ch11 - Intermolecular Forces - (7ed)

12/17/20
Intermolecular Attractions and the

Properties of Liquids and Solids
Ki1101 Kimia Dasar 1A

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Intermolecular Forces (1 of 3)
• Important differences between gases, solids,
and liquids:
o Gases
• Expand to fill their container
o Liquids
• Retain volume, but not shape
o Solids
• Retain volume and shape
Copyright ©2014 John Wiley & Sons, Inc. 2
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• Physical state of molecule depends on
o Average kinetic energy of particles
• Recall KE µ Tave
o Intermolecular Forces
• Energy of Inter-particle attraction
• Physical properties of gases, liquids and solids
determined by
o How tightly molecules are packed together
o Strength of attractions between molecules
Intermolecular Attractions
• Converting gas ® liquid or solid
o Molecules must get closer together
• Cool or compress
• Converting liquid or solid ® gas
o Requires molecules to move farther apart
• Heat or reduce pressure
• As T decreases, kinetic energy of molecules decreases
o At certain T, molecules don’t have enough energy to
break away from one another’s attraction
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Inter versus Intra-Molecular Forces

• Intramolecular forces
o Covalent bonds within molecule
o Strong
o DHbond (HCl) = 431 kJ/mol
• Intermolecular forces
o Attraction forces between molecules
o Weak
o DHvaporization (HCl) = 16 kJ/mol
Electronegativity Review
Electronegativity: Measure of attractive force that one
atom in a covalent bond has for electrons of the bond
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Bond Dipoles
• Two atoms with different electronegativity values share
electrons unequally
• Electron density is uneven
o Higher charge concentration around more electronegative atom
• Bond dipoles
o Indicated with delta (δ) notation H F
o Indicates partial charge has arisen
d+ d-
Net Dipoles
• Symmetrical molecules
o Even if they have polar bonds
o Are non-polar because bond dipoles cancel
• Asymmetrical molecules
o Are polar because bond dipoles do not cancel
o These molecules have permanent, net dipoles
• Molecular dipoles
o Cause molecules to interact
o Decreased distance between molecules increases amount of interaction
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• When substance melts or boils
o Intermolecular forces are broken
o Not covalent bonds
• Responsible for non-ideal behavior of gases

• Responsible for existence of condensed states of matter
• Responsible for bulk properties of matter
o Boiling points and melting points
o Reflect strength of intermolecular forces
Types of Intermolecular Attractions

Intermolecular attractions arise from attractions between opposite electrical
charges; dipole-dipole attractions.
They are called van der Waals forces, after J. D van der Waals.
There are two type of dipoles; permanent and instantaneous dipoles.
Permanent dipoles for polar molecules, and instantaneous dipoles for nonpolar
molecules.
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Three Important Types of Intermolecular Forces

1. Dipole-dipole forces in polar molecules
o Hydrogen bonds
2. London dispersion forces in nonpolar molecules
3. Ion-dipole forces
o Ion-induced dipole forces
11
Dipole-Dipole Attractions (1 of 3)
• Occur only between polar
molecules
o Possess dipole moments
• Molecules need to be close
together
• Polar molecules tend to align
their partial charges
o Positive to negative
• As dipole moment increases,
intermolecular force increases
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• Tumbling molecules
o Mixture of attractive and repulsive dipole-dipole forces
o Attractions (- -) are maintained longer than repulsions(- -)
o Get net attraction
o ~1–4% of covalent bond
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• Interactions between net dipoles in polar molecules
• About 1–4% as strong as a covalent bond
oDecrease as molecular distance increases
• Dipole-dipole forces increase with increasing polarity
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Hydrogen Bonds
• Special type of dipole-dipole Interaction
o Very strong dipole-dipole attraction
o ~10% of a covalent bond
• Occurs between H and highly electronegative atom (O, N, or F)
o H — F, H — O, and H — N bonds very polar
• Electrons are drawn away from H, so high partial charges
• H only has one electron, so δ + presents almost bare proton H
• δ – almost full –1 charge

X
• Element’s small size, means high charge density
• Positive end of one can get very close to negative end of another
15
Examples of Hydrogen Bonding
534 Chapter 12 | Intermolecular Attractions and the Properties of Liquids and Solids
Thymine Adenine Cytosine Guanine
O H NH N HN H O N
N H N NH N H N NH
HN N HN N
O O H NH
16
(a)
C G
G C
8
P–
C
Backbones 5'
P– 3'
C
G C P–
C
G C P–
C
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Hydrogen Bonding in Water
• Responsible for expansion of water as it freezes

• Hydrogen bonding produces strong attractions in liquid
• Hydrogen bonding (dotted lines) between water molecules in ice form
tetrahedral configuration
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London Forces (1 of 2)
• When atoms near one another, their
valence electrons interact
• Repulsion causes electron clouds in
each to distort and polarize
• Instantaneous dipoles result from this
distortion
o Effect enhanced with increased
volume of electron cloud size
o Effect diminished by increased
distance between particles and
compact arrangement of atoms
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London Forces (2 of 2)
• Instantaneous dipole-induced dipole attractions
o London Forces
o Dispersion forces
• Operate between all molecules
o Neutral or net charged
o Nonpolar or polar
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London Dispersion Forces

• Ease with which dipole moments can be induced and
thus London Forces depend on
1. Polarizability of electron cloud
2. Points of attraction
o Number atoms
o Molecular shape (compact or elongated)
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Your Turn! 1 (1 of 2)
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
21
Which of the following is the weakest of all
intermolecular forces?
A. Hydrogen-bonds
B. Answer: London dispersion forces
D. Ion-dipole attractions
E. Ion-Ion attractions
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Polarizability
• Ease with which the
electron cloud can be
distorted
• Larger molecules often
more polarizable
o Larger number of less
tightly held electrons
o Magnitude of resulting
partial charge is larger
o Larger electron cloud
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Table 11.1 Boiling Points of Halogens and

Noble Gases
Larger molecules have stronger London forces and thus higher
boiling points.
Table 11.1 Boiling Points of the Halogens and Noble Gases
Group 7 A Boiling Point (°C) Group 8A Boiling Point (°C)

F2 −188.1 He −268.9
Cl2 −34.6 Ne −245.9
Br2 58.8 Ar −185.7
I2 184.4 Kr −152.3
Xe −107.1
Rn −61.8
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12.2 | Types of Intermolecular Forces 531
Table 12.2 Boiling Points of Some Hydrocarbonsa

Molecular Formula Boiling Point at 1 atm (°C)
Number ofCHAtoms in Molecule
161.5 4
+ – + –
C2H6 88.6
C3H8 42.1
• London forces Cdepend
4H10
on number atoms in0.5molecule
+ – + –
C5H12 36.1
• Boiling point ofC6Hhydrocarbons
14
demonstrates
68.7 this trend
Figure 12.4 | Effect of molecu-
C10H22 174.1 lar size on the strengths of
Formula BP at 1 atm, °C Formula BP at 1 atm, °C London dispersion forces. A large
electron cloud is more easily
C22H46 327
CH4 –161.5 C5H12 36.1 deformed than a small one, so in a
a
The molecules of each hydrocarbon in this table have carbon large molecule the charges on
C2H6 chains–88.6
of the type C C C C etc.; C6that
H14is, one carbon follows 68.7 opposite ends of an instantaneous
another and there are no branches in the carbon–carbon chain.
dipole are larger than in a small
C3H8 –42.1 : : molecule. Large molecules,
C4H10 –0.5 C22H46 327 therefore, experience stronger
London forces than
small molecules.
A second factor that affects the strengths of London forces is the number of atoms in a
molecule. For molecules containing the same elements, London forces increase with the
number of atoms, as illustrated
Copyright by theJohn
©2014 hydrocarbons listed in Table 12.2. As the number
Wiley & Sons, Inc. 25
of atoms increases, there are more places along their lengths where instantaneous dipoles
25 can develop and lead to London attractions (Figure 12.5). Even if the strength of attrac-
tion at each location is about the same, the total attraction experienced between the longer
molecules is greater.1
The third factor that affects the strengths of London forces is molecular shape. Even
with molecules that have the same number of the same kinds of atoms, those that
have compact shapes experience weaker London forces than long chain-like molecules
(Figure 12.6). Presumably, because of the compact shape of the (CH3)4C molecule, the
How Intermolecular Forces Determine
area that can interact with a neighboring molecule is smaller than that of the chain-like
CH3(CH2)3CH3 molecule.
Physical Properties
* * * *
* * *
*
* *
* *
* * Figure 12.5 | The number of atoms in a

