Liquids and Intermolecular Forces: Lecture Presentation

Lecture Presentation
Chapter 11
Liquids and
Intermolecular
Forces
James F. Kirby
Quinnipiac University
Hamden, CT
© 2015 Pearson Education, Inc.
States of Matter
 The fundamental
difference between states
of matter is the strength of
the intermolecular forces
of attraction.
 Stronger forces bring
molecules closer together.
 Solids and liquids are
referred to as the
condensed phases.
Intermolecular
Forces

Differences in the
States of Matter
Intermolecular
Forces

Which State of Matter?
• The answer to this
question largely
relies on the
 balance between the
kinetic energies of
the particles.
 interparticle energies
of attraction.
Intermolecular
Forces

Intermolecular Forces
• The attractions between molecules are not nearly as

strong as the intramolecular attractions (bonds) that
hold compounds together.
• Many physical properties reflect intermolecular
forces, like boiling points, melting points, viscosity,
surface tension, and capillary action. Intermolecular
Forces

Types of Intermolecular Force
• Weakest to strongest forces:
 dispersion forces (or London dispersion
forces)
 dipole–dipole forces
 hydrogen bonding (a special dipole–dipole
force)
 ion–dipole forces
o Note: The first two types are also referred
to collectively as van der Waals forces.
Intermolecular
Forces

Dispersion Forces
• The figure below shows how a nonpolar particle
(in this case a helium atom) can be temporarily
polarized to allow dispersion force to form.
• The tendency of an electron cloud to distort is
called its polarizability.
Intermolecular
Forces

Factors Which Affect Amount of
Dispersion Force in a Molecule
• number of electrons in
an atom (more electrons,
more dispersion force)
• size of atom or
molecule/molecular
weight
• shape of molecules with
similar masses (more
compact, less dispersion
force) Intermolecular
Forces

Polarizability & Boiling Point
• If something is easier
to polarize, it has a
lower boiling point.
• Remember: This
means less
intermolecular force
(smaller molecule:
lower molecular
weight, fewer
electrons). Intermolecular
Forces

Dipole–Dipole Interactions
• Polar molecules have a more positive
and a more negative end–a dipole (two
poles, δ+ and δ−).
• The oppositely charged ends attract
each other.
Intermolecular
Forces

Dipole–Dipole Interactions
For molecules of approximately equal mass

and size, the more polar the molecule, the
higher its boiling point. Intermolecular
Forces

Which Have a Greater Effect:
Dipole–Dipole Interactions or
Dispersion Forces?
• If two molecules are of comparable size
and shape, dipole–dipole interactions
will likely be the dominating force.
• If one molecule is much larger than
another, dispersion forces will likely
determine its physical properties.
Intermolecular
Forces

What Does This Graph Show Us?
• In a group, the period
3/4/5 elements have
higher boiling points
as the group member
gets larger.
• What happens with
the period 2
elements? For group
4A, the trend is
continued. What about
for the other groups? Intermolecular
Forces

Hydrogen Bonding
• The dipole–dipole interactions
experienced when H is
bonded to N, O, or F are
unusually strong.
• We call these interactions
hydrogen bonds.
• A hydrogen bond is an
attraction between a hydrogen
atom attached to a highly
electronegative atom and a
nearby small electronegative
atom in another molecule or Intermolecular
chemical group. Forces

What Forms Hydrogen Bonds?
• Hydrogen bonding arises in part from the
high electronegativity of nitrogen, oxygen,
and fluorine.
• These atoms interact with a nearly bare
nucleus (which contains one proton).
Intermolecular
Forces

Ion–Dipole Interactions
• Ion–dipole interactions are found in solutions of ions.
• The strength of these forces is what makes it
possible for ionic substances to dissolve in polar
solvents.
Intermolecular
Forces

Summarizing Intermolecular Forces
Intermolecular
Forces

Liquid Properties Affected by
Intermolecular Forces
• boiling point (previously discussed) and
melting point
• viscosity
• surface tension
• capillary action
Intermolecular
Forces

Viscosity
• Resistance of a liquid to flow is called
viscosity.
• It is related to the ease with which
molecules can move past each other.
• Viscosity increases with stronger
intermolecular forces and decreases
with higher temperature.
Intermolecular
Forces

Surface Tension
• Water acts as if it
has a “skin” on it
due to extra inward
forces on its
surface. Those
forces are called the
surface tension.
Intermolecular
Forces

Cohesion and Adhesion
• Intermolecular forces that bind similar
molecules to one another are called
cohesive forces.
• Intermolecular forces that bind a
substance to a surface are called
adhesive forces.
• These forces are important in capillary
action.
Intermolecular
Forces

Capillary Action
• The rise of liquids up
narrow tubes is called
capillary action.
• Adhesive forces attract
the liquid to the wall of
the tube.
• Cohesive forces attract
the liquid to itself.
• Water has stronger
adhesive forces with glass;
mercury has stronger
cohesive forces with itself. Intermolecular
Forces

