Chapter 11

Liquids and Intermolecular

Forces

11.1 A Molecular Comparison of Gases, Liquids, and Solids

11.2 Intermolecular Forces
11.3 Select Properties of Liquids
11.4 Phase Changes
11.5 Vapor Pressure
11.6 Phase Diagrams
11.7 Liquid Crystals
Lecture Goal
• Understanding the nature and strength of “intermolecular
forces”
▪ Attractive and repulsive forces existing between molecules

▪ Implication of these forces on the composition and structure of a

substance

Figure 11.1 A microscopic view of a water

droplets on the surface of a lotus leaf.
2
11.1 A Molecular Comparison of Gases, Liquids, and Solids

• Gas vs. Liquids vs. Solids

▪ Intermolecular forces in liquids and solids are much stronger than
those in gases

▪ In liquids, the intermolecular attractive forces are strong enough to

hold particles close together, but are not strong to keep the
particles from moving past one another

▪ In solids, the intermolecular attractive forces are strong enough to

hold particles close together and to lock them virtually in place

3
11.1 A Molecular Comparison of Gases, Liquids, and Solids

• Gas vs. Liquids vs. Solids

4
11.1 A Molecular Comparison of Gases, Liquids, and Solids

• Three states of matter

▪ The state of a substance depends largely on the balance between
the kinetic energies and the interparticle energies of attraction

➢ Kinetic energies tend to keep the particles apart and moving, which
depend on temperature

✓ As the temperature decreases, the average kinetic energy decreases,

allowing the attractions to draw the particles close together, forming a
liquid or solid

➢ Interparticle attractions tend to draw the particles together

✓ Interparticle attraction: Gases < Liquids < Solids

5
Figure 11.2
Gases, liquids, and
solids.
6
11.2 Intermolecular Forces

• Strengths of intermolecular forces

▪ Generally, much weaker than intramolecular forces (ionic, metallic,
or covalent bonds)

➢ Intermolecular attraction in liquid HCl is 16 kJ/mol, but the energy

required to break the covalent bond in HCl is 431 kJ/mol

➢ When a molecular HCl changes from solids to liquids to gas, the

molecules remain intact

Figure 11.3
Intermolecular and intramolecular interactions.
7
11.2 Intermolecular Forces

• Physical properties (boiling, melting point, …)

▪ Reflect the strength of the intermolecular forces

➢ The stronger the attractive forces, the higher the temperature at

which the liquid boils

➢ The melting points of solids increase as the strengths of the

intermolecular forces increase

8
11.2 Intermolecular Forces

• Types of intermolecular attractions

▪ Dispersion forces
Van der Waals force
▪ Dipole-dipole attraction

▪ Hydrogen bonding

• All intermolecular interactions are electrostatic, involving

attractions between positive and negative species
▪ The charges responsible for intermolecular forces are generally
much smaller than the charges in ionic compounds

▪ The distance between molecules are often larger than the

distances between atoms held together by chemical bonds 9
Dispersion Forces

• Dispersion force
▪ Attractive interaction among neutral, nonpolar atoms (or molecules)

▪ Fritz London proposed that the motion of electrons in an atom or

molecule can create an instantaneous dipole moment

10
Figure 11.4 Dispersion forces.
Dispersion Forces

• Dispersion force
▪ Also called London dispersion force or induced dipole – induced
dipole interaction

▪ It is significant only when molecules are very close together

▪ Polarizability (분극화) : Instantaneous dipole formed due to distortion

of the charge distribution

▪ More palarizable molecules have larger dispersion forces

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Dispersion Forces

• The strength of dispersion force

▪ Polarizability increases as the number of electrons in an atom or
molecule increases

▪ The strength of dispersion forces tends to increase with increasing

molecular weight

Figure 11.5 Boiling points of the

halogens and noble gases. 12
Dispersion Forces

• The strength of dispersion force

▪ Molecular shape influences the magnitude
of dispersion forces

▪ Both n-pentane and neopentane have the same

molecular formula, C5H12.

