INTERMOLECULAR FORCES

AND CONDENSED STATES

I. Intermolecular Forces
A. Types of Intermolecular Forces.
1. Van der Waals forces = attractive forces that exist between neutral molecules.
a. Are much weaker than the intramolecular force of the covalent bond.( 150 - 1100 kJ/mol)
b. Weaker than ion-ion forces (Lattice energies, 200 - 4000 kJ/mol)
2. Dipole-dipole forces.
a. Exist between polar molecules. Due to the attraction of the negative end of one dipole
and the positive end of another.
b. Vary as 1/d2 ( d = distance ). Fairly strong ( 5-25 kJ/mol), should depend on the dipole
moments of the molecules.
c. Especially important in understanding the behavior of small polar molecules.
3. Dipole-induced dipole forces.
a. The permanent dipole in one molecule can distort, or polarize, the electron density in a
neighboring molecule creating, or inducing, a dipole. The resulting force of attraction is called
dipole-induced dipole attraction. It can take place between a polar and a nonpolar molecule
or between two polar molecules.

- +

polar molecule nonpolar molecule

Polarization

+ - +
-
dipole induced dipole

dipole - induced dipole

! attraction

b. These forces of attraction will increases as the polarizability of the molecule increases.
The polarizability is a measure of the ease of distortion of the electron density of a molecule.
c. The polarizability increases as

1
 1) the number of electrons increases.
2) the size of the molecule increases
d. Forces ∝ 1/r6 and are fairly weak (2-10 kJ/mol).
They are important in that they are responsible for the solubility of nonpolar gases,
such as O2 in polar solvents, such as water.
4. Induced dipole-induced dipole forces (London dispersion forces).
a. A dipole created by an instantaneous asymmetry in the electron density of one molecule can
induce a dipole in a neighboring molecule, giving rise to a force of attraction.
b. Example.
Consider two He atoms. Each He has two electron in spherically symmetric 1s orbitals.
However, it is possible to have an instantaneous asymmetry in the electron density of
one of the He atoms. This will induce an asymmetry in neighboring He atoms. If the
electrons move in a synchronous manner, there will always be a weak attractive force
between the He atoms.

+2

Symmetric
He 1s 2

+ -- + -
+
- -
+
+2 +2
+
- + -
+
+ - + -
Instantaneous Dipole Induced dipole
Induced Dipole - Induced Dipole
Attraction
This type of attractive forces are called London Dispersion Forces or Induced Dipole-
Induced Dipole forces.

2
 c. Such forces should increase as the polarizabilities of the molecules increase. It is
found in all molecules, polar and nonpolar. It is the only type of attractive forces
that exist between nonpolar molecules. Forces ∝ 1/d6 (0.05-40 kJ/mol).
5. Hydrogen Bonding.
a. Special force of attraction that exists between unshielded nuclear charge on a H,
when it is covalently bonded to an O, N or F and the lone pair of electrons on a
neighboring O, N, or F.
Range is 10-40 kJ/mol. This is in addition to the other van der Waals forces.
b. F, O, and N are the three most electronegative elements in the Periodic Table and are
also the smallest members of their respective groups. Therefore any lone pairs on
these atoms will be in small concentrated orbitals.
1) When these electronegative elements form covalent bonds with hydrogen, the
electron density in the bonds will be greatly polarized away from the H atom.
2) Since H has only one electron (no core electrons) the polarization of the bonds will
mean that the side of the H opposite a bond to F, O, or N will be greatly depleted of
electron density, leaving an unshielded, "bare", nucleus.
3) The hydrogen bond arises from and attraction of a lone pair on F, O, or N with the
unshielded nuclear charge on hydrogen (due to its covalent bonding to another F, O,
or N).
c. Hydrogen bonding is unique for H bonded to F, O, or N. It is in addition to any dipole-
dipole, dipole-induced dipole or London forces. There are geometric constraints on the
atoms involved in hydrogen bonding.
X−H ------- : X (X = F, O, or N)
Hydrogen Bond Lone Pair
d. Some examples of molecules that undergo hydrogen bonding in their pure states (the
hydrogen atoms capable of undergoing hydrogen bonding are in bold).

O H O
|| | ||
CH3C-O-H CH3N-H H-C-O-H H2O HF NH3.