Phase Changes
• Conversion from one
state of matter to
another is called a
phase change.
• Energy is either added
or released in a phase
change.
• Phase changes:
melting/freezing,
vaporizing/condensing,
subliming/depositing.
Intermolecular
Forces

Energy Change & Change of State
• The heat of fusion is the energy required to change
a solid at its melting point to a liquid.
• The heat of vaporization is the energy required to
change a liquid at its boiling point to a gas.
• The heat of sublimation is the energy required to
change a solid directly to a gas.
Intermolecular
Forces

Heating Curves
• A plot of temperature vs.
heat added is called a
heating curve.
• Within a phase, heat is
the product of specific
heat, sample mass, and
temperature change.
• The temperature of the
substance does not rise
during a phase change.
• For the phase changes, the product of mass Intermolecular
and the heat of fusion of vaporization is heat. Forces

Supercritical Fluids
• Gases liquefies when
pressure is applied.
• The temperature beyond
which a gas cannot be
compressed is called its
critical temperature.
The pressure needed to
compress the liquid at
critical temperature is
called critical pressure.
• The state beyond this
temperature is called a Intermolecular
supercritical fluid. Forces

Vapor Pressure
• At any temperature,
some liquid molecules
have enough energy to
escape the surface and
become a gas.
• As the temperature
rises, the fraction of
molecules that have
enough energy to break
free increases.
Intermolecular
Forces

Vapor Pressure
• As more molecules
escape the liquid,
the pressure they
exert increases.
• The liquid and vapor
reach a state of
dynamic equilibrium:
liquid molecules
evaporate and vapor
molecules condense
at the same rate.
Intermolecular
Forces

Vapor Pressure
• The boiling point of
a liquid is the
temperature at which
its vapor pressure
equals atmospheric
pressure.
• The normal boiling
point is the
temperature at which
its vapor pressure is
760 torr.
Intermolecular
Forces

Vapor Pressure
• The natural log of the
vapor pressure of a liquid
is inversely proportional to
its temperature.
• This relationship is
quantified in the
Clausius–Clapeyron
equation.
Intermolecular
Forces

Example 11.4: Determine the DHvap of
dichloromethane given the vapor pressure vs.
temperature data
• Enter the data into a spreadsheet and calculate
the inverse of the absolute temperature and
natural log of the vapor pressure
Intermolecular
Forces
Tro: Chemistry:
© 2015 PearsonAEducation,
Molecular Inc. Approach, 2/e 31
Example 11.4: Determine the DHvap of
dichloromethane given the vapor pressure vs.
temperature data
• Use the slope of the line to determine the heat of
vaporization
– slope ≈ −3800 K, R = 8.314 J/mol∙K
Intermolecular
Forces
Tro: Chemistry:
Clausius–Clapeyron Equation
2-Point Form
• The equation below can be used with just two
measurements of vapor pressure and temperature
– however, it generally gives less precise results
• fewer data points will not give as precise an average because there is
less averaging out of the errors
o as with any other sets of measurements
• It can also be used to predict the vapor pressure if you
know the heat of vaporization and the normal boiling point
– remember: the vapor pressure at the normal boiling point is 760
torr
Intermolecular
Forces
Tro: Chemistry:
Example 11.5: Calculate the vapor pressure of
methanol at 12.0 °C
Given: T1 = BP = 337.8
64.6 °C,
K, P11 = 760 torr, DHvap
vap = 35.2 kJ/mol,
T2 = 285.2
12.0 °CK
Find: P2, torr
Conceptual P1, T1, DHvap P2
Plan:
Relationships: T(K) = T(°C) + 273.15

Solution:
Check: the units are correct, the size makes sense because the
vapor pressure is lower at lower temperatures
Intermolecular
Forces
Tro: Chemistry:
Supercritical Fluid
• As a liquid is heated in a sealed container, more vapor
collects, causing the pressure inside the container to rise
– and the density of the vapor to increase
– and the density of the liquid to decrease
• At some temperature, the meniscus between the liquid and
vapor disappears and the states commingle to form a
supercritical fluid
• Supercritical fluids have properties of both gas and liquid
states
Intermolecular
Forces
Tro: Chemistry:
Heat of Fusion
• The amount of heat energy required to melt one mole of the
solid is called the Heat of Fusion, DHfus
– sometimes called the enthalpy of fusion
• Always endothermic, therefore DHfus is +
• Somewhat temperature dependent
· DHcrystallization = −DHfusion
· Generally much less than DHvap
· DHsublimation = DHfusion + DHvaporization
Intermolecular
Forces
Tro: Chemistry:
Heating Curve of Water
Intermolecular
Forces
Tro: Chemistry:
Segment 1
• Heating 1.00 mole of ice at −25.0 °C up to the
melting point, 0.0 °C
• q = mass x Cs x DT
– mass of 1.00 mole of ice = 18.0 g
– Cs = 2.09 J/mol∙°C
Intermolecular
Forces
Tro: Chemistry:
Segment 2
• Melting 1.00 mole of ice at the melting point,
0.0 °C
• q = n∙DHfus
– n = 1.00 mole of ice
– DHfus = 6.02 kJ/mol
Intermolecular
Forces
Tro: Chemistry:
Segment 3
• Heating 1.00 mole of water at 0.0 °C up to the
boiling point, 100.0 °C
– mass of 1.00 mole of water = 18.0 g
– Cs = 2.09 J/mol∙°C
Intermolecular
Forces
Tro: Chemistry:
Segment 4
• Boiling 1.00 mole of water at the boiling point,
100.0 °C
• q = n∙DHvap
– n = 1.00 mole of ice
– DHfus = 40.7 kJ/mol
Intermolecular
Forces
Tro: Chemistry:
Segment 5
• Heating 1.00 mole of steam at 100.0 °C up to
125.0 °C
– mass of 1.00 mole of water = 18.0 g
– Cs = 2.01 J/mol∙°C
Intermolecular
Forces
Tro: Chemistry:
Practice – How much heat, in kJ, is needed to
raise the temperature of a 12.0 g benzene
sample from −10.0 °C to 25.0 °C?
Intermolecular
Forces
Tro: Chemistry:
Practice – How much heat is needed to raise the temperature
of a 12.0 g benzene sample from −10.0 °C to 25.0 °C?
Given: 12.0 g benzene, seg 1 =(T0.2325