➢ Linear molecule, with a larger surface area,

increases dispersion force

➢ Spherical molecule, with a smaller surface area,

decreases dispersion force

Figure 11.6 Molecular shape

affects intermolecular attraction.
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Dipole-Dipole Interactions

• In polar molecules have permanent dipole moments

▪ Dipole-dipole interactions are effective only when molecules are very
close together

▪ Acetonitrile (CH3CN, MW 41 u vs. propane (CH3CH2CH3, MW 44 u)

➢ Acetonitrile is polar molecule with dipole-dipole interactions (a dipole

moment of 3.9 D)

➢ Propane is essentially nonpolar without dipole-dipole interactions

➢ Boiling point : Acetonitrile (355 K) > propane (231 K)

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Dipole-Dipole Interactions

• Dipole-dipole interactions in the solid and liquid

▪ In the solid, the molecules are arranged with the negatively charged
end of each molecules close to the positively charged of its
neighbors

▪ In the liquid, the molecules are free to move with respect to one
another, and their arrangement becomes more disordered

Figure 11.7 Dipole-dipole

interactions. 15
 Dipole-Dipole Interactions

• Dipole-dipole interactions
▪ For molecules of approximately equal mass and size, the strength of
intermolecular attractions increases with increasing polarity

Figure 11.8 Molecular weights, dipole moments, and boiling points of several simple
organic substances. 16
Hydrogen Bonding

• Binary compounds containing hydrogen and the elements in

groups 14 – group 17

Figure 11.9 Boiling points of the

covalent hydrides of the
elements in groups 14 – 17 as a
function of a molecular weight.
17
Hydrogen Bonding

• Hydrogen bond
▪ Strong intermolecular attractions
in HF, H2O, and NH3

▪ Attraction between a hydrogen atom

attached to a highly electronegative
atom (usually F, O, or N) and a nearby
small electronegative atom in another
molecule or chemical group

Figure 11.10 Hydrogen bonding.

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Hydrogen Bonding
Figure 11.12 Expansion of
• Hydrogen bonding in H2O water upon freezing.

▪ Density of ice at 0 oC (0.917 g/mL) is less than that of liquid water at

0 oC (100 g/mL)

Figure 11.11 Hydrogen bonding in ice. The empty

channels in the structure of ice make water less
dense as a solid than as a liquid.
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Ion-Dipole Forces

• Between an ion and a polar molecule

▪ Each ions are attracted to the oppositive
end of a polar molecule

▪ Magnitude of the attraction increases as

either the ionic charge or the magnitude of
the dipole moment increases

Figure 11.13 Ion-dipole

forces. 20
Comparing Intermolecular Forces

• Intermolecular forces
▪ Dispersion forces are found in all substances
: 0.1 – 30 kJ/mol

▪ Dipole-dipole interactions are in polar molecules

: 2 – 15 kJ/mol

▪ Hydrogen bonds are between hydrogen and highly electronegative

atoms
: 10 – 40 kJ/mol

▪ Ion-dipole forces are between ionic substance and polar molecules

: > 50 kJ/mol
21
Comparing Intermolecular Forces

• Intermolecular forces

Figure 11.14 Checklist for determining intermolecular forces. Multiple types of

intermolecular forces can be operating in a given substance or mixture. Note that
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dispersion forces occur in all substances.
Comparing Intermolecular Forces

• The effects of the intermolecular forces

are additive
▪ Both acetic acid and 1-propanol have
the same molecular weight, 60 u, and
can form hydrogen bonds.

▪ A pair of acetic acid molecules can form two

hydrogen bonds, whereas a pair of 1-propanol
molecules can form only one

▪ The boiling point of acetic acid is higher than

Figure 11.15 Hydrogen
that of 1-propanol
bonding in acetic acid
and 1-propanol.
23
Comparing Intermolecular Forces

• When comparing the relative strengths of intermolecular

attractions, consider these generalizations:
1. When the molecules of two substances have comparable
molecular weights and shapes, dispersion forces are
approximately equal in the two substances.

2. When the molecules of two substances differ widely in molecular

weights, and there is no hydrogen bonding, dispersion forces
tend to determine which substance has the stronger
intermolecular attractions.

24
11.3 Select Properties of Liquids

• The intermolecular attractions can help us understand

many familiar properties of liquids
▪ Viscosity (점도)

▪ Surface tension (표면장력)

▪ Capillary action (모세관 현상)

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Viscosity

• Viscosity is the resistance of a liquid to flow

▪ The greater a liquid’s viscosity, the slower it flows

▪ SI unit for viscosity is kg/m-s.