* * *
* * *
* * molecule affects London forces. The C6H14
C H molecule, left, shown as both a ball-and-stick
model and a space-filling model, has more sites
(indicated by asterisks, *) along its chain where it
can be attracted to other molecules nearby than
does the shorter C3H8 molecule, right. As a result,
the boiling point of C6H14 (hexane, 68.7 °C) is
higher than that of C3H8 (propane, 42.1 °C).
Hexane, C6H14 Propane, C3H8

°
° the total strengths of London forces can be compared
1
BP 68.7 C
The effect of large numbers of atoms on BP –42.1 C to the bond
between loop and hook layers of Velcro. Each loop-to-hook attachment is not very strong, but when large
numbers of them are involved, the overall bond between Velcro layers is quite strong.
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Molecular Shape
• Increased surface area available for contact = increased
London forces
• London dispersion forces between spherical molecules
are lower than chain-like molecules
o More compact molecules
• Hydrogen atoms not as free to interact with hydrogen atoms on
other molecules
o Less compact molecules
• Hydrogen atoms have more chance to interact with
hydrogen atoms on other molecules
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Physical Origin of Shape Effect
• Small area for interaction • Larger area for interaction

More compact – lower BP Less compact – higher BP
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List all intermolecular forces for CH3CH2OH.
A. Hydrogen-bonds
B. Hydrogen-bonds, dipole-dipole attractions, London
dispersion forces
D. London dispersion forces
E. London dispersion forces, dipole-dipole attractions
29
List all intermolecular forces for CH3CH2OH.
A. Hydrogen-bonds
B. Answer: Hydrogen-bonds, dipole-dipole attractions,
London dispersion forces
D. London dispersion forces
E. London dispersion forces, dipole-dipole attractions
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In the liquid state, which species has the strongest
intermolecular forces, CH4, Cl2, O2 or HF?
A. CH4
B. Cl2
C. O2
D. HF
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In the liquid state, which species has the strongest
intermolecular forces, CH4, Cl2, O2 or HF?
A. CH4
B. Cl2
C. O2
D. Answer: HF
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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
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What is the strongest type of intermolecular force in
CHCl3?
A. ion-dipole
B. Answer: dipole-dipole
C. dispersion
D. Hydrogen bonding
34
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Which of the following has dispersion forces as its
strongest intermolecular force?
A. CH4
B. CO2
C. O2
D. All of the above
35
Which of the following has dispersion forces as its
strongest intermolecular force?
A. CH4
B. CO2
C. O2
D. Answer: All of the above
36
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Ion-Dipole Attractions
• Attractions between ion and charged end of polar molecules
o Attractions can be quite strong as ions have full charges 12.2 | Types ofForces
12.2 | Types of Intermolecular 535
Intermolecular Forces 53
Figure 12.10 | Ion–dipole

Figure 12.10 | Ion–dipole
attractions between water
attractions between water
molecules and ions. (a) The
molecules and ions. (a) The
negative ends of water dipoles
negative ends of water dipoles
surround a cation and are attracted
surround a cation
to the ion. (b) The positive ends of and are attr
to the ion.
water molecules surround an (b) The positive en
anion, which gives water molecules surround an
a net attraction.
anion, which gives a net attrac
(a) (b)
(a) Negative
(a) ends of water dipoles surround (b)cation
Ion–Dipole and Ion–Induced Dipole Forces of Attraction
(b) Positive ends of water dipoles surround anion
Ion–Dipole
In addition andthat
to the attractions Ion–Induced
exist between neutral Dipole
molecules, Forces
which weof Attraction
discussed
above, there are also forces that arise when ions interact with molecules. For example, ions
In to
are able addition to the
attract the charged ends Copyright
attractions that©2014
of polar John
exist Wiley & Sons,
between
molecules to give Inc.
neutral molecules,
ion–dipole attractionswhich
. This we discussed 37
occursabove, there
in water, are also when
for example, forcesionic
thatcompounds
arise whendissolve
ions interact with molecules.
to give hydrated For example, ions
ions. Cations
37 become aresurrounded
able to attract
by waterthemolecules
charged thatendsareof oriented
polar molecules to give ends
with the negative of theirattractions. This Al
ion–dipole
3
dipoles pointing
occurs toward
in water, forthe cation. when
example, Similarly, anions
ionic attract the
compounds positive
dissolve to ends of water ions. Cations
give hydrated
dipoles. This is surrounded
illustrated in Figure 12.10. These same interactions can persist Al3
become by water molecules that are oriented with into
the the solid ends of their
negative
state as well. For
dipoles example,
pointing aluminum
toward chloride Similarly,
the cation. crystallizes anions
from water as athe
attract hydrate with ends of water
positive
formula AlCl3·6H2O. In it the Al3 ion is surrounded by water molecules at the vertices of
dipoles. This is illustrated in Figure 12.10. These same interactions
an octahedron, as illustrated in Figure 12.11. They are held there by ion–dipole attractions.
can persist into the solid
state as well. For example, aluminum
Ions are also capable of distorting nearby electron chloride
clouds, thereby creating dipoles in neigh- hydrate with
crystallizes from water as a
formula AlCl ·6H
boring particles (like molecules
3 2O. In it the Al 3
ion is
of a solvent, or even othersurrounded
ions). This by water
leads molecules
to ion–induced at the Figure
dipole vertices12.11
of | Ion–dipole
Example: Ion-Dipole Attractions:
an octahedron,
attractions, which can beasquite
Ions are alsocharges
like the instantaneous
illustrated in Figure
strong because
capableresponsible
of distorting
the12.11.
charge on They
nearby electron
for ordinary
the are
ion held
doesn’tthere
clouds, thereby
London dispersion
byonion–dipole
flicker and off attractions.
forces. creating dipoles
attractions hold water molecules
inin neigh- Water molecules are
a hydrate.
AlCl ·6H O
boring particles (like molecules of a solvent, or even other ions). This leads to ion–induced
attractions,3 which can 2 be quite strong because the charge on the ion doesn’t flicker octahedron
arranged
dipole Figure
at the vertices of an12.11 | Ion–dipole
on and offaroundattractions
an aluminumhold water molec
Estimating
• like the Effects
the instantaneous
Attractions between chargesof
ion Intermolecular
responsible
and for ordinary London dispersion forces. ion in AlCl3·6H2O.in a hydrate. Water molecule
Forces
In thispolar
section molecules
we have described a number of different types of intermolecular attractive arranged at the vertices of an
forces and the kinds of substances in which they occur (see the summary in Table 12.3). octahedron around an alumin
3+ ion in AlCl3·6H2O.
With• Estimating
Positive
this charge
knowledge, youthe of Effects
shouldAlnow be oftoIntermolecular
ionable make some estimate of the Forces
nature and
relative strengths of intermolecular attractions if you know the molecular structure of a Types of intermolecular forces
Inattracts partial
this section we havenegative charges
described a number of different types of intermolecular attractive
forces and
– on O
Tableδ12.3 the kinds
of water
Summary of
molecules inAttractions
substances
of Intermolecular which they occur (see the summary in Table 12.3).
With this
Intermolecular
knowledge, you should
Types of Substances that
now be able to make some estimate of the nature and
relative strengths of intermolecular
• Ion-dipole attractions hold water
Attraction Exhibit Attraction attractions if youStrength
knowRelative
the molecular
to a Covalentstructure
Bond of a Types of intermolecular force
molecules to
London metalmolecules,
All atoms, ion in and hydrate
ions experi- Depends on sizes and shapes of mol-
Table
dispersion Summary
12.3 ence
forces these kindsof of
Intermolecular Attractions
attractions. They are ecules. For large molecules, the cumula-
o Water molecules are found at
Intermolecular present in all substances.
Types of Substances that tive effect of many weak attractions can
vertices of octahedron
Attraction
around
Exhibit Attraction lead to a largeStrength
net attraction.
Relative to a Covalent Bond
aluminum ion
Dipole–dipole
London Occur between molecules
All atoms, that have
molecules, andper- 1–5%
ions experi- Depends on sizes and shapes of mol-
attractions manent dipoles
dispersion forces (i.e.,kinds
ence these polar molecules).
of attractions. They are ecules. For large molecules, the cumula-
Hydrogen present
Occurs when in all substances.
molecules contain N H, 5–10% tive effect of many weak attractions can
bonding F H, and O H bonds. lead to a large net attraction.
38
Ion–dipole
Dipole–dipoleOccur when ions interact with polar
Occur About 10%; depends on ion charge and
between molecules that have per- 1–5%
attractions molecules. polarity of molecule.
attractions manent dipoles (i.e., polar molecules).
Ion–induced Occur when an ion creates a dipole in Variable, depending on the charge on the
dipoleHydrogen
attractions Occurs
a neighboring whenwhich
particle, molecules
may becontain
a N and
ion 5–10% of its neighbor.
H,the polarizability
bonding moleculeFor another
H, andion.
O H bonds.
19
Ion–dipole Occur when ions interact with polar About 10%; depends on ion charge and
dipole attractions a neighboring particle, which may be a ion and the polarizability of its neighbor.
molecule or another ion.
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Ion-Induced Dipole Attractions