3
 Liquid State

I. Properties of Liquids.
A. Kinetic Molecular Theory and its Application to Liquids.
1. In liquid state molecules cannot move independently of one another. Molecules
condense together and can move only in the body of the liquid.
a. Because of the motion collisions take place and there is a distribution of kinetic
energies much like that in gases.
b. The average kinetic energy per mole is much less than that required to
overcome attractive forces and go into the gas phase.
However, at any instant in time a certain fraction of molecules will have
sufficient kinetic energy to escape into the gaseous state
If such a high energy molecule is on the surface, it can escape from the liquid
and go into the gas phase.
c. This process is called evaporation.
1) Evaporation is a surface phenomenon.
2) Evaporation is a cooling process. The high kinetic energy molecules leave
which lowers the average kinetic energy per mole, and hence the temperature.
2. Evaporation in a closed container--Vapor Pressure.
a. In a closed container, as evaporation puts more molecules in the vapor phase above the
liquid, the probability that a gas molecule, through random collision, will end up back
in the liquid state increases.
b. Therefore, as evaporation continues, the rate of condensation will increase. A point
will be reached when the rate of evaporation = rate of condensation. At this point a
dynamic equilibrium is established and the concentration of vapor molecules above
the liquid will reach a constant value.
c. The partial pressure of vapor above the liquid will therefore reach a constant value,
called the equilibrium vapor pressure of the liquid (or the vapor pressure).
This is the same pressure that is required to liquefy the gas at the particular
temperature.
It is independent of the size of the container but increases as the temperature increases.
d. Boiling point = the temperature at which the vapor pressure equals atmospheric
pressure. At that temperature evaporation can take place in the body of the liquid and
the phenomenon of boiling takes place.

4
 Normal boiling point = temperature at which the vapor pressure is equal to 1 atm
(760 Torr)
e. Substances having strong intermolecular forces of attraction (having large values of a
in the van der Waals equation, high critical temperatures and critical pressures) will
have low vapor pressures and high normal boiling points.
B. Variation of Vapor Pressure with Temperature -- The Clausius-Clapeyron Equation.
1. Consider the equilibrium at constant pressure
Liquid Vapor
a. ΔH for this process = Molar heat of vaporization = ΔHvap
b. The partial pressure of the vapor in equilibrium with the liquid is
ΔHvap
lnP = - RT + B
where B is a temperature independent constant. This equation is called
the Clausius-Clapeyron Equation.
1
2. ΔHvap is always positive (evaporation is endothermic), therefore, a plot of lnP vs. T
ΔHvap
will be a straight line with a slope of - R , that is, a negative slope.
a. A convenient form of the equation for calculations is
P2 ΔHvap
ln ( P1 ) = - R [ T12 - T11 ]
b. Example. The molar heat of vaporization of H2O is 40.79 kJ/mol and its normal boiling
point is 100.0 °C. Calculate the vapor pressure of H2O at 27.0 °C.
P2 = 760 Torr T2 = 100.0 + 273.1 = 373.1 K
P1 = ? T1 = 27.0 + 273.1 = 300.1 K
760 40.79 1 1
ln( P1 ) = - 8.314x10-3 [ 373.1 - 300.1 ] = 3.199
760 3.199 = 24.5
P1 = e
760
P1 = 24.5 = 31.0 Torr.
The actual vapor pressure of H2O at 27 °C = 27.0 Torr. The discrepancy is due to the
fact that ΔHvap is not exactly temperature independent.