1 = −10.0
kJ,°C, T2 = 5.5 °C),
seg 2 = 1.51
melting,
kJ, seg 3 (T
= 0.3978
1 = 5.5 °C,
kJ T22 = 25.0 °C)
Find: kJ
kJ
1
Conceptual Seg 231 g mol

J kJ
Plan:
DHfus 9.8 kJ/mol, 1 mol = 78.11 g, 1 kJ = 1000 J, q = m∙Cs∙DT

Relationships:
Cs,sol = 1.25 J/g°C, Cs,liq = 1.70 J/g°C
Solution:
Intermolecular
Forces
Tro: Chemistry:
Phase Diagram
• A phase diagram is a graph of pressure vs.
temperature for a substance. It shows
– melting, boiling, and sublimation points at different
pressures.
– the triple point and critical point.
Intermolecular
Forces

Phase Diagram of Water
• Note the high critical

temperature and critical
pressure.
– These are due to the
strong van der Waals
forces between water
molecules.
Intermolecular
Forces

Phase Diagram of Water
• Unusual feature for water:

 The slope of the solid–
liquid line is negative.
 This means that as the
pressure is increased, the
melting point decreases.
Intermolecular
Forces

Phase Diagram of Carbon Dioxide
• Unusual features for

carbon dioxide:
 cannot exist in the
liquid state at
pressures below
5.11 atm (triple point)
 CO2 sublimes at
normal pressures.
Intermolecular
Forces

Sample Exercise 11.6 Interpreting a Phase diagram
Referring to Figure 11.28, describe any changes in the phases present when
H2O is (a) kept at 0 °C while the pressure is increased from that at point
1 to that at point 5 (vertical line), (b) kept at 1.00 atm while the
temperature is increased from that at point 6 to that at point 9
Solution
(horizontal line).
Analyze: We are asked to use the phase diagram provided to deduce what
phase changes might occur when specific pressure and temperature changes
are brought about.
Plan: Trace the path indicated on the phase diagram, and note what
phases and phase changes occur.
Solve:
(a) At point 1, H2O exists totally as a vapor. At point 2 a solid–vapor
equilibrium exists. Above that pressure, at point 3, all the H2O is
converted to a solid. At point 4 some of the solid melts and equilibrium
between solid and liquid is achieved. At still higher pressures all the
H2O melts, so only the liquid phase is present at point 5.
(b) At point 6 the H2O exists entirely as a solid. When the temperature
reaches point 4, the solid begins to melt and equilibrium exists between
the solid and liquid phases. At an even higher temperature, point 7, the
Practice
solid hasExercise
been converted entirely to a liquid. A liquid–vapor
equilibrium
(Using Figure exists at point
11.27(b), 8. Upon
describe whatfurther heating
happens to point
when the 9, the
following H2O
changes
is
areconverted
made in aentirely to the
CO2 sample: (a) vapor phase.
Pressure increases from 1 atm to 60 atm at a
Check:
constant The indicated of
temperature phases and (b)
–60 °C. phase changes are
Temperature consistent
increases with our
from
knowledge
–60 °C to of –20the
°C properties of water.
at a constant pressure of 60 atm.
Answer: (a) CO2(g) → CO2(s); (b) CO2(s) → CO2(l)
Chemistry: The Central Science, Eleventh Edition Copyright ©2009 by Pearson Education, Inc.
By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy Upper Saddle River, New Jersey 07458
With contributions from Patrick Woodward All rights reserved.
Liquid Crystals
• Some substances do not go directly from the

solid state to the liquid state.
• In this intermediate state, liquid crystals have
some traits of solids and some of liquids.
• Molecules in liquid crystals have some degree
of order.
Intermolecular
Forces

Liquid
Crystals
• In nematic liquid
crystals, molecules
are only ordered in
one dimension, along the long axis.
• In smectic liquid crystals, molecules are
ordered in two dimensions, along the long axis
and in layers.
• In cholesteryic liquid crystals, nematic-like
crystals are layered at angles to each other. Intermolecular
Forces