(attractions between ion and nonpolar molecules)
• Attractions between ion and dipole it induces on
neighboring molecules
o Depends on
• Ion charge and
• Polarizability of its neighbor
o Attractions can be quite strong as ion charge is constant,
unlike instantaneous dipoles of ordinary London forces
o Example, I – and Benzene
39
Summary of Intermolecular Attractions
Dipole-dipole
• Occur between neutral molecules with permanent dipoles
• About 1–4% of covalent bond
• Mid range in terms of intermolecular forces
Hydrogen bonding N — H, H — F and O — H bonds
o Special type of dipole-dipole interaction
o Occur when molecules contain
o About 10% of a covalent bond
40
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Summary of Intermolecular Attractions

London dispersion
• Present in all substances
• Weakest intermolecular force
• Weak, but can add up to large net attractions
Ion-dipole
• Occur when ions interact with polar molecules
• Strongest intermolecular attraction
Ion-induced dipole
• Occur when ion induces dipole on neighboring particle
• Depend on ion charge and polarizability of its neighbor
41
Using Intermolecular Forces

• Often can predict physical properties (like BP, MP and many
others) by comparing strengths of intermolecular attractions
o Ion-Dipole
o Hydrogen Bonding
o Dipole-Dipole
o London Forces
• Larger, longer, and therefore heavier molecules often have

stronger intermolecular forces
• Smaller, more compact, lighter molecules have generally
weaker intermolecular forces
42
21
dipoles pointing toward the cation. Similarly, anions attract the positive ends of water
dipoles. This is illustrated in Figure 12.10. These same interactions can persist into the solid
state as well. For example, aluminum chloride crystallizes from water as a hydrate with
formula AlCl3·6H2O. In it the Al3 ion is surrounded by water molecules at the vertices of
an octahedron, as illustrated in Figure 12.11. They are held there by ion–dipole attractions.
Ions are also capable of distorting nearby electron clouds, thereby creating dipoles in neigh-
boring particles (like molecules of a solvent, or even other ions). This leads to ion–induced dipole Figure 12.11 | Ion–dipole
attractions, which can be quite strong because the charge on the ion doesn’t flicker on and off attractions hold water molecules12/17/20
like the instantaneous charges responsible for ordinary London dispersion forces. in a hydrate. Water molecules are
arranged at the vertices of an
octahedron around an aluminum
Estimating the Effects of Intermolecular Forces ion in AlCl3·6H2O.
In this section we have described a number of different types of intermolecular attractive

forces and the kinds of substances in which they occur (see the summary in Table 12.3).
Relative strength of intermolecular attractions

With this knowledge, you should now be able to make some estimate of the nature and
relative strengths of intermolecular attractions if you know the molecular structure of a Types of intermolecular forces
Table 12.3 Summary of Intermolecular Attractions

Intermolecular Types of Substances that
Attraction Exhibit Attraction Strength Relative to a Covalent Bond
London All atoms, molecules, and ions experi- Depends on sizes and shapes of mol-
dispersion forces ence these kinds of attractions. They are ecules. For large molecules, the cumula-
present in all substances. tive effect of many weak attractions can
lead to a large net attraction.
Dipole–dipole Occur between molecules that have per- 1–5%
attractions manent dipoles (i.e., polar molecules).
Hydrogen Occurs when molecules contain N H, 5–10%
bonding F H, and O H bonds.
Ion–dipole Occur when ions interact with polar About 10%; depends on ion charge and
dipole attractions a neighboring particle, which may be a ion and the polarizability of its neighbor.
molecule or another ion.
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Physical Properties that Depend on How

Tightly Molecules Pack
• Compressibility
o Measure of ability of substance to be forced into smaller volume
o Determined by strength of intermolecular forces
o Gases highly compressible
• Molecules far apart
• Weak intermolecular forces
o Solids and liquids nearly incompressible
• Molecules very close together
• Stronger intermolecular forces
44
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Diffusion (1 of 2)
• Movement that spreads
one gas though another
gas to occupy space
uniformly
• Spontaneous intermingling
of molecules of one gas
with molecules of another
gas
o Occurs more rapidly in gases than in liquids
o Hardly at all in solids
45
Diffusion (2 of 2)
• In Gases
o Molecules travel long distances between collisions
o Diffusion rapid
• In Liquids
o Molecules closer
o Encounter more collisions
o Takes a long time to move
from place to place
• In Solids
o Diffusion close to zero at
room temperature
o Will increase at high temperature
46
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Intermolecular Forces Determine Strength

of Many Physical Properties
• Retention of volume and shape
o Solids retain both volume and shape
• Strongest intermolecular attractions
• Molecules closest
o Liquids retain volume, but not shape
• Attractions intermediate
o Gases, expand to fill their containers
• Weakest intermolecular attractions
• Molecules farthest apart
47
Intermolecular Forces and Temperature