C. Other Properties.

5
 1. Surface Tension, γ.
a. A molecule in the bulk liquid is stabilized by the attraction of the other liquid
molecules. Therefore, a molecule on the surface will be at a higher energy than one
in the bulk of the liquid.
b. Surface tension = excess energy per unit area of the surface = force required to stretch
the surface of the liquid per unit area. Dimensions of γ are Newton/meter.
c. Surface tension is responsible for the rise of a liquid such as H2O in a thin glass
capillary (water "wets" or adheres to glass). This also gives rise to a meniscus when
water or an aqueous solution is in a pipette or a burette.
d. Surface tension should be large for a liquid having high attractive forces.
2. Viscosity.
a. Viscosity is the resistance to flow of a liquid.
b. When a liquid flows down a tube, the molecules slide over one another. The higher
the forces of attraction, the less of a tendency the liquid will have to flow, and the
higher will be the viscosity.
c. Viscosity will also depend on the size and shape of the molecules.
3. The following Table lists some properties as some common liquids.
Properties of Liquids.
Liquid NBP,°C ΔHvap(kJ/mol) γ (N/m) Viscosity (centipoise)
Ethyl Ether 34.5 26.0 17.0x103 0.222
(CH3OCH3)
Methanol 65.0 37.4 22.6x103 0.547
(CH3OH)
Ethanol 78.5 39.2 22.8x103 1.100
(CH3CH2OH)
Benzene 80.1 33.9 28.9x103 0.608
(C6H6)
Water 100.0 40.7 72.8x103 0.890
(HOH)
II. Intermolecular Attraction.
A. General intermolecular attractive forces.
1. The intermolecular forces that exist in the liquid state are the same as found among gases.
a. Dipole-dipole forces.
b. Dipole-induced dipole forces.
c. Induced dipole-induced dipole (London dispersion) forces

2. The first two are important in polar liquids while the last one exists in all liquids.

6
 3. In some liquids, such as H2O, hydrogen bonding is also important.
B. Effects of Hydrogen Bonding on the Properties of Water.
1. Abnormally high melting points, boiling points, and ΔHvap.
a. Compared to the other group 16 hydrides, H2O has unusually high melting and
boiling points.
b. NH3 and HF also show these abnormalities.
2. The density of H2O(s) is less than that of H2O(l).
a. In H2O(s) each O is tetrahedrally surrounded by four H's; two are covalently bonded
and two are hydrogen bonded.
b. Because of the orientation requirements imposed by hydrogen bonding, the H2O
molecules are not packed together in ice in the spatially most efficient way.
c. When ice melts, the hydrogen bonds are broken and the ice lattice structure collapses
in on itself. Therefore, the density increases.
3. Between 0°C and 4°C, the density of H2O(l) increases as the temperature increases.
a. For most substances density decreases as the temperature increases ( things expand on
heating).
b. In H2O(l) between 0 and 4°C there are still large domains of water molecules
involved in ice-like hydrogen bonded structures. As the temperature increases from 0
to 4°C,these domains are progressively broken down and the liquid contracts. The
maximum density occurs at 3.98°C (1.000 g/ml), as the temperature increases from
this point, the natural tendency of a substance to expand on heating dominates and the
density decreases.
4. Other Effects.
a. Protein Structure.
Hydrogen bonding is one of the main forces stabilizing the α-helix structure of
proteins.
b. Genetic Code.
Base pair recognition in DNA and RNA is through hydrogen bonding.

7
 Phase Diagrams
I. Phase Diagram.
A. Diagrams on a pressure vs. temperature scale that show the conditions under which a phase
will be stable or in equilibrium with other phases.
B. Phase diagram of H2O (not to scale).
Consists of three areas that are divided by lines (A-O, O-B, and O-C) that intersect at a

point (point O).

C
B
760
Pressure, Torr

Liquid

Solid

O
4.58 Vapor

0 0.01 Temperature, o C 100

1. Areas. At any temperature and pressure that falls in an area, only one phase is stable.
Any other phase will spontaneously convert to the particular stable phase.
2. Lines. Delineate temperatures and pressures in which two phases are in equilibrium.
a. Line A-O. H2O(s) H2O(g)
1) A plot of the sublimation pressure of the solid as a function of temperature.
2) Governed by a Clausius-Clapeyron type of equation.

!Hsub !Ssub
lnP = - +
RT R
ΔHsub = ΔHvap + ΔHfus

8
 b. Line O-B. H2O(l) H2O(g)
1) A plot of the vapor pressure of the liquid as a function of temperature, or a plot
of the boiling point of the liquid as a function of pressure.
2) The plot is governed by the Clausius-Clepeyron equation. The line O-B stops at
the critical temperature and critical pressure of the substance.
c. Line O-C. H2O(s) H2O(l)
1) A plot of the freezing point of the liquid, or melting point of the solid, as a function
of pressure.
2) For H2O the freezing point decreases as the temperature increases. This is because
the density of H2O(s) is less than the density of H2O(l). This is predicted from
Le Chatelier's Principle (when a stress is placed on a system in equilibrium the
equilibrium will shift so as to counteract the stress). The molar volume of H2O(s)
is greater than that of H2O(l). Therefore, when pressure is applied the equilibrium
H2O(s) H2O(l) will shift to the side having the smaller molar volume,
that is, to the liquid and the temperature would have to be decreased in order to
reestablish equilibrium.
3. Point O. Triple Point.
a. At this temperature and pressure all three phases coexist in equilibrium, that is, the
melting point and the boiling point coincide. This is a unique point for a substance.
b. Note that the liquid phase can not exist at pressures below that of the triple point.
c. For H2O the pressure of the triple point is quite low, 4.58 Torr. However, the triple
point for CO2 is at 5.2 atm and -57 °C. Therefore, while ice melts on heating at normal
atmospheric pressure, CO2(s) will sublime, and hence the name "dry ice".

