density:

103.8 g/mol
2.4 x 10−23 cm3 6.02 x 1023 atoms

7.18 g/cm3
3-D Simple Cubic Lattice
Unit Cell

Portion of lattice— Space filling

open view model
Other Cubic Lattices

Face Centered Body Centered

Cubic Cubic
Ionic Solids
Lattices of Alternating charges
• Want cations next to anions
• Maximizes electrostatic attractive forces
• Minimizes electrostatic repulsions
• Based on one of three basic lattices:
• Simple cubic
• Face centered cubic (FCC)
• Body centered cubic (BCC)
Common Ionic Solids
Rock salt or NaCl
• Face centered cubic lattice of Cl ions (green)
• Na+ ions (blue) in all octahedral holes
Other Common Ionic Solids

Cesium Chloride, Zinc Sulfide, Calcium

CsCl ZnS Fluoride, CaF2
Spaces In Ionic Solids Are Filled With
Counter Ions
• In NaCl
• Cl ions form face-
centered cubic unit cell
• Smaller Na+ ions fill
spaces between Cl ions
• Count atoms in unit cell
• Have 6 of each or 1:1
Na+:Cl ratio
Counting Atoms per Unit Cell
• 4 types of sites in unit cell
• Central or body position – atom is completely contained
in one unit cell
• Face site – atom on face shared by two unit cells
• Edge site – atom on edge shared by four unit cells
• Corner site – atom on corner shared by eight unit cells

Site Counts as Shared by X unit cells

Body 1 1
Face 1/2 2
Edge 1/4 4
Corner 1/8 8
Example: NaCl

Edge Corner
Face
Site # of Na+ # of Cl
Body 1 0
Face 0 6  1 2   3
Edge 12  1 4   3 0
Corner 0 8  1 8   1
Total 4 4
Center
Learning Check:
Determine the number of each type of ion in
the unit cell.

1:1 4:4 4:8

CsCl ZnS CaF2
Some Factors Affecting Crystalline
Structure

• Size of atoms or ions involved

• Stoichiometry of salt
• Materials involved
• Some substances do not form crystalline solids
Amorphous Solids (Glass)
• Have little order, thus referred to as “super cooled
liquids”
• Edges are not clean, but ragged due to the lack of order
Ionic Crystals (ex. NaCl, NaNO3)

• Have cations and anions at lattice sites

• Are relatively hard
• Have high melting points
• Are brittle
• Have strong attractive forces between ions
• Do not conduct electricity in their solid states
• Conduct electricity well when molten
Your Turn!

Yitterbium crystallizes with a face centered cubic

lattice. The atomic radius of Yitterbium is 175 pm.
Determine the unit cell length.

A. 495 pm
B. 700 pm
C. 350 pm
D. 990 pm
E. 247 pm
Your Turn! - Solution

diagonal of cube = 4r where r = atomic radius

diagonal of cube = 2 a where a = side of cube
4r 4 x 175 pm
a=   495 pm
2 2
Covalent Crystals
• Lattice positions occupied by atoms that are
covalently bonded to other atoms at neighboring
lattice sites
• Also called network solids
• Interlocking network of covalent bonds extending all
directions
• Covalent crystals tend to
• be very hard
• have very high melting points
• have strong attractions between
covalently bonded atoms
Ex. Covalent (Network) Solid

• Diamond (all C)
• shown
• SiO2 silicon oxide
• Alternating Si and O
• Basis of glass and quartz
• Silicon carbide (SiC)
Metallic Crystals
• Simplest models
• Lattice positions of metallic crystal
occupied by positive ions
• Cations surrounded by “cloud” of
electrons
• formed by valence electrons
• extends throughout entire solid
Learning Check:

Classify the following in terms of most likely type of solid.

Substance ionic molecular covalent metallic
X: pulverizes when struck;
non-conductive of heat
and electricity 
Y: White crystalline solid
that conducts electrical
current when molten or

dissolved
Z: shiny, conductive,
malleable with high
melting temperature

Your Turn!