• Decrease with increasing temperature
o Increasing kinetic energy overcomes attractive forces
o If allowed to expand, increasing temperature increases
distance between gas particles and decreases attractive
forces
48
24
invisible “skin
If you push on
“skin” appears
as illustrated i
Surface ten
Liquids with
energy betwee
12/17/20
surprisingly, w
at the same tem
of dipole–dipo
of gasoline, w
ence only Lon
Wetting of a
A property we
is the spreadin
Surface Tension (1 of 3) such as the w
Figure 12.16a
forms tiny dro
Why does H2O bead up on a freshly For wetting
must be of abo
waxed car instead of forming a layer? equality exists
lots of oxygen
• Inside body of liquid of the energy
by the format
o Intermolecular forces are the When the
same in all directions drop become
(Figure 12.16
• Molecules at surface Figure 12.15 | Surface tension which are wea
in a liquid. Surface tension allows water are mu
o Potential energy increases when a glass to be filled with water above surface. The w
removing neighbors the rim. (Michael Watson) within liquid
o Molecules move together to
reduce surface area and
potential energy
jespe_c12_527-584hr.indd 538
49
Surface Tension (2 of 3)
• Causes a liquid to take the shape (a sphere) that
minimizes its surface area
o Molecules at surface have higher potential energy than
those in bulk of liquid and move to reduce the potential
energy
• Wax = nonpolar
• H2O = polar
• Water beads in order to reduce potential
energy by reducing surface area
the surface tension of a liquid is proportional

to the energy needed to expand its surface area.
50
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Surface Tension (3 of 3)
• Liquids containing molecules with strong
intermolecular forces have high surface tension
o Allows us to fill glass above rim
• Gives surface rounded appearance
• Surface acts as “skin” that lets water pile up
• Surface resists expansion and pushes back
• Surface tension increases as intermolecular forces increase
• Surface tension decreases as temperature increases
51
Wetting (1 of 2)
• Ability of liquid to spread
across surface to form thin film
• Greater similarity in
attractive forces between
liquid and surface, yields
greater wetting effect
• Occurs only if intermolecular

attractive force between
surface and liquid about as
strong as within liquid itself
52
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Wetting (2 of 2)
Example: H2O wets clean glass surface as it forms H–
bonds to SiO2 surface
• Does not wet greasy glass, because grease is nonpolar
and water is very polar
o Only London forces
o Forms beads instead
Surfactants
• Added to detergents to lower surface tension of H2O
• Now water can spread out on greasy glass
53
Surfactants (Detergents)
• Substances that have both polar and non-polar characteristics
• Long chain hydrocarbons with polar tail
O
O- Na+
O
S
O O- Na+
O
• Nonpolar end dissolves in nonpolar grease
• Polar end dissolves in polar H2O
• Thus increasing solubility of grease in water
54
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Viscosity (1 of 2)
• Resistance to flow
• Measure of fluid’s resistance to flow or changing form
• Related to intermolecular attractive forces
• Also called internal friction
o Depends on intermolecular attractions
55
Viscosity (2 of 2)
• Viscosity decreases when temperature increases
• Most people associate liquids with viscosity
Syrup more viscous than water
o
• Gases have viscosity
o Respond almost instantly to form-changing forces
• Solids, such as rocks and glass have viscosity

o Normally respond very slowly to forces acting to change
their shape
56
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Effect of Intermolecular Forces on Viscosity
Acetone Ethylene glycol

• Polar molecule • Polar molecule
o Dipole-dipole and o Hydrogen-bonding
o London forces o Dipole-dipole and
o London forces
Which is more viscous?
57
For each pair given, which is more viscous?
CH3CH2CH2CH2OH or CH3CH2CH2CHO
C6H14 or C12H26
NH3(l ) or PH3(l )
A. CH3CH2CH2CH2OH C6H14 NH3(l )

B. CH3CH2CH2CH2OH C12H26 NH3(l )
C. CH3CH2CH2CHO C6H14 PH3(l )
D. CH3CH2CH2CHO C12H26 NH3(l )
58
29
12/17/20
For each pair given, which is more viscous?
CH3CH2CH2CH2OH or CH3CH2CH2CHO
C6H14 or C12H26
NH3(l ) or PH3(l )
A. CH3CH2CH2CH2OH C6H14 NH3(l )

B. Answer: CH3CH2CH2CH2OH C12H26 NH3(l )
C. CH3CH2CH2CHO C6H14 PH3(l )
D. CH3CH2CH2CHO C12H26 NH3(l )
59
Solubility
• “Like dissolves like”
o To dissolve polar substance, use polar solvent
o To dissolve nonpolar substance, use nonpolar solvent
• Compare relative polarity
o Similar polarity means greater ability to dissolve in each other
o Differing polarity means that they don’t dissolve, they are
insoluble
• Surfactants
o Both polar and non-polar characteristics
o Used to increase solubility
60
30
12/17/20
Which of the following are not expected to be soluble in
water?
A. HF
B. CH4
C. CH3OH
D. All are soluble
61
Which of the following are not expected to be soluble in
water?
A. HF
B. Answer: CH4
C. CH3OH
D. All are soluble
62
31
12/17/20
What type of intermolecular attraction causes KI to
dissolve in water?
A. Hydrogen bonding
B. dipole-dipole
C. dispersion
D. ion-dipole
63
What type of intermolecular attraction causes KI to
dissolve in water?
A. Hydrogen bonding
B. dipole-dipole
C. dispersion
D. Answer: ion-dipole
64
32
Molecular size
factor in determin
oil (almost entirel
forces in the mater
oils, like the olive
12/17/20
are also large but
water.
As the temperature drops, Viscosity also
molecules move more slowly and increases. When w
intermolecular forces become more
its viscosity increa
effective at restraining flow.
operators of vehic
weather.
Evaporation
Phase Changes (1 of 4) One of the most i
undergo a change
• Changes of physical state is called evaporatio
without going th
o Deal with motion of molecules commonly called
limes, changing di
• As temperature changes moth flakes, is ano
o Matter will undergo phase changes To understand
molecules. In a so
• Liquid ® Gas liding with their n
of kinetic energie
o Evaporation, vaporization on page 259 appl
perature a small f
o As heat is added, H2O, forms steam or water vapor Naphthalene sublimes when very high velociti
o Requires energy or source of heat heated and the vapor condenses moving outward f
directly to a solid when it vapor state. We s
encounters a cool surface. stance is a solid).
Cooling by Evapo
Copyright ©2014 John Wiley & Sons, Inc. 65 One of the things
effect. You’ve expe
65 The evaporation o
evaporation of per
We can see wh
which illustrates t
Phase Changes (2 of 4)
• Solid ® Gas
o Sublimation
o Ice cubes in freezer, leave in long enough disappear
o Endothermic
• Gas ® Liquid
o Condensation
o Dew is H2O vapor condensing onto cooler ground
o Exothermic
o Often limits lower night time temperature
66
33
12/17/20
Rate of Evaporation
• Depends on
o Temperature
o Surface area
o Strength of intermolecular
attractions
• Molecules that escape from
liquid have larger than
minimum escape KE
• When they leave
o Average KE of remaining
molecules is less and so T lower
67
Effect of Temperature on Evaporation Rate

• For given liquid
o Rate of evaporation per
unit surface area
increases as T increases
• Why?
o At higher T, total fraction
of molecules with KE
large enough to escape is
larger
o Result: rate of evaporation is larger
68
34
12/17/20
Kinetic Energy Distribution in Two Different Liquids
• Smaller intermolecular forces • Larger intermolecular forces

• Lower KE required to escape liquid • Higher KE required to escape liquid
• A evaporates faster • B evaporates slower
69
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
70
35
12/17/20
Before System Reaches Equilibrium

• Liquid is placed in empty,
closed, container
o Begins to evaporate
• Once in gas phase
o Molecules can condense by
o Striking surface of liquid
and giving up some kinetic
energy
71
System At Equilibrium
• Rate of evaporation =
rate of condensation
• Occurs in closed
systems where
molecules cannot escape
72
36
12/17/20
Similar Equilibria Reached in Melting