Crystalline State
I. Structure of Solids.
A. Crystal lattice.
1. Crystalline solids (true solids) are characterized by both short range and long range order.
a. The particles that make up the solid (ions, molecules, or atoms) are arranged in definite
repeating geometric patterns.
b. This internal order gives rise to an external order in that crystalline solids possess plane
faces that intersect at definite angles.
2. The internal geometric order can be shown by the crystal lattice (or space lattice).
a. The lattice is a network of lines connecting the centers of the particles that make up the
solid.
b. Shown below is a two dimensional array of spheres forming a monolayer "solid"

9
 and its corresponding lattice.

Solid

Lattice
3. Unit Cell.
a. It is not necessary to consider the complete space lattice. We are only interested in the
smallest part of the space lattice which, when repeated, will generate the complete
lattice. This is called the unit cell.
b. The unit cell is the smallest part of the space lattice (that is the solid) that has all the
properties of the solid. That is, it has
1) the same geometry or morphology as the solid.
2) the same stoichiometry as the solid.
3) the same density as the solid.
c. The unit cell can be determined experimentally from X-ray diffraction.
1) X-rays are scattered by the electrons of the atoms in a solid. The process acts like
the X-rays were being scattered (or diffracted) by the lines on a grating ( the "lines"
are the rows of atoms in the solid).
2) Depending on the wavelength of the X-rays, the angle of incidence of the X-ray

10
 beam, and the geometry of the solid, the diffracted beam could be in phase and are
detectable, or out of phase and not detectable. This gives rise to a diffraction
pattern.
3) By analyzing the diffraction pattern of the X-rays of a particular wavelength,
the structure of the solid, that is the unit cell, can be determined.
B. Systems of Unit Cells.
1. There are seven systems of unit cells. These are described in the following Figure.
We will be concerned only with the Cubic System.
2. In the cubic system the basic shape of the unit cell is that of a cube (all sides of equal
length and meeting at right angles). There are three unit cells in the cubic system.
a. Simple Cubic Unit Cell (Primitive Cubic).
1) The unit cell consists of eight particles, one at each of the corners of the unit cell.
2) Since each of the eight particles belong to eight unit cells, only 1/8 of each particle
is contained within a particular unit cell.
The total number of particles per simple cubic unit cell = 1/8(8) = 1
3) Therefore, there is one unit cell per particle. If one had a mole of a solid that
crystallized in a simple cubic unit cell, there would be 6.03x1023 unit cells in the
solid.
4) In a simple cubic unit cell the particles are in contact along the edge of the unit cell.
The radius of the particle, r, and the length of the unit cell, a, are related by
a
2r = a or r = 2
5) The simple cubic unit cell is rather rare in nature. The only metal crystallizing in
this unit cell is Po.
b. Body Centered Cubic (bcc) Unit Cell.
1) The unit cell consists of the eight particles at the corners plus another particle
directly in the center of the unit cell.
2) There are 1/8(8) + 1 = 2 particles per body centered cubic unit cell.
3) The particles are in contact along the diagonal of the cube. There are three particles
stacked along this diagonal.
Let d = the length of the diagonal; r = the radius of a particle and a = the length of
the edge of the unit cell. Then
2 2 2
d= a +a +a = 3 a

d = 4r
3
! 4r = 3 a or r = a
4

11
 4) Iron, among other metals, crystallize in a bcc unit cell.
c. Face Centered Cubic (fcc) Unit Cell.
1) The unit cell consists of the eight particles at the corners of the unit cell plus a
particle in the center of each of the six faces of the cube. Each particle on a face is
in common with two unit cells and contributes 1/2 per unit cell.
2) The unit cell contains 1/8(8) + 1/2(6) = 4 particles.
3) Contact between the particles is along the diagonal of the face of the cube.
Let d = the diagonal of a face; r = the radius of the particle; and a = the length of the
edge of the unit cell. Then

2 2
d= a +a = 2 a

4r = d
2
! 4r = 2 a or r = a
4
4) Al, Cu, Au, Ag, and many other substances, crystallize in a fcc unit cell.