Water – An Extraordinary Substance
• Water is a liquid at room temperature
 most molecular substances with similar molar masses are gases at
room temperature
 e.g. NH3, CH4
 due to H-bonding between molecules
• Water is an excellent solvent – dissolving many ionic and
polar molecular substances
 because of its large dipole moment
 even many small nonpolar molecules have some solubility in water
 e.g. O2, CO2
• Water has a very high specific heat for a molecular substance
 moderating effect on coastal climates
• Water expands when it freezes
 at a pressure of 1 atm
 about 9%
 making ice less dense than liquid water
Tro: Chemistry: A Molecular Approach, 2/e 52 Copyright  2011 Pearson Education, Inc.
Solids
Properties &
Structure
Tro: Chemistry: A Molecular Approach, 2/e Copyright  2011 Pearson Education, Inc.
Crystal Lattice
• When allowed to cool slowly, the particles in a
liquid will arrange themselves to give the
maximum attractive forces
 therefore minimize the energy
• The result will generally be a crystalline solid
• The arrangement of the particles in a
crystalline solid is called the crystal lattice
• The smallest unit that shows the pattern of
arrangement for all the particles is called the
unit cell
Unit Cells
• Unit cells are 3-dimensional
 usually containing 2 or 3 layers of particles
• Unit cells are repeated over and over to give the
macroscopic crystal structure of the solid
• Starting anywhere within the crystal results in the same
unit cell
• Each particle in the unit cell is called a lattice point
• Lattice planes are planes connecting equivalent points in
unit cells throughout the lattice
7 Unit Cells
c c c
c
b b
b
a a a a b
Cubic Tetragonal Orthorhombic Monoclinic
a=b=c a=c<b a¹b¹c a¹b¹c
all 90° all 90° all 90° 2 faces 90°
c c
c
b b
b
a a a
Hexagonal Rhombohedral Triclinic
a=c<b a=b=c a¹b¹c
2 faces 90° no 90° no 90°
1 face 120° 56 Copyright  2011 Pearson Education, Inc.
Unit Cells
• The number of other particles each particle is in
contact with is called its coordination number
 for ions, it is the number of oppositely charged ions an
ion is in contact with
• Higher coordination number means more
interaction, therefore stronger attractive forces
holding the crystal together
• The packing efficiency is the percentage of
volume in the unit cell occupied by particles
 the higher the coordination number, the more efficiently
the particles are packing together
Cubic Unit Cells
• All 90° angles between corners of the unit cell
• The length of all the edges are equal
• If the unit cell is made of spherical particles
 ⅛ of each corner particle is within the cube
 ½ of each particle on a face is within the cube
 ¼ of each particle on an edge is within the cube
Cubic Unit Cells -
Simple Cubic
• Eight particles, one at each
corner of a cube
• 1/8th of each particle lies in the
unit cell
 each particle part of eight cells 2r
 total = one particle in each unit
cell
8 corners x 1/8
• Edge of unit cell = twice the
radius
• Coordination number of 6
Simple Cubic
Cubic Unit Cells -
Body-Centered Cubic
• Nine particles, one at each
corner of a cube + one in center
• 1/8th of each corner particle lies
in the unit cell 4r
 two particles in each unit cell 3
8 corners x 1/8
+ 1 center
• Edge of unit cell = (4/Ö 3) times
the radius of the particle
Body-Centered Cubic
Cubic Unit Cells -
Face-Centered Cubic
• 14 particles, one at each corner
of a cube + one in center of
each face
• 1/8th of each corner particle +
1/2 of face particle lies in the
unit cell 2r 2
 4 particles in each unit cell
8 corners x 1/8
+ 6 faces x 1/2
• Edge of unit cell = 2 2 times
the radius of the particle
Face-Centered Cubic
Example 11.6: Calculate the density of Al if it
crystallizes in a fcc and has a radius of 143 pm
Given: face-centered
face-centeredcubic,
cubic,Vr==6.618
143 pm
1.43 xx10
10−8−23cm,
cmm3
,m
= 1.792
=1.792x x1010
−22
gg
−22
Find: density,
density,g/cm
g/cm3 3
Conceptual fcc mass r l V

Plan:
# atoms x mass of 1 atom l = 2r√2 V=l3
m, V d
Relationships: d = m/V
1 cm = 10 m, 1 pm = 10−12 m V = l 3, l = 2r√2, d = m/V
2
fcc = 4 atoms/uc, Al = 26.982 g/mol, 1 mol = 6.022 x 10 23 atoms

Solution:
Check: the accepted density of Al at 20°C is 2.71 g/cm3, so the

answer makes sense
Practice – Estimate the density of Rb if it crystallizes
in a body-centered cubic unit cell and has an atomic
radius of 247.5 pm
Practice – Estimate the density of Rb if it
crystallizes in a bcc and has a radius of 247.5 pm
Given: body-centered
body-centered
body-centered cubic, V=rr=
cubic,
cubic, 1.868 x 10
=2.475
247.5xpm
10 cmcm,
−22 −8 3
, m=
m 2.839 x 10
= 2.839 10g−22 g
x −22
Find: density,
density,g/cm
density, g/cm
g/cm
333
Conceptual bcc mass r l V