• Melting Point (mp)
o Solid begins to change
into liquid as heat added
• Dynamic equilibria exists
between solid and liquid
states
o Melting (red arrows) and
freezing (black arrows)
o As long as no heat added
or removed from
equilibrium mixture
73
Equilibria Reached in Sublimation
At equilibrium
• Molecules sublime
from solid at same
rate as molecules
condense from vapor
74
37
12/17/20
75
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
76
38
12/17/20
Heating Curve
• Heat added at constant rate
• Horizontal lines
o Phase changes
o Melting point
o Boiling point
• Diagonal lines
o Heating of solid, liquid or gas
77
Cooling Curve
• Heat removed at constant rate
• Horizontal lines
o Phase changes
o Melting point
o Boiling point
• Diagonal lines
o Cooling of solid,
liquid or gas
• Supercooling
o Temperature of liquid dips below its freezing point
78
39
12/17/20
Enthalpy Of Phase Changes

Endothermic Phase Changes
1. Must add heat
2. Energy entering system (+)
Sublimation: DHsub > 0
Vaporization: DHvap > 0
Melting or Fusion: DHfus > 0
Exothermic Phase Changes
1. Must give off heat
2. Energy leaving system (–)
Deposition: DH < 0 = –DHsub
Condensation: DH < 0 = –DHvap
Freezing: DH < 0 = –DHfus
79
• As T changes, matter undergoes phase changes
• Phase Change
o Transformation from one phase to another
• Liquid-Vapor Equilibrium
o Molecules in liquid
• Not in rigid lattice
• In constant motion
• Denser than gas, so more collisions
• Some have enough kinetic energy to escape, some don’t
80
40
12/17/20
Liquid-Vapor Equilibrium
• At any given T,
o Average kinetic energy of
molecules is constant
o But particles have a
distribution of kinetic
energies
o Certain number of
molecules have enough
KE to escape surface
• As T increases, average KE increases
and number molecules with enough KE to escape increases
81
Vapor Pressure
• Pressure molecules exert when they evaporate or escape into gas (vapor) phase
• Pressure of gas when liquid or solid is at equilibrium with its gas phase
• Increasing temperature increases vapor pressure because

vaporization is endothermic
o liquid + heat of vaporization ↔ gas
Equilibrium Vapor Pressure

• VP once dynamic equilibrium reached
• Usually referred to as simply vapor pressure
82
41
12/17/20
Vapor Pressure Diagram

• Variation of vapor pressure
with T
• Ether
o Volatile
o High vapor pressure near RT
• Propylene glycol
o Non-volatile
o Low vapor pressure near RT
83
Effect of Volume on VP
A. Initial V
• Liquid – vapor equilibrium exists
B. Increase V
• Pressure decreases
• Rate of condensation decreases
C. More liquid evaporates
• New equilibrium
established
84
42
12/17/20
Do Solids Have Vapor Pressures?

• Yes
• At given temperature
o Some solid particles have enough KE to escape into vapor
phase
• When vapor particles collide with surface
o They can be captured
• Equilibrium vapor pressure of solid
o Pressure of vapor in equilibrium with solid
85
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
86
43
12/17/20
Effects of Hydrogen Bonding

• Boiling points of
hydrogen compounds of
elements of Groups 4A,
5A, 6A, and 7A.
• Boiling points of
molecules with hydrogen
bonding are much higher
than expected
87
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
88
44
12/17/20
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. Answer: All of these
E. None of these
89
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
90
45
12/17/20
boiling point?
A. Answer: LiCl
B. Cl2
C. HCl
D. CO2
91
boiling point?
A. F2
B. Cl2
C. I2
D. Br2
92
46
12/17/20
boiling point?
A. F2
B. Cl2
C. Answer: I2
D. Br2
93
Energies of Phase Changes

• Expressed per mole
• Molar heat of fusion (DHfus)
o Heat absorbed by one mole of solid when it melts to give liquid at
constant T and P
• Molar heat of vaporization (DHvap )
o Heat absorbed when one mole of liquid is changed to one mole of
vapor at constant T and P
• Molar heat of sublimation (DHsub )
o 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
94
47
8.16 London of water and ammonia are very large, which is just
15.1 London what we would expect for hydrogen-bonded sub-
stances. By comparison, CH4, a nonpolar substance
16.9 London
composed of atoms of a size similar to those of H2O 12
30.1 London and NH3, has a very small heat of vaporization. Note
also that polar substances such as HCl and SO2 have 12/17/20
the attractions, fairly large heats of vaporization compared The Clausius–Clapeyron
with nonpolar substances. equationFor provides
example, a convenient
com- graphical metho
tential energy will mining heats of vaporization
pare HCl with Cl2. Even though Cl2 contains two relatively large atoms and therefore from experimentally measured vapor pressure–t
he molecules become data. Toforces
would be expected to have larger London see this,
than let’s
HCl,rewrite
HClthehasequation
the largeras follows:
Hvaporization.
the larger will be the
This must be due to dipole–dipole attractions between polar HCl molecules—attractions H vap 1
that are absent in nonpolar Cl2. ln P C
R T
Heat of Vaporization
Heats of vaporization also 12
552 Chapter reflect
| the factors
Intermolecular that control
Attractions the strengths
and the Properties of and
of Liquids London
Solids
forces. For example, the data in Recall
Table 12.4 show the effect of chain length on the inter-
from algebra that a straight line is represented by the general 8
molecular attractions between
Table 12.4 Somehydrocarbons;
equation
Typical Heats as
of the chain
Vaporization length increases
Energyfrom one
Changes 7
carbon in CH4 to six carbons in HC6H14, the heat of vaporization also increases, and showing
Intermolecular Attractio
that the London Substance
vaporization
forces also increase.
(kJ/mol) Similarly, Typethe
yvaporization
heats ofForce
of Attractive
mx b of the halogens 6
When a liquid evaporates or a solid sublim
in Table 12.4 show H2Othat the strengths 43.9 ofx London
where y areforces
and Hydrogen increase
variables,
bonding mandisas theslope,
the
London electron
andclouds
ticles is theof
b from
go interceptin of
a situation
In P 5
which the attra
the particles become
NH3larger. the21.7 line with Hydrogen
the y axis. In this
bonding andcase, we canaremake
London the substitutions
very strong 4
to one in which the attractiv
HCl 15.6 Dipole–dipole and London so small they can almost be ignored. Th 3
1 H vapof H
values
SO2 24.3 y lnDipole–dipole
P x and London m b Cand Hsublimation give
vaporization
2
T R energy needed to separate molecules
the
12.8 | Determining Heats of Vaporization
F2
Cl2
5.9
10.0
Therefore,
London
weLondon
have
other. We can examine such values to obt
comparisons of the strengths of inte
2.
Br2 15.0 London attractions.