C. Calculations on Cubic unit cells.

Aluminum (At. wt. = 27.0) crystallizes in a fcc unit cell and has a density of 2.7 g/cc.
Calculate,
1. the molar volume V .
27.0 g/mol
V = 2.7 g/cc = 10.0 cm3/mol
2. the cm3 per atom of Al.
10.0 cm3/mol
cm3 per atom = 6.02x1023 atoms/mol = 1.67x10-23 cm3/atom
3. the cm3 per unit cell, that is the volume of the unit cell, Vuc.
Vuc = (1.67x10-23 cm3/atom)(4 atoms/uc) = 6.7x10-23 cm3/uc
4. the length of the edge of the unit cell, a.
3
Vuc = a ! a = 3 Vuc

3 -23 3 -8
a= 6.7x10 cm = 4.05x10 cm = 405 pm
5. the radius of an Al atom, r.
In a fcc unit cell,
2 2
r= a= (405 pm) = 142 pm
4 4

12
II. Close Packing.
Many common metals and salts crystallize in structures that can be understood by considering
how spheres of equal size can be packed together in the spatially most efficient way possible.
This is called close packing.
A. They will stack in Layers.
1. First Layer (layer a).
a. Each sphere in the layer is touching six other spheres in that layer.
b. This layer is shown in Figure 1.
2. Second Layer (layer b).
a. Each sphere in this layer will come to rest in the crevice formed by the juncture of
three spheres in layer a (see Figure 2).
b. Each sphere is then in contact with 12 other spheres,
6 in the same layer + 3 in the layer below + 3 in the layer above.
1) The number of nearest neighbor spheres (the number of spheres touching a
particular sphere) is called the coordination number (CN).
2) In close packing the coordination number = 12.
c. All space is not occupied by the spheres. There are holes, or cavities, between the
two layers. There are two types of such cavities.
1) Tetrahedral Cavities are formed by the juncture of three spheres in one layer and
one sphere in an adjacent layer (see Figure 3).
- If a particle were in this cavity it would be tetrahedrally coordinated by the four
spheres.
- They are the smaller of the two types of cavities.
- They are more numerous than the other type of cavity. The number of tetrahedral
holes twice is equal to the number of spheres in the close packed array (one cavity
above and below each sphere)
2) Octahedral Cavities are formed by the juncture of three spheres in one layer and
three spheres in an adjacent layer (see Figure 4).
- If a particle were in this cavity it would be octahedrally surrounded by the six
spheres.
- They are larger but less numerous than tetrahedral cavities.
- The number of octahedral cavities is equal to the number of spheres in the close
packed array.

13
First Layer Sphere

Second Layer Sphere

Figure 1. Layer a in a close packed array.

Figeue 2. Layers a and b in a close packed array.

Figure 3. Tetrahedral cav ities.

Figure 4. An octahedral cavity.