▪ Viscosity is increases with molecular weight

▪ Viscosity decreases with increasing temperature

Figure 11.16 Comparing

viscosities.
26
Surface Tension

• The energy required to increase

the surface area of a liquid
▪ Molecules in the interior are attracted
equally in all directions, but those at
the surface experience a net inward
force

▪ Water has a high surface tension

because its strong hydrogen bonds

▪ Mercury has even higher surface tension

because of stronger metallic bonds Figure 11.18 Molecular-level view
of surface tension.
between the Hg atoms
27
Capillary Action

• Capillary action
▪ Cohesive force (응집력) : intermolecular forces that bind similar
molecules to one another (e.g., hydrogen bonding in water)

▪ Adhesive force (접착력) : Intermolecular forces that bind a substance

to a surface (e.g., a glass tube)

▪ Water in a glass (SiO2) tube adheres to the glass because the

adhesive forces are greater than the cohesive forces (U-shaped
surface)

▪ Hg atoms can form bonds with one another but not with the glass, so
cohesive forces are much greater than the adhesive forces (inverted
U-shaped surface) 28
Capillary Action

• Capillary action

Figure 11.19 Meniscus shapes for water and mercury in glass tubes. 29
Capillary Action

• Capillary action
▪ When a small-diameter glass tube is placed in water, water rises in
the tube until the force of gravity on the liquid balances the adhesive
and cohesive forces

▪ Capillary action is the rise of liquids up very narrow tubes

▪ The surface tension of the liquid tends to reduce the area, thereby
pulling the liquid up the tube

30
11.4 Phase Changes

• Each state of matter (solid, liquid, and gas) can transform

into either of the other two states

Figure 11.20 Phase changes and the

names associated with them.
31
Energy Changes Accompany Phase Changes

• Every phase change is accompanied by a change in the

energy of the system
▪ Heat of fusion (enthalpy of fusion, ∆𝐻𝑓𝑢𝑠 ) : 용융열

➢ energy required for the transition of the solid to the liquid

▪ Heat of vaporization (enthalpy of vaporization, ∆𝐻𝑣𝑎𝑝 ) : 기화열

➢ energy required for the transition of the liquid to the vapor

▪ Heat of sublimation (enthalpy of sublimation, ∆𝐻𝑠𝑢𝑏 ) : 승화열

➢ energy required for the transition of the solid directly into the gas

32
Energy Changes Accompany Phase Changes

• Phase of changes
▪ 𝐻2 𝑂 𝑠 ⟶ 𝐻2 𝑂 𝑙 ∆𝐻𝑓𝑢𝑠 = 6.01 𝑘𝐽

▪ 𝐻2 𝑂 𝑙 ⟶ 𝐻2 𝑂 𝑔 ∆𝐻𝑣𝑎𝑝 = 40.7 𝑘𝐽

▪ 𝐻2 𝑂 𝑠 ⟶ 𝐻2 𝑂 𝑔 ∆𝐻𝑠𝑢𝑏 = 47 𝑘𝐽 ∆𝑯𝒔𝒖𝒃 = ∆𝑯𝒇𝒖𝒔 + ∆𝑯𝒗𝒂𝒑

∆𝐻𝑣𝑎𝑝 > ∆𝐻𝑓𝑢𝑠

In the transition from liquid to gas,

particles must essentially sever all
their interparticle attractions,
however, in the transition from solid
to liquid, many of these attractions
remain operative.
Figure 11.21 Heats of fusion, vaporization, and
33
sublimation.
Energy Changes Accompany Phase Changes

• Phase of changes
▪ Enthalpy of vaporization
= - (Enthalpy of condensation)

▪ Enthalpy of fusion
= - (Enthalpy of freezing)

▪ Enthalpy of sublimation
= - (Enthalpy of deposition)

Figure 11.20 Phase changes and the

names associated with them.
34
Heating Curves

• Heating curve
▪ A graph of temperature versus amount of heat added

➢ AB : Heating increases temperature

of H2O(s) from -25 to 0 oC

➢ BC : Heating converts H2O(s) to

H2O(l) as the ice melts at a
constant temperature of 0 oC

➢ CD : Heating increases temperature

of H2O(l) from 0 to 100 oC

Figure 11.22 Heating curve for water.

35
Heating Curves

• Heating curve
▪ A graph of temperature versus amount of heat added

➢ DE : Heating converts H2O(l) to

H2O(g) as the water boils at a
constant temperature of 100 oC

➢ EF : Heating increases temperature

of H2O(g) from 100 to 125 oC

Figure 11.22 Heating curve for water.

36
Heating Curves

• Heating curve
▪ A graph of temperature versus amount of heat added

➢ Specific heat of water is greater

than that of ice, so the slope of
line CD is less than that of line AB

➢ In line BC and DE, the added

energy is used to overcome the
attractive forces between molecules
rather than to increase their average
kinetic energy

Figure 11.22 Heating curve for water.