The way the vaporI2 pressure varies 22.0
with temperature,
London which was described
H vap 1in Section
In Table12.5
12.4, notice that the heats of v
and Figure 12.23,CHdepends on the heat
8.16 of ln Pof a substance. Theof relationship
vaporization
London C and ammonia are very large,The
water w
4 R T valu
between vapor pressure what we would expect for hydrogen-bo
C 2 6 and temperature,
H 15.1 however, is not a simple proportionality. Instead,
London
stances. By comparison, CH4, a nonpola
it involves naturalClogarithms,
3H8 which are logarithms
16.9 Londonto the base e, as compared to the more
familiar base-10 logarithms.
C6H14 (If you30.1
are unfamiliar withy natural logarithms,
London m x composed
bNHrefer
please
and
of atoms of a size similar to tho
, hasto
Figure
a very small heat of vaporiz
3
Appendix A.) also that polar substances such as equatio HCl an
Thus, a graphfairly
The stronger the attractions, of lnlarge
P versus 1/T should give
heats of vaporization compared a straight line that
with nonpolar has acetone
substances. For exa
95 aVaporization
slope
the more the potential energy
12.8 | Determining Heats of
will equalpare to553 HvapCl
HCl with /R.2. Even
Suchthough
straight-line
Cl2 contains relationships
two relativelyarelarge atoms an
increase when the molecules become
The Clausius–Clapeyron Equation
separated, and the largerillustrated
will be the
would be12.28,
in Figure
This must
expectedintowhich
be due to
have larger
experi
dipole–dipole
London
mental forces
attractions
thanare
data
between
HCl, HCl has
plotted
polar HCl
forthewater,
larger a
molecules—
value of H. ethanol. Fromthat thearegraphs
absent
in Figure Cl
in nonpolar
12.28, the calculated values of Hvap are
Rudolf Clausius (1822–1888), a German physicist, and 1Benoit Clapeyron 2. (1799–1864),
enient graphical method for deter- for water, 43.9 kJ Heats ; for acetone,
molof vaporization also32.0
reflectkJthemol 1
; and
factors thatfor ethanol,
control 40.5 kJ
the strengths
a French engineer, used the principles of thermodynamics
Using Equation 12.2, (a subject
a “two-point” that’s
the data in form
discussed
of the inthe
Clausius–Clapeyron equa
asured vapor pressure–temperature forces. For example, Table 12.4 show effect of chain length o
Chapter 19) to derive the following equationthat that relates the
to vapor pressure, heat of vapor
vapor-
Determining Heat of Vaporization derived can be used calculate if the
Hhydrocarbons; pressure is known at tw
molecular attractions between vap as the chain length increases
ization ( Hvap), and temperature: temperatures.carbon in CH4 to six
This equation is carbons in C6H14, the heat of vaporization also increas
that the London forces also increase. Similarly, the heats of vaporization of th
C Clausius-Clapeyron Equation HinvapTable 12.4 show thatPthe strengths H vapof London forces increase as the electro
ln P the C become ln
particles
1
larger.
1(12.2) 1
RT P2 R T2 T1
y the general The
8 quantity ln P is the natural logarithm of the vapor pressure, R is the gas constant
expressed in energy units (R 8.314
7
If we know
C is a constant. Scientists call thislate
J molthe
thethe
1 value
12.8
K 1), Tof|isthe
theheat
vapor pressure equation
Clausius–Clapeyron
of vaporization,
absolute Equation
Heats
temperature, and of 12.3 can also be us
at some. particular temperature (say, P2Vaporizat
Determining at a temperatu
6 already knowThe theway
vapor pressure P
the vapor pressureat a temperature T .
1 varies with temperature,
1 which was described in S
Acetone
and Figure 12.23, depends on the heat of vaporization of a substance. The r
e intercept of In P 5 between vapor pressure and temperature, however, is not a simple proportional
ubstitutions 4 it involves natural logarithms, which are logarithms to the base e, as compared
Ethanol
familiar base-10 logarithms. (If you are unfamiliar with natural logarithms, pl
3 Appendix
Water A.) Calculating
b C
552
2
2.8 2.9 3.0 3.1 3.2 3.3 3.4 3.5 3.6
from Temperatu
11/24/10 5:01 PM
1/T ( 103 K –1
)
The Clausius–Clapeyron Equation
Methanol, CH3OH, experiences hydrogen bonding, dipole–dipole intera
Rudolf Clausius (1822–1888), a German physicist, and Benoit Clapeyron (17
London forces. At 64.6 °C, it has a vapor pressure of 1.00 atm, and at 12.0
a French engineer, used the principles of thermodynamics (a subject that’s d
vapor pressureChapter
of 0.0992
19) toatm.
deriveWhat is the equation
the following heat of vaporization for methanol?
that relates the vapor pressure, he
The numbers along the horizontal axis are equal toization
1/T ( H ), and temperature:
96 Analysis:
values multiplied by 1000 to make the We
axis easier to are given
label.
vap
two temperatures
and two vapor pressures and we a
find the heat of vaporization. We will need to useHthe vap Clausius–Clapeyron
ln P C
solve this problem. RT
Figure 12.28 | Plotting the Clausius–Clapeyron
equation. A graph showing plots of lnAssembling the
for Tools:
The quantity ln The
P is the
mainnatural
toollogarithm
that we ofwill
the use
vapor pressure,
will be theR applica
is the g
P versus 1/T
expressed in energy units (R 8.314 J mol 1 K 1), T is the absolute 48 tempe
Clausius–Clapeyron equation, Equation 12.3, to find the heat of vaporization
line that has acetone, ethanol, and water. C is a constant. Scientists call this the Clausius–Clapeyron equation.
tionships are P1 H vap 1 1
ln
are plotted for water, acetone, and P2 R T2 T1
ted values of Hvap are as follows:
P1 H vap 1 1
ln (12.3)
P2 R T2 T1
Clausius–Clapeyron
If we know the value of the heat of vaporization, Equation 12.3 can also be used to calcu-
late the vapor pressure at some particular temperature (say, P2 at a temperature T2) if we 12/17/20
already know the vapor pressure P1 at a temperature T1.
Example
Calculating the Heat of Vaporiza
Using the Clausius-Clapeyron Equation
from Temperatures and Vapor Press
Methanol, CH3OH, experiences hydrogen bonding, dipole–dipole interactions, and
London forces. At 64.6 °C, it has a vapor pressure of 1.00 atm, and at 12.0 °C, it has a
vapor pressure of 0.0992 atm. What is the heat of vaporization for methanol?
Analysis: We are given two temperatures and two vapor pressures and we are asked to
find the heat of vaporization. We will need to use the Clausius–Clapeyron equation to
solve this problem.
Assembling the Tools: The main tool that we will use will be the application of the
Clausius–Clapeyron equation, Equation 12.3, to find the heat of vaporization.
P1 H vap 1 1
ln
P2 R T2 T1
97
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 kJ/mol
A. 5483 J
B. 5638 J
C. 2304 J
D. 2364 J
E. 62,400 J
98
49
12/17/20
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 kJ/mol
2.108 J 10 K
10.00 g H 2O = 210.8 J
A. 5483 J g K 1
B. Answer: 5638 J 10.00 g H 2O
1 mol 6010 J
= 3335 J
18.02 g H 2O 1 mole
C. 2304 J
4.184 J 50 K
D. 2364 J 10.00 g H 2O
g K 1
= 2092 J
E. 62,400 J 210.8 J + 3335 J + 2092 J = 5638 J
99
How much energy is required to vaporize 12.00 g of NH3
ΔHvap is 21.70 kJ/mol?
A. 4435 kJ
B. 32.47 kJ
C. 30.79 kJ
D. 9.42 kJ
E. 15.29 kJ
100
50
12/17/20
How much energy is required to vaporize 12.00 g of NH3
ΔHvap is 21.70 kJ/mol?
A. 4435 kJ
B. 32.47 kJ
1 mol 21.70 kJ
12.00 g NH 3 = 15.29 kJ
C. 30.79 kJ 17.03 g NH 3 1 mol
D. 9.42 kJ
E. Answer: 15.29 kJ
101
Phase Diagrams
• Show the effects of both pressure and temperature on phase
changes
• Boundaries between phases indicate equilibrium
• Triple point:
o The temperature and pressure at which s, l, and g are all at
equilibrium
• Critical point:
o The temperature and pressure at which a gas can no longer be
condensed
o TC = temperature at critical point
o PC = pressure at critical point
102
51
12/17/20
Phase Diagram
• X axis – temperature
• Y axis – pressure
• As P increases (T constant),
solid most likely
o More compact
• As T increases (P constant),
gas most likely
o Higher energy
• Each point = T and P
o B = 0.01 °C, 4.58 torr
o E = 100 °C, 760 torr
o F = −10 °C, 2.15 torr
103
Phase Diagram of Water