Plan:
# atoms x mass of 1 atom l = 4r/√3 V=l3
m, V d
Relationships: d = m/V
1 cm = 10 m, 1 pm = 10−12 m V = l 3, l = 4r/√3, d = m/V
2
bcc = 2 atoms/uc, Rb = 85.47 g/mol, 1 mol = 6.022 x 10 23 atoms

Solution:
Check: the accepted density of Rb at 20°C is 1.53 g/cm3, so the answer

makes sense
Sample Exercise 11.7 Determining the Contents of a Unit Cell
Determine the net number of Na+ and Cl– ions in the NaCl unit cell (Figure
11.36).
Solution
Analyze: We must sum the various contributing elements to determine the
number of Na+ and Cl– ions within the unit cell.
Plan: To find the total number of ions of each type, we must identify
the different locations within the unit cell and determine the fraction
Solve:
of the There is one-fourth
ion that lies withinof anunit
the Na+ cell boundaries.
on each edge, a
whole Na+ in the center of the cube
(refer also to
Figure 11.35), one-eighth of a Cl–
on each corner, and
one-half of a Cl– on each face.
Thus, we have the
following:
Thus, the unit cell contains
Check: Since individually the ions

form a face
centered cubic lattice [see Figure
11.35(a)], as do the
ions [see Figure 11.35(b)], we would
expect there to
be four ions of each type in the
unit The
Chemistry: cell. More Eleventh Edition
Central Science, Copyright ©2009 by Pearson Education, Inc.
important, the presence
By Theodore E. Brown, H. ofBruce
Eugene LeMay, equalE. Bursten, and Catherine J. Murphy Upper Saddle River, New Jersey 07458
amounts of the two
Sample Exercise 11.7 Determining the Contents of a Unit Cell
Practice Exercise
The element iron crystallizes in a form called -iron, which has a body-
centered cubic unit cell. How many iron atoms are in the unit cell?
Answer: two
Sample Exercise 11.8 Using the Contents and dimensions of a Unit Cell to
Calculate Density
The geometric arrangement of ions in crystals of LiF is the same as that
in NaCl. The unit cell of LiF is 4.02 Å on an edge. Calculate the density
of LiF.
Solution
Analyze: We are asked to calculate the density of LiF from the size of
the unit cell.
Plan: Density is mass per volume, and this is true at the unit cell
level as well as the bulk level. We need to determine the number of
formula units of LiF within the unit cell. From that, we can calculate
the total
Solve: Themass within the
arrangement unit in
of ions cell. Because we know the mass and can
calculate thethe
LiF is volume
same of
as the unit cell, we can then calculate density.
that in NaCl (Sample Exercise 11.7),
so a unit cell of
LiF contains
Density is mass per unit volume.

Thus, we can
calculate the density of LiF from
the mass contained
in a unit cell and the volume of the
unit cell. The
mass contained in one unit cell is
The volume of a cube of length a on

an edge is a3, so
the Chemistry:
volume Theof the
Central unit
Science, cell
Eleventh is (4.02
Edition Copyright ©2009 by Pearson Education, Inc.
Å) . We
3
By Theodore canH. now
E. Brown, Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy Upper Saddle River, New Jersey 07458
calculate the density, converting to
Calculate Density
Solution (continued)
Check: This value agrees with that found by simple density measurements,
2.640 g/cm3 at 20 °C. The size and contents of the unit cell are therefore
consistent with the macroscopic density of the substance.
Practice Exercise
The body-centered cubic unit cell of a particular crystalline form of iron
is 2.8664 Å on each side. Calculate the density of this form of iron.
Answer: 7.8753 g/cm3
Calculate Density
The geometric arrangement of ions in crystals of LiF is the same as that
in NaCl. The unit cell of LiF is 4.02 Å on an edge. Calculate the density
of LiF.
Solution
Analyze: We are asked to calculate the density of LiF from the size of
the unit cell.
Plan: Density is mass per volume, and this is true at the unit cell
level as well as the bulk level. We need to determine the number of
formula units of LiF within the unit cell. From that, we can calculate
the total
Solve: Themass within the
arrangement unit in
of ions cell. Because we know the mass and can
calculate thethe
LiF is volume
same of
as the unit cell, we can then calculate density.
that in NaCl (Sample Exercise 11.7),
so a unit cell of
LiF contains
Density is mass per unit volume.