Molecular crystals can contain all of the listed

attraction forces except:
A. Dipole-dipole attractions
B. Electrostatic forces
C. London forces
D. Hydrogen bonding
Interaksi Antar Molekul dan
Struktur Padatan
1. Tentukan semua interaksi antar molekul senyawa-senyawa di
bawah ini, lalu garis bawahi interaksi antar molekul yang paling
kuat yang terdapat dalam masing-masing senyawa tersebut.
a. N2 (g)
b. NaCl (s)
c. NaCl (aq) f.
d. He (g)
e. H2O (l) g.
Interaksi Antar Molekul dan
Struktur Padatan
2. Urutkan titik didih senyawa-senyawa dibawah ini dari paling tinggi
hingga paling rendah. Kemudian tentukan senyawa manakah yang
mempunyai tekanan uap jenuh paling tinggi pada masing-masing
kelompok senyawa (a, b, dan c).
a. NH3; PH3, AsH3
b. CH4; SiH4, GeH4; SnH4
c. HF; HCl; HBr; HI

3. Jelaskan dengan singkat mengapa dalam keadaan STP, Br2 berada

dalam fasa cairan, sedangkan I2 berada dalam fasa padat?
Interaksi Antar Molekul dan
Struktur Padatan
4. Berikut adalah senyawa-senyawa yang mempunyai rumus kimia C4H10.
Tentukan senyawa yang manakah yang memiliki titik didih lebih tinggi.
Jelaskan dengan singkat alasannya.

(a) (b)

5. Berikut adalah data tekanan uap dari beberapa senyawa:

Urutkan senyawa-senyawa di
samping berdasarkan interaksi
antar molekulnya dari yang
paling kuat ke paling lemah.
Interaksi Antar Molekul dan
Struktur Padatan
6. Kalor molar penguapan (∆Hvap) acetone, C3H6O, adalah 30,3 kJ/mol
pada titik didihnya. Berapa kilojoule kalor akan terlepaskan oleh
proses kondensasi 5,00 g acetone?
7. Hitung Energi yang diperlukan untuk mengubah 100 gram es pada
suhu -10 oC menjadi uap air pada suhu 120 oC?
ΔHvap of H2O = 40.7 kJ/mol
ΔHfus of H2O = 6.02 kJ/mol
Cm air (s) = 37.6 J/mol°C
Cm air (l) = 75.3 J/mol°C
Cm air (g) = 36.5 J/mol°C
Interaksi Antar Molekul dan
Struktur Padatan
8. Rangkumkan tiga tipe unit sel dari kisi kristal berbentuk kubus,
yaitu kubus sederhana, kubus berpusat muka (FCC), dan kubus
berpusat badan (BCC).
• Gambar satu sel satuannya
• Jumlah atom dalam satu sel satuan
• Gambar posisi-posisi atom (tidak perlu semua atomnya) yang
saling bersinggungan untuk menunjukkan hubungan antara
panjang rusuk kubus dengan jari-jari atom
• Berikan contoh atom-atom logam yang mengkristal dengan
tipe kubus sederhana, BCC, dan FCC (masing-masing dua
contoh).
Interaksi Antar Molekul dan
Struktur Padatan
9. NaCl mengkristal membentuk kisi kristal kubus yang mirip dengan
kubus berpusat muka.
a. Gambarkan struktur satu unit sel kristalnya.
b. Berapakah jumlah ion Na+ dan Cl- masing-masing dalam satu
sel satuan (unit cell) dan uraikan jumlah ionnya untuk posisi di
badan, muka, rusuk dan sudut?
c. Jika jari jari ion Na+= 97 pm dan jari jari ion Cl- =181 pm.
Tentukan panjang rusuk sel satuan kristal NaCl?

10. Kalsium (Ca) adalah salah satu contoh logam yang mengkristal
dengan kisi kristal tipe kubus berpusat muka. Diketahui jari-jari
atom Ca adalah 197 pm.
a. Tentukan massa (gram) atom logam Kalsium (Ca) dalam
satu sel satuan.
b. Tentukan kerapatan (massa jenis (g/cm3)) dari Kalsium.
Interaksi Antar Molekul dan
Struktur Padatan
11. Gunakan data pada Tabel di bawah ini untuk menjawab pertanyaan
berikut.
No Senyawa Tekanan uap pada
20oC
1 Asam asetat, CH3COOH 11,7 torr
2 Aseton, CH3COCH3 184,8 torr
3 Dietil eter, C2H5OC2H5 442,2 torr
a. Urutkan senyawa tersebut berdasarkan titik didihnya, mulai dari
yang paling rendah.
b. Tentukan jenis interaksi antar melekul yang paling kuat pada dua
senyawa pertama.
c. Urutkan senyawa tersebut berdasarkan kekuatan interaksi antar
molekulnya mulai dari yang paling lemah.
Interaksi Antar Molekul dan
Struktur Padatan
12. Nikel memiliki jari-jari atom 124 pm dan mengkristal dengan
membentuk sel satuan kubus berpusat muka.
a. Gambarkan satu sel satuan nikel.
b. Hitung panjang rusuk kubus sel satuan tersebut.
c. Hitung massa nikel (dalam gram) dalam satu sel satuan.
Perhatikan jumlah atom dalam sel satuan tersebut.
d. Hitung massa jenis kristal nikel ini dalam gram/cm3