14
 3. Third Layer. There are two possibilities.
a. Spheres in the third layer cover tetrahedral holes.
1) When one third layer comes to rest over a tetrahedral hole, all other spheres in that
layer must cover tetrahedral holes. Every sphere in the third layer will be directly
over a sphere in the first layer. Therefore, the third layer is just a repeat of the first
layer, layer a.
2) When each succeeding layer covers tetrahedral cavities, the layer sequence is
ababab …
3) This type of close packing is called Hexagonal Close Packing (hcp). The unit
cell of the resulting solid is in the hexagonal system.
4) Examples of hcp solids are Zn, Cd, and H2(s).
b. Spheres in the third layer cover octahedral holes.
1) When one sphere comes to rest over an octahedral cavity, all other spheres in that
layer must cover octahedral cavities. The spheres in the third layer are not over
spheres in either the first or the second layer. This in a unique layer, called layer c.
2) When octahedral holes are covered by each succeeding layers, the layer sequence
is abcabcabc…
3) This type of close packing is called Cubic Close Packing (ccp). The unit cell is
face centered cubic.
4) Examples: Al, Cu, Ag, Au, and many others.
B. Structures of Ionic Compounds.
1. The structures of many ionic compounds can be understood in terms of one ion forming a
close packed array and the other ion occupying the one of the cavities in that array.
a. Since anions are larger than cations, most of the time, but not all the time, the anions
form the close packed array and the smaller cations are in the cavities.
b. In ionic compounds, The coordination number of an ion is defined as the
number of nearest neighbor counter-ions.
1) The coordination number of an ion in a tetrahedral cavity = 4.
2) The coordination number of an ion in a octahedral cavity = 6.
2. Examples.
a. NaCl (rock salt)
1) The Cl- ions form a ccp array and the Na+ ions occupy all the octahedral cavities in
the Cl- close packed array.
2) The coordination number of Na+ = 6
Since there are just as many Na+ ions as Cl- ions, there also must six Na+ ions
around each Cl-. Therefore, the coordination number of Cl- = 6. (NaCl could

15
 also be described as an array of close packed Na+ ions with the Cl- ions occupying
octahedral holes.)
3) Per unit cell there are 4 Cl- ions (the Cl- ions crystallize in a fcc unit cell) and 4
Na+ ions.
4) Many MX type salts crystallize in the NaCl structure. This is called the rock salt
structure or a 6:6 structure. The 6:6 refers to the coordination numbers of the cation
and anion, respectively.
b. Li2O
1) The O2- ions form a ccp array with the Li+ ions occupying all the tetrahedral
cavities in the O2- array.
2) The coordination number of Li+ = 4.
Since there are twice as many Li+ ions as there are O2- ions, there must be twice as
many Li+'s around an O2- as there are O2-'s around a Li+. Therefore the
coordination number of O2- = 8.
3) Per unit cell there are 4 O2- ions (O2- forms a fcc unit cell) and 8 Li+ ions.
4) This structure is called an antifluorite structure. The mineral fluorite, CaF2, has a
structure in which the Ca2+ ions are ccp and the F- ions occupy the tetrahedral
cavities.
c. MgAl2O4 (Spinel).
1) The O2- ions form a ccp array with the Mg2+ ions in the tetrahedral holes and the
Al3+ ions in octahedral holes.
2) Not all the cavities are occupied. Per formula unit there are four O2- ions which
gives rise to eight tetrahedral and four octahedral holes. Therefore, the Mg2+ ion
1 1
occupy only 8 of the tetrahedral and the Al3+ ions occupy 2 of the octahedral
cavities.
3) Per unit cell there are 4 O2- ions, 1 Mg2+ ion and 1 Al3+ ion.
4) This structure is called the spinel structure. There are a number of minerals of the
formula AB2O4 , where A is a divalent ion and B is a trivalent ion, that have the
spinel structure.
IV. Solid State Defects.
A. Defects in chemically pure substances.
1. Vacancies. Some of the lattice sites are not occupied.
2. Interstitials. Due to thermal motion, a particle can move into a type of cavity that is not
ordinarily occupied, an interstitial position. The introduction of these types of defects on
heating of a solid is important in determining the melting point of the solid.
3. Dislocations. The planes of atoms are not perfectly aligned.