• AB = vapor pressure curve for ice
• BD = vapor pressure curve for
liquid water
• BC = melting point line
• B = triple point: T and P where all
three phases are in equilibrium
• D = critical point
o T and P above which liquid does
not exist
104
52
12/17/20
Case Study: An Ice Necklace

• A cube of ice may be suspended on a string simply by
pressing the string into the ice cube. As the string is
pressed onto the surface, it becomes embedded into the
ice.
• Why does this happen?
105
Phase Diagram – CO2

• Now line between solid and
liquid slants to right
• More typical
• Where is triple point?
• Where is critical point?
106
53
12/17/20
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
107
Le Chatelier’s Principle
• Equilibria are often disturbed or upset
• When dynamic equilibrium of system is upset by a
disturbance
o System responds in direction that tends to counteract
disturbance and, if possible, restore equilibrium
• Position of equilibrium
o Used to refer to relative amounts of substance on each
side of double (equilibrium) arrows
108
54
12/17/20
Liquid Vapor Equilibrium

Liquid + Heat D Vapor
• Increasing T
o Increases amount of vapor
o Decreases amount of liquid
• Equilibrium has shifted
o Shifted to the right
o More vapor is produced at expense of liquid
• Temperature-pressure relationships can be represented
using a phase diagram
109
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
110
55
12/17/20
At 89 °C and 760 mmHg, what physical state is present?
A. Solid
B. Answer: Liquid
C. Gas
D. Supercritical fluid
E. Not enough information is given
111
Measuring DHvap
• Clausius-Clapeyron equation
• Measure pressure at various temperatures, then plot
æ DH vap ö 1
ln P = - ç ÷ +C
è R øT
P1 DH vap æ 1 1 ö
• Two point form of Clausius-Clapeyron equation

ln
P2
= ç - ÷
R è T2 T1 ø
• Measure pressure at two temperatures and solve equation
112
56
12/17/20
Learning Check 1
The vapor pressure of diethyl ether is 401 mm Hg at 18.00 °C, and
its molar heat of vaporization is 26 kJ/mol. Calculate its vapor
pressure at 32.00 °C.
T1 = 273.15 + 18 = 291.15 K
P DH vap æ 1 1 ö
ln 1 = ç - ÷ T2 = 273.15 + 32 = 305.15 K
P2 R è T2 T1 ø
P1 2.6 ´ 104 J / mol æ 1 P 1 ö

= -=P = -0.4928
1
ln
P2 8.314 J / K × mol è 305.15 K 291.15 K ÷ø
( ) ç
2
0.6109
P1
= e -0.4928 = 0.6109
P2
401 mm Hg
P2 = = 6.6 ´ 102 mm Hg
0.6109
113
Determine the enthalpy of vaporization, in kJ/mol, for
benzene, using the following vapor pressure data.
A. 32.2 kJ/mol T = 60.6 °C; P = 400. mmHg

B. 14.0 kJ/mol T = 80.1 °C; P = 760. mmHg
C. –32.4 kJ/mol
D. 0.32 kJ/mol
E. –14.0 kJ/mol
114
57
12/17/20
Determine the enthalpy of vaporization, in kJ/mol, for
benzene, using the following vapor pressure data.
A. Answer: 32.2 kJ/mol T = 60.6 °C; P = 400. mmHg

B. 14.0 kJ/mol T = 80.1 °C; P = 760. mmHg
C. –32.4 kJ/mol
D. 0.32 kJ/mol
E. –14.0 kJ/mol
115
Your Turn! - Solution (1 of 2)
P1 ΔH vap æ1 1ö
ln = ç - ÷
P2 R è T2 T1 ø
400 m m Hg ΔH vap æ 1 1 ö
ln = -
760 m m Hg 8.314 J è 353.1 K 333.6 K ÷ø
ç
K mol
ΔH vap = 32, 235 J / mol or 32.2 kJ / mol
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Types of Solids
• Crystalline Solids
o Solids with highly regular arrangements of components
• Amorphous Solids
o Solids with considerable disorder in their structures
117
Crystal Structures Have Regular Patterns

• Lattice
o Many repeats of unit cell
o Regular, highly
symmetrical system
o Three (3) dimensional
system of points
designating positions
of components
• Atoms
• Ions
• Molecules
118
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Crystalline Solids
• Unit Cell
o Smallest segment that repeats
regularly
o Smallest repeating unit of
lattice
o Two-dimensional unit
cells
119
12.11 | Structures of Crystalline Solids 563
Crystal Lattice
Table 12.6 Types
Crystal Lattice
The 7 Lattices
Types
The 14 Lattice Types
Simple Body-Centered Base-Cenrered Face-Centered

Triclinic a1 a2 a3
12 23 31 90°
a3
a2
a1
Monoclinic a1 a2 a3
23 31 90° a3 a3
12 90°
a2 a2
a1 a1
Orthorhombic a1 a2 a3
12 23 31 90° a3 a3 a3
a3
a2 a2 a2 a2
a1 a1 a1 a1
Tetragonal a1 a2 a3
12 23 31 90° a3
a3
a1 a2 a1 a2
Trigonal a1 a2 a3
12 23 31 120° 90° a3
120 a1 a2
Hexagonal a1 a2 a3
120°
12
23 31 90° a3
60
a2
a1
Cubic a1 a2 a3
12 23 31 90° a3 a3 a3
Monoclinic a1 a2 a3
23 31 90° a3 a3
12 90°
a2 a2
a1 a1
Orthorhombic a1 a2 a3 12/17/20
12 23 31 90° a3 a3 a3
a3
a2 a2 a2 a2
a1 a1 a1 a1
Tetragonal a1 a2 a3
12 23 31 90° a3
a3
Crystal Lattice Types a1 a2 a1 a2
Trigonal a1 a2 a3
12 23 31 120° 90° a3
a1 a2
Hexagonal a1 a2 a3
12 120°
23 31 90° a3
a2
a1
Cubic a1 a2 a3
12 23 31 90° a3 a3 a3
a1 a2 a1 a2 a1 a2
a3
121 31 23
a2
a1
12
Three Types Of 3-D Unit Cells

jespe_c12_527-584hr.indd 563 11/15/10 2:34 PM
• Simple cubic
o Has one host atom at each corner
o Edge length a = 2r
o Where r is radius of atom or ion
• Body-centered cubic (BCC)
o Has one atom at each corner and one in center
o Edge length a = 4r
3
• Face-centered cubic (FCC)
o Has one atom centered in each
face, and one at each corner
o Edge length a = 4r / 2
122
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Close Packing of Spheres

1st layer 2nd layer
• Most efficient arrangement of spheres in two dimensions

• Each sphere has 6 nearest neighbors
• Second layer with atoms in holes on the first layer
123
Two Ways to Put on Third Layer

Cubic lattice: 3-dimensional arrays
1. Directly above spheres in first layer 2. Above holes in first layer
Hexagonal Face centered cubic
124
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3-D Simple Cubic Lattice

Unit Cell
Portion of lattice—open view Space filling model
125
Other Cubic Lattices

Face Centered Cubic Body Centered Cubic
126
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Ionic Solids
Lattices of alternating charges
• Want cations next to anions
o Maximizes electrostatic attractive forces
o Minimizes electrostatic repulsions
• Based on one of three basic lattices:
o Simple cubic
o Face centered cubic
o Body centered cubic
127
Common Ionic Solids

Rock salt or NaCl
• Face centered cubic lattice of

Cl – ions (green)
+
• Na ions (blue) in all octahedral holes
128
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Tipe CsCl
129
Tipe CaF2 (fluorite)
Bk kation = 8 dan bk anion = 4