37
Heating Curves

• Heating curve
▪ Supercooling

➢ As we remove heat from a liquid, we can temporarily cool it below its

freezing point without forming a solid

➢ When the heat is removed so rapidly that the molecules have no time
to assume the ordered structure of a solid

➢ A supercooled liquid is unstable; particles of dust entering the solution

or gentle stirring is often sufficient to cause the substance to solidify
quickly

38
Critical Temperature and Pressure

• A gas liquefies when a certain pressure and temperature

▪ Water vapor forms liquid water at 100 oC with 101.3 kPa, at 110 oC
with 143.3 kPa, and at 374 oC with 22.06 Mpa

▪ Above 374 oC, no amount of pressure causes a distinct liquid

phase to form, and the gas becomes steadily more compressed

• Critical point
▪ The critical temperature (임계온도) : the highest temperature at
which a distinct liquid phase can form

▪ The critical pressure (임계압력) : the pressure required to bring

about liquefaction at this critical temperature
39
 Critical Temperature and Pressure

Nonpolar and low

molecular weight

Hydrogen
bonding

※ When the temperature and pressure exceeds the critical values, the substance is
in a state called a supercritical fluid (초임계유체), which can expand to fill its
container (like a gas), but the molecules are still quite closely spaced (likely a liquid)
40
11.5 Vapor Pressure

• Molecules can escape from the surface of a liquid into the

gas phase by evaporation
▪ Vapor pressure is the pressure exerted by its vapor when the
liquid and vapor are in dynamic equilibrium

▪ A liquid and its vapor are in

dynamic equilibrium when
evaporation and condensation
occur at equal rates

Figure 11.23 Vapor pressure over a

liquid 41
Volatility, Vapor Pressure, and Temperature

• Volatility
▪ When vaporization occurs in an open system, the vapor continues
to form until the liquid evaporates to dryness

▪ Substances with high vapor pressure evaporate more quickly than

substances with low vapor pressure

▪ Liquids that evaporate readily are volatile (휘발성)

▪ As the temperature increase, the molecules move more

energetically and more of them can break free from their neighbors
and enter the gas phase, increasing the vapor pressure

42
Volatility, Vapor Pressure, and Temperature
Intramolecular attraction
• Volatility Ethylene glycol > Water > Ethyl alcohol > Diethyl ether

Figure 11.24 The effect of temperature Figure 11.25 Vapor pressure for four
on the distribution of kinetic energies in a liquids as a function of temperature.
liquid. 43
Vapor Pressure and Boiling Point

• Boiling point (끓는점)

▪ Temperature at which its vapor pressure equals the external
pressure, acting on the liquid surface

➢ The normal boiling point is the temperature at which its vapor

pressure is 760 torr (101.3 kPa)

➢ The boiling point increases as the external pressure increases

44
Vapor Pressure: A Closer Look [Page 499]

• The Clausius – Clapeyron Equation

▪ The natural log of the
vapor pressure of a liquid
is inversely proportional
to its absolute temperature
−∆𝐻𝑣𝑎𝑝
ln 𝑃 = +𝐶
𝑅𝑇
𝑃 is the vapor pressure
𝑇 is the absolute temperature (K)
𝑅 is the gas constant (8.314 J/mol-K)
∆𝐻𝑣𝑎𝑝 is the molar enthalpy of vaporization, and
Figure 11.26 The natural logarithm of
𝐶 is a constant
vapor pressure versus 1/T for ethanol.
45
11.6 Phase Diagrams
• Phase diagram
▪ A graphic way to summarize the conditions under which equilibria
exist between the different states of matter

▪ Allow us to predict which phase of a substance is present at any

given temperature and pressure

Figure 11.27 Generic phase

diagram for a pure substance.
46
11.6 Phase Diagrams
• Vapor-pressure curve (red curve)
▪ Represent equilibrium between the liquid and gas phase

▪ The curve starts at the triple point (T) and ends at the critical point (C)

▪ Each point along this line

is the boiling point, which
is pressure-dependent

▪ Beyond the critical point,

the substance is
a supercritical fluid
(초임계유체)
47
11.6 Phase Diagrams
• Sublimation curve (green curve)
▪ Represent a condition of equilibrium between the solid and gas

▪ Below the triple point (T) the substance CANNOT exist in the liquid
state

▪ Each point along this line

is the sublimation point
at each pressure

48
11.6 Phase Diagrams
• Melting curve (blue curve)
▪ Represent the change in melting point of the solid with increasing
pressure