Thus, we can
calculate the density of LiF from
the mass contained
in a unit cell and the volume of the
unit cell. The
mass contained in one unit cell is
The volume of a cube of length a on

an edge is a3, so
the Chemistry:
volume Theof the
Central unit
Science, cell
Eleventh is (4.02
Edition Copyright ©2009 by Pearson Education, Inc.
Å) . We
3
By Theodore canH. now
E. Brown, Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy Upper Saddle River, New Jersey 07458
calculate the density, converting to
Calculate Density
Check: This value agrees with that found by simple density measurements,
2.640 g/cm3 at 20 °C. The size and contents of the unit cell are therefore
consistent with the macroscopic density of the substance.
Practice Exercise
The body-centered cubic unit cell of a particular crystalline form of iron
is 2.8664 Å on each side. Calculate the density of this form of iron.
Answer: 7.8753 g/cm3
Sample Integrative Exercise Putting Concepts Together
The substance CS2 has a melting point of –110.8 °C and a boiling point of
46.3 °C. Its density at 20 °C is 1.26 g/cm3. It is highly flammable. (a)
What is the name of this compound? (b) List the intermolecular forces that
CS2 molecules would have with each other. (c) Predict what type of
crystalline solid CS2(s) would form. (d) Write a balanced equation for the
combustion of this compound in air. (You will have to decide on the most
likely oxidation products.) (e) The critical temperature and pressure for
CS2 are 552 K and 78 atm, respectively. Compare these values with those
for CO2 (Table 11.5), and discuss the possible origins of the differences.
Solution
(f)
(a) Would you expect
The compound the density
is named carbon of CS2 at 40in°Canalogy
disulfide, to be greater
with theornaming
less
than at 20
of other °C? What
binary accounts
molecular for thesuch
compounds difference?
as carbon dioxide . (Section
2.8)
(b) Only London dispersion forces affect CS2; it does not have a dipole
moment, based upon its molecular shape, and obviously cannot undergo
hydrogen bonding.
(c) Because CS2(s) consists of individual CS2 molecules, it will be a
molecular solid.
(d) The most likely products of the combustion will be CO2 and SO2.
(Sections 3.2 and 7.8) Under some conditions SO3 might be formed, but
this would be the less likely outcome. Thus, we have the following
equation for combustion:
CS2(l) + 3 O2(g) → CO2(g) + 2 SO2(g)
(e) The critical temperature and pressure of CS2 (552 K and 78 atm) are
both higher
Chemistry: thanScience,
The Central those given
Eleventh Editionfor CO2 in Table 11.5 (304 K and ©2009
Copyright 73 atm).
by Pearson Education, Inc.
The With
difference in critical temperatures is especially notable. The
contributions from Patrick Woodward All rights reserved.
Sample Integrative Exercise Putting Concepts Together
(f) The density would be lower at the higher temperature. Density
decreases with increasing temperature because the molecules possess
higher kinetic energies. Their more energetic movements result in larger
average distances between molecules, which translate into lower
densities.
Closest-Packed Structures
First Layer
• With spheres, it is more efficient to offset each
row in the gaps of the previous row than to line
up rows and columns
Second Layer
• The second layer atoms can sit directly over the
atoms in the first layer– called an AA pattern
• Or the second layer can sit over the holes
in the first layer – called an AB pattern
Third Layer – with Offset 2nd Layer
• The third layer atoms can align directly over the
atoms in the first layer– called an ABA pattern
• Or the third layer can sit over the uncovered
holes in the first layer– called an ABC
pattern
Cubic Closest-Packed
Hexagonal Closest-Packed
Face-Centered Cubic
Hexagonal Closest-Packed
Structures
Cubic Closest-Packed Structures
Classifying Crystalline Solids
• Crystalline solids are classified by the kinds of