Diadopsi juga oleh: MCl2 (M= alkali
tanah), BaCl2, dioksida logam blok-f
(CeO2, ThO2, dll).
Jika posisi kation dan anion terbalik,

diperoleh M2X. Kisi ini disebut
antifluorite.
Contoh: oksida dan sulfida logam
alkali (M2O dan M2S), kecuali Cs2O.
Anion (warna hijau)
menempati rongga Th
dari kisi kation.
130
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Tipe ZnS (zinc blende)
Mirip seperti fluorite, tetapi hanya

setengah rongga Th yang terisi anion.
Tipe kisi ini sama dengan struktur
intan.
131
Spaces In Ionic Solids Are Filled With Counter Ions

• In NaCl
o Cl – ions form face-centered
cubic unit cell
o Smaller Na + ions fill spaces
between Cl – ions
• Count atoms in unit cell
o Have 6 of each or
1:1 Na + : Cl – ratio
132
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Counting Atoms per Unit Cell

• Four types of sites in unit cell
o Central or body position – atom is completely contained in one unit cell
o Face site – atom on face shared by two unit cells

o Edge site – atom on edge shared by four unit cells
o Corner site – atom on corner shared by eight unit cells
Site Counts as Shared by X unit cells

Body 1 1
1
Face 2 2
1
Edge 4
4
1
Corner 8
8
133
Example: NaCl
Site # of Na + # of Cl –
Body 1 0
Face 0 (6 ´ 12 ) = 3
Edge (12 ´ 1 4 ) = 3 0
Corner 0 (8 ´ 18 ) = 1
Total 4 4
134
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Learning Check: 2
Determine the number of each type of ion in the unit cell.
1:1 4:4 4:8

CsCl ZnS CaF2
135
Some Factors Affecting Crystalline

Structure
• Size of atoms or ions involved
• Stoichiometry of salt
• Materials involved
o Some substances do not form crystalline solids
136
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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
137
X-Ray Crystallography
• X rays are passed through
crystalline solid
• Some x rays are absorbed,
most re-emitted in all
directions
• Some emissions by atoms are
in phase, others out of phase
• Emission is recorded on film
138
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X-ray Diffraction
Experimental Setup Diffraction Pattern
139
Interpreting Diffraction Data (1 of 2)

• As x rays hit atoms
in lattice they are
deflected
• Angles of
deflections related
to lattice spacing
• So we can estimate
atomic and ionic radii
from distance data
140
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Interpreting Diffraction Data (2 of 2)

Bragg Equation
• nλ=2d sinθ
o n = integer (1, 2, …)
o l = wavelength of
X rays
o d = interplane spacing
in crystal
o q = angle of incidence
and angle of reflectance
of X rays to various
crystal planes
141
Example: Diffraction Data

The diffraction pattern of copper metal was measured with
X-ray radiation of wavelength of 131.5 pm. The first order
(n = 1) Bragg diffraction peak was found at an angle θ of
50.5 °. Calculate the spacing between the diffracting
planes in the copper metal.
nl = 2d sin q
1(131.5 pm) = 2 × d × sin(50.5 °)
d = 283 pm
142
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Example: Using Diffraction Data (1 of 2)

X-ray diffraction measurements reveal that copper crystallizes
with a face-centered cubic lattice in which the unit cell length
is 362 pm. What is the radius of a copper atom expressed in
picometers?
This is basically a geometry problem.

143
Example: Using Diffraction Data (2 of 2)

Pythagorean theorem: a 2 + b 2 = c 2
Where a = b = 362 pm sides and c = diagonal
2a2 = c2 and c = 2a 2 = 2a
diagonal = 2 ´ (362 pm) = 512 pm
diagonal = 4 ´ rCu = 512 pm
rCu = 128 pm
144
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Learning Check 3
Silver packs together in a faced center cubic fashion. The
interplanar distance, d, corresponds to the length of a side
of the unit cell, and is 407 pm. What is the radius of a
silver atom?
a = 2 2r
407 pm = 2 2r
r = 53.6 pm
145
Ionic Crystals (Example: 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
146
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Covalent Crystals
• Lattice positions occupied by atoms that are covalently
bonded to other atoms at neighboring lattice sites
• Also called network solids
o Interlocking network of covalent bonds extending all
directions
• Covalent crystals tend to
o Be very hard
o Have very high melting points
o Have strong attractions between covalently bonded atoms
147
Example: Covalent (Network) Solid

• Diamond (all C)
o Shown
• SiO2 silicon oxide
o Alternating Si and O
o Basis of glass and quartz
• Silicon carbide (SiC)
148
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Metallic Crystals (1 of 2)
• Simplest models
o Lattice positions of metallic
crystal occupied by positive ions
o Cations surrounded by
“cloud” of electrons
• Formed by valence electrons
• Extends throughout entire solid
149
Metallic Crystals (2 of 2)
• Conduct heat and electricity
o By their movement, electrons transmit kinetic energy
rapidly through solid
• Have the luster characteristically associated with metals
o When light shines on metal
o Loosely held electrons vibrate easily
o Re-emit light with essentially same frequency and
intensity
150
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Learning Check: 4
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 ü
electricity
Y: White crystalline solid that
conducts electrical current ü
when molten or dissolved
Z: Shiny, conductive,
malleable with high melting ü
temperature
151
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
152
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Yitterbium crystallizes with a face centered cubic lattice.
The atomic radius of yitterbium is 175 pm. Determine the
unit cell length.
A. Answer: 495 pm
B. 700 pm
C. 350 pm
D. 990 pm
E. 247 pm
153
Your Turn! - Solution (2 of 2)

diagonal of cube = 4r where r = atomic radius
diagonal of cube = 2 a where a = side of cube

4r 4 ´ 175 pm
a= = = 495 pm
2 2
154
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Molecular crystals can contain all of the listed attraction
forces except:
A. Dipole-dipole attractions
B. Electrostatic forces
C. London forces
D. Hydrogen bonding
155
Molecular crystals can contain all of the listed attraction
forces except:
A. Dipole-dipole attractions
B. Answer: Electrostatic forces
C. London forces
D. Hydrogen bonding
156
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Copyright
Copyright © 2014 John Wiley & Sons, Inc.
All rights reserved. Reproduction or translation of this work beyond that permitted in
Section 117 of the 1976 United States Act without the express written permission of the
copyright owner is unlawful. Request for further information should be addressed to the
Permissions Department, John Wiley & Sons, Inc. The purchaser may make back-up
copies for his/her own use only and not for distribution or resale. The Publisher assumes
no responsibility for errors, omissions, or damages, caused by the use of these programs or
from the use of the information contained herein.
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Intermolecular Attractions and the

Ki1101 Kimia Dasar 1A

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Inter versus Intra-Molecular Forces

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• Responsible for non-ideal behavior of gases

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Types of Intermolecular Attractions

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Three Important Types of Intermolecular Forces

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• δ – almost full –1 charge

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Examples of Hydrogen Bonding

Thymine Adenine Cytosine Guanine

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Hydrogen Bonding in Water

• Responsible for expansion of water as it freezes

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London Dispersion Forces

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Table 11.1 Boiling Points of Halogens and

Group 7 A Boiling Point (°C) Group 8A Boiling Point (°C)

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12.2 | Types of Intermolecular Forces 531

Table 12.2 Boiling Points of Some Hydrocarbonsa

* * Figure 12.5 | The number of atoms in a

Hexane, C6H14 Propane, C3H8

jespe_c12_527-584hr.indd 531 11/15/10 2:33

Copyright ©2014 John Wiley & Sons, Inc. 27

Physical Origin of Shape Effect

• Small area for interaction • Larger area for interaction

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Figure 12.10 | Ion–dipole

Ion-Induced Dipole Attractions

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Summary of Intermolecular Attractions

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Summary of Intermolecular Attractions

Using Intermolecular Forces

• Larger, longer, and therefore heavier molecules often have

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