▪ Less pressure-dependent

▪ This curve usually slopes

slightly to the right as
pressure increases for
most substances, because
the solid is denser than
liquid

49
11.6 Phase Diagrams
• Triple point (T, 삼중점)
▪ Where the three curves intersect, and here all three phases are in
equilibrium

▪ Any other point of the curves

represent equilibrium
between two phases

▪ Any point on the diagram

that does not fall on one of
the curves corresponds to
conditions under which
only one phase is present
50
The Phase Diagrams of H2O and CO2

• Phase diagrams of H2O

▪ The melting curve (blue line) is atypical

➢ Slanting slightly to the left (that is, the melting point decreases) with
increasing pressure

➢ It is because that water has more compact than ice

High critical temperature and critical

pressure due to strong intermolecular
101.3 kPa forces between H2O molecules

Triple point at low pressure (0.611 kPa)

Freeze-dry at P < triple point

Figure 11.28 Phase diagram of H2O.

51
The Phase Diagrams of H2O and CO2

• Phase diagrams of CO2

▪ The melting curve (blue line) is typical

➢ Slanting to the right (that is, the melting point increases) with
increasing pressure

➢ At the atmospheric pressure (101.3 kPa), it does not exist as a liquid

Solid CO2 does not melt when heated,

but instead sublimes (dry ice)
It does not have a normal melting point;
101.3 kPa and has a normal sublimation point,
-78.5 oC

Figure 11.29 Phase diagram of CO2.

52
11.7 Liquid Crystals

• Friedrich Reinitzer discovered that

cholesteryl benzoate is
▪ Solid : T < 145 oC

▪ Liquid crystalline (액정) state

(viscous milky liquid) : 145 oC < T < 179 oC

▪ Liquid phase : T > 179 oC

▪ Intermediate phase has some of the structure

of solids and some of the freedom of motion
of liquids (viscous and intermediate properties
between solids and liquids) Figure 11.31 Cholesteryl
benzoate in its liquid and
53
liquid crystalline states.
Types of Liquid Crystals

• Molecules in liquid crystals

▪ Substances that form liquid crystals are composed of rod-shaped
molecules that are somewhat rigid

➢ The lengths of these molecules are much greater than their widths

➢ Double bonds add rigidity to the molecules and the benzene rings help
the molecule stack with one another

➢ The polar –OCH3 and –COOH groups promote alignment of the

molecule (dipole-dipole interaction)

Figure 11.33 Molecular structure and

liquid crystal temperature range for two
typical liquid crystalline materials. 54
Types of Liquid Crystals

• Arrangement of the molecules in liquid phase and liquid

crystalline phase
▪ In the liquid phase, these molecules are oriented randomly

▪ In the liquid crystalline phase, the molecules are arranged in

specific patterns

▪ Depending on the nature of the ordering, liquid crystals are

classified as nematic, smectic A, smectic C, or cholesteric

55
Types of Liquid Crystals

Figure 11.32 Molecular order in nematic, smectic, and cholesteric liquid crystals. In the
liquid phase of any substance, the molecules are arranged randomly, whereas in the
liquid crystalline phases the molecules are arranged in a partially ordered way. 56
Types of Liquid Crystals

• Nematic and smectic liquid crystal

▪ In nematic liquid crystal, molecules are only ordered in one
dimension (일정 방향), along the long axis

▪ In smectic liquid crystal, molecules maintain the long-axis alignment

and in addition they pack into layers

▪ In smectic liquid crystals, the intermolecular forces (dispersion force,

dipole-dipole attractions, and hydrogen bonding) limit the ability of
the molecules to slide past one another

57
Types of Liquid Crystals

• Cholesteric liquid crystal

▪ In cholesteric liquid crystal, the molecules are arranged in layers,
with their long axes parallel to the other molecules within the same
layer

▪ Upon moving from one layer to the next,

the orientation of the molecules rotates
by a fixed angle, resulting in a spiral pattern

▪ The arrangement produces unusual

coloring patterns with visible light,
changes in temperature and
Figure 11.34 Electronic paper
pressure change the color (e-paper) based on cholesteric
liquid crystal technology.
58
 Homework : Chap 11

• Exercise [Page 507 ~ ]

▪ 12, 17, 22, 34, 42, 52, 60, 61, 65, 68

▪ Due : ~ 6/5 (Mon) 09:00

▪ Blackboard system – 과제 및 시험

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