particles found
• Some of the categories are sub-classified by
the kinds of attractive forces holding the
particles together
Classifying Crystalline Solids
• Molecular solids are solids whose composite
particles are molecules
• Ionic solids are solids whose composite
particles are ions
• Atomic solids are solids whose composite
particles are atoms
 nonbonding atomic solids are held together by
dispersion forces
 metallic atomic solids are held together by metallic
bonds
 network covalent atomic solids are held together by
covalent bonds
Molecular Solids
• The lattice sites are occupied by molecules
 CO2, H2O, C12H22O11
• The molecules are held together by
intermolecular attractive forces
 dispersion forces, dipole–dipole attractions, and
H-bonds
• Because the attractive forces are weak, they
tend to have low melting points
 generally < 300 °C
Ionic Solids
• Lattice sites occupied by ions
• Held together by attractions between oppositely charged ions
 nondirectional
 therefore every cation attracts all anions around it, and vice-versa
• The coordination number represents the number of close
cation–anion interactions in the crystal
• The higher the coordination number, the more stable the solid
 lowers the potential energy of the solid
• The coordination number depends on the relative sizes of the
cations and anions that maintains charge balance
 generally, anions are larger than cations
 the number of anions that can surround the cation is limited by the
size of the cation
 the closer in size the ions are, the higher the coordination number is
Ionic Crystals
CsCl NaCl
coordination number = 8 coordination number = 6
Cs+ = 167 pm Na+ = 97 pm
Cl─ = 181 pm Cl─ = 181 pm
Lattice Holes
Tetrahedral
Hole
Octahedral
Hole
Simple Cubic
Hole
Lattice Holes
• In hexagonal closest-packed or cubic closest-
packed lattices there are eight tetrahedral holes
and four octahedral holes per unit cell
• In a simple cubic lattice there is one cubic hole
per unit cell
• Number and type of holes occupied determines
formula (empirical) of the salt
= Octahedral
= Tetrahedral
Cesium Chloride Structures
• Coordination number = 8
• ⅛ of each Cl─ (184 pm) inside
the unit cell
• Whole Cs+ (167 pm) inside the
unit cell
 cubic hole = hole in simple
cubic arrangement of Cl─ ions
• Cs:Cl = 1: (8 x ⅛), therefore
the formula is CsCl
Rock Salt Structures
• Cl─ ions (181 pm) in a face-centered
cubic arrangement
 ⅛ of each corner Cl─ inside the unit cell
 ½ of each face Cl─ inside the unit cell
• Na+ (97 pm) in holes between Cl─
 octahedral holes
 1 in center of unit cell
 1 whole particle in every octahedral hole
 ¼ of each edge Na+ inside the unit cell
• Na:Cl = (¼ x 12) + 1: (⅛ x 8) + (½ x 6)
= 4:4 = 1:1,
• Therefore the formula is NaCl
Zinc Blende Structures
• S2─ ions (184 pm) in a face-centered
cubic arrangement
 ⅛ of each corner S2─ inside the unit cell
 ½ of each face S2─ inside the unit cell
• Each Zn2+ (74 pm) in holes between
S2─
 tetrahedral holes
 1 whole particle in ½ the holes
• Zn:S = (4 x 1) : (⅛ x 8) + (½ x 6) =
4:4 = 1:1,
• Therefore the formula is ZnS
Fluorite Structures
• Ca2+ ions (99 pm) in a face-centered
cubic arrangement
 ⅛ of each corner Ca2+ inside the unit cell
 ½ of each face Ca2+ inside the unit cell
• Each F─ (133 pm) in holes between
Ca2+
 tetrahedral holes
 1 whole particle in all the holes
• Ca:F = (⅛ x 8) + (½ x 6): (8 x 1) =
4:8 = 1:2,
• Therefore the formula is CaF2
 fluorite structure common for 1:2 ratio
• Usually get the antifluorite structure
when the cation:anion ratio is 2:1
 the anions occupy the lattice sites and
the cations occupy the tetrahedral holes
Practice – Gallium arsenide crystallizes in a cubic
closest-packed array of arsenide ions with gallium ions
in ½ the tetrahedral holes. What is the ratio of gallium
ions to arsenide ions in the structure and the empirical
formula of the compound?
As = cpp = 4 atoms per unit cell

Ga = ½ (8 tetrahedral holes per unit cell)
Ga = 4 atoms per unit cell
Ga:As = 4 atoms :4 atoms per unit cell = 1:1
The formula is GaAs
Nonbonding Atomic Solids
• Noble gases in solid form
• Solid held together by weak dispersion forces
 very low melting
• Tend to arrange atoms in closest-packed
structure
 either hexagonal cp or cubic cp
 maximizes attractive forces and minimizes energy
Metallic Atomic Solids
• Solid held together by metallic bonds

 strength varies with sizes and charges of cations
coulombic attractions
• Melting point varies
• Mostly closest-packed arrangements of the
lattice points
 cations
Metallic Structure
Metallic Bonding
• Metal atoms release their valence
electrons
• Metal cation “islands” fixed in a “sea” of
mobile electrons
+ + + + + + + + +
e- e- e- e- e- e- e- e-
+ + + + + + + + +
e- e- e- e- e- e- e- e-
+ + + + + + + + +
Network Covalent Solids
• Atoms attached to their nearest neighbors by
covalent bonds
• Because of the directionality of the covalent
bonds, these do not tend to form closest-packed
arrangements in the crystal
• Because of the strength of the covalent bonds,
these have very high melting points
 generally > 1000 °C
• Dimensionality of the network affects other
physical properties
The Diamond Structure:
a 3-Dimensional Network
• The carbon atoms in a diamond each have four
covalent bonds to surrounding atoms
 sp3
 tetrahedral geometry
• This effectively makes each crystal one giant
molecule held together by covalent bonds
 you can follow a path of covalent bonds from any
atom to every other atom
Properties of Diamond
• Very high melting point, ~3800 °C
 need to overcome some covalent bonds
• Very rigid
 due to the directionality of the covalent
bonds
• Very hard
 due to the strong covalent bonds holding
the atoms in position
 used as abrasives
• Electrical insulator
• Thermal conductor
 best known
• Chemically very nonreactive
The Graphite Structure:
a 2-Dimensional Network
• In graphite, the carbon atoms in a sheet are
covalently bonded together
 forming six-member flat rings fused together
 similar to benzene
 bond length = 142 pm
 sp2
 each C has three sigma and one pi bond
 trigonal-planar geometry
 each sheet a giant molecule
• The sheets are then stacked and held together by
dispersion forces
 sheets are 341 pm apart
Properties of Graphite
• Hexagonal crystals
• High melting point, ~3800 °C
 need to overcome some covalent bonding
• Slippery feel
 because there are only dispersion forces
holding the sheets together, they can slide
past each other
 glide planes
 lubricants
• Electrical conductor
 parallel to sheets
• Thermal insulator
• Chemically very nonreactive
Silicates
• ~90% of Earth’s crust

• Extended arrays of SiO
 sometimes with Al substituted for Si – aluminosilicates
• Glass is the amorphous form
Quartz
• SiO2 in pure form
 impurities add color
• 3-dimensional array of Si covalently bonded
to 4 O
 tetrahedral
• Melts at ~1600 °C
• Very hard
Micas
• There are various kinds of mica that have slightly
different compositions – but are all of the general
form X2Y4-6Z8O20(OH,F)4
 X is K, Na, or Ca or less commonly Ba, Rb, or Cs
 Y is Al, Mg, or Fe or less commonly Mn, Cr, Ti, Li, etc.
 Z is chiefly Si or Al but also may include Fe3+ or Ti
• Minerals that are mainly 2-dimensional arrays of Si
bonded to O
 hexagonal arrangement of atoms
• Sheets
• Chemically stable
• Thermal and electrical insulator
Practice – Pick the solid in each pair with the
highest melting point
a)a) KCl
KCl ionic SCl
SCl
2 molecular
2
b)b) C(s,graphite)
C(s, graphite)cov. network S8 molecular
c)c) KrKratomic KK metallic
d)d) SrClionic
SrCl2
2 SiO 2 (s,
SiO 2
quartz)
(s, quartz) cov. network
Band Theory
• The structures of metals and covalent network

solids result in every atom’s orbitals being
shared by the entire structure
• For large numbers of atoms, this results in a
large number of molecular orbitals that have
approximately the same energy; we call this an
energy band
Band Theory
• When two atomic orbitals combine they
produce both a bonding and an antibonding
molecular orbital
• When many atomic orbitals combine they
produce a band of bonding molecular orbitals
and a band of antibonding molecular orbitals
• The band of bonding molecular orbitals is
called the valence band
• The band of antibonding molecular orbitals is
called the conduction band
Molecular Orbitals of Polylithium
Band Gap
• At absolute zero, all the electrons will occupy
the valence band
• As the temperature rises, some of the electrons
may acquire enough energy to jump to the
conduction band
• The difference in energy between the valence
band and conduction band is called the band
gap
 the larger the band gap, the fewer electrons there
are with enough energy to make the jump
Types of Band Gaps and
Conductivity
Band Gap and Conductivity
• The more electrons at any one time that a substance has in
the conduction band, the better conductor of electricity it is
• If the band gap is ~0, then the electrons will be almost as
likely to be in the conduction band as the valence band and
the material will be a conductor
 metals
 the conductivity of a metal decreases with temperature
• If the band gap is small, then a significant number of the
electrons will be in the conduction band at normal
temperatures and the material will be a semiconductor
 graphite
 the conductivity of a semiconductor increases with temperature
• If the band gap is large, then effectively no electrons will be
in the conduction band at normal temperatures and the
material will be an insulator
Doping Semiconductors
• Doping is adding impurities to the semiconductor’s
crystal to increase its conductivity
• Goal is to increase the number of electrons in the
conduction band
• n-type semiconductors do not have enough
electrons themselves to add to the conduction
band, so they are doped by adding electron-rich
impurities
• p-type semiconductors are doped with an
electron-deficient impurity, resulting in electron
“holes” in the valence band. Electrons can jump
between these holes in the valence band, allowing
conduction of electricity.
Diodes
• When a p-type semiconductor adjoins an n-type

semiconductor, the result is an p-n junction
• Electricity can flow across the p-n junction in
only one direction – this is called a diode
• This also allows the accumulation of electrical
energy – called an amplifier

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• The attractions between molecules are not nearly as

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For molecules of approximately equal mass

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and the heat of fusion of vaporization is heat. Forces

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Relationships: T(K) = T(°C) + 273.15

Given: 12.0 g benzene, seg 1 =(T0.2325

Conceptual Seg 231 g mol

DHfus 9.8 kJ/mol, 1 mol = 78.11 g, 1 kJ = 1000 J, q = m∙Cs∙DT

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• Note the high critical

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• Unusual feature for water:

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• Unusual features for

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• Some substances do not go directly from the

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Conceptual fcc mass r l V

fcc = 4 atoms/uc, Al = 26.982 g/mol, 1 mol = 6.022 x 10 23 atoms

Check: the accepted density of Al at 20°C is 2.71 g/cm3, so the

Conceptual bcc mass r l V

bcc = 2 atoms/uc, Rb = 85.47 g/mol, 1 mol = 6.022 x 10 23 atoms

Check: the accepted density of Rb at 20°C is 1.53 g/cm3, so the answer

Thus, the unit cell contains

Check: Since individually the ions

Density is mass per unit volume.

The volume of a cube of length a on

Density is mass per unit volume.

The volume of a cube of length a on

• Crystalline solids are classified by the kinds of

As = cpp = 4 atoms per unit cell

• Solid held together by metallic bonds

• ~90% of Earth’s crust