16
 a. Edge dislocations. A plane of particles will not go all the way through the crystal.
b. Screw dislocation. The planes of particles are warped about an axis such that they form
a spiral like the pitch of a screw.
B. Chemical Impurities.
1. Nonstoichiometric solids.
a. These defects can occur in salts where the metal cation can exist in several oxidation
states. Some examples are TiO1.7-1.8 and Fe0.95O. Small amounts of the higher
oxidation state metal could replace the lower oxidation state metal in the lattice. In
order to maintain electrical neutrality, some metal sites must be vacant. For example,
Fe0.95O is due to the presence of Fe3+ being in some of the Fe2+ sites. There are also
some metal rich nonstiochiometric compounds, such as, Cu1.7S and Cu1.65Te.
b. Many of the heavier metal hydrides can have varying amounts of hydrogen. An
example is VH0.56 Other metals, such as, Fe, Pd, and Pt are permeable to hydrogen. It
is thought that hydrogen atoms diffuse through these metals by occupying interstitial
sites in the metal lattice.
2. Chemical doping - semiconductors.
a. n-type semiconductor.
1) Formed when small amounts of a group 15 element are introduced into a group 14
element's lattice. The group 14 solid is said to be doped with the group 15 element.
An example is Si doped with P
2) The Si is sp3 hybridized and forms covalent bonds with four other silicons. When a
P replaces a Si in this lattice, four of its valence electrons are involved in covalent
bonding while the extra P electron is free to move in the crystal. The doped Si then
becomes a good conductor of electricity.
b. p-type semiconductor.
1) Formed when a group 14 crystal is doped with a group 13 element. An example is
Si doped with B.
2) The B has only three valence electrons and when it replaces a Si atom in the Si
crystal there will be a vacancy of one electron or a "hole" into which a electron
from a neighboring bond could migrate. In this way the vacancy, or hole, could
move through the crystal in a direction opposite to that of electron motion; this will
have the effect of a "positive hole" moving through the crystal giving rise to p-type
semiconduction.

17
V. Types of Solids.
It is possible to classify solids not according to their structures, but according to the particles
occupying the lattice sites.

Molecular _Ionic Covalent __Metallic

Units that occupy Molecules Cations Atoms Metal cations
Anions in electron sea

Binding Forces Van der Waals Electrostatic Covalent Electrical

(dipole-dipole, attraction attraction between
London) + ions and - electrons

Properties Very soft Hard and Very Hard Hard to soft

brittle
Low melting High melting Very High Very variable
points points points melting points
Volatile
Good Insula- Good insula- Nonconduc- Good
tors tors tors conductors

Examples H2, H2O, NaCl, KBr, C(diamond), Na, K, Al,

CO2 Fe(NO3)2 Carborundum Fe
(SiC), Quartz
(SiO2)

18
 Condensed Phases

Problem Set
1. Consider the following diagram of the logarithm of the vapor pressure vs. the reciprocal
of the temperature for several substances. ( Note (l) = liquid, (s) = solid )

12
C(l)

10 B(l)
(P in torr)

8 C(s)
ln P

A(l)
6

4
.0020 .0025 .0030 .0035 .0040 .0045
1/T,K-1
a. Which liquid is the most volatile at 127 °C ? (liquid C)
b. At what temperature will liquid A abd B have the same vapor pressure ? (≈526 K)
c. Estimate the normal boiling point of A. (350 K)
d. Which liquid has the highest value of ΔHvap ? (liquid A)
e. Estimate the temperature and pressure of the triple point of C.(303 K, 3.63x104 Torr)
2. The vapor pressure of a liquid obeys the relation
4000
ln P = - + 7.881
T
where P is the vapor pressure in torr.
a. What is the value of ΔHvap for this liquid ? (3.33x104 J/mol)
b. What is the normal boiling point of the liquid ? (3206 K)

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3. The vapor pressure of a liquid is 5.2 torr at 25.0 °C and 35.6 torr at 40.0 °C. Calculate
a. the value of ΔHvap of the liquid.(9.95x104 J/mol)
b. The vapor pressure of the liquid at 60.0 °C. (353 Torr)
4. Consider the following liquids: C6H6, CH4, C6H5Cl, CH3Cl. Arrange the liquids in order of
a. increasing normal boiling points. (CH4<C6H6<CH3Cl<C6H5Cl)
b. increasing surface tension. (CH4<C6H6<CH3Cl<C6H5Cl)
c. decreasing ΔHvap. (C6H5Cl>CH3Cl>C6H6>CH4)
d. increasing vapor pressure at 25 °C. (C6H5Cl<CH3Cl<C6H6<CH4)
5. Of the two isomers of dichlorobenzene shown below, which one will have the higher
viscosity ? ( Justify your answer)
Cl Cl
Cl

Cl
1,4-dichlorobenzene 1,2-dichlorobenzene
(1,2-dichlorobenzene)
6. Of the two compounds CH3OCH3 and CH3CH2OH, which one will have the highest
normal boiling point ?( Justify your answer ) (CH3CH2OH)

7. Silver crystallizes in a face centered cubic unit cell, the length of the edge of the unit
cell
is 408.7 pm. Calculate the density of silver. (10.5 g/cc)
8. Gold has a radius of 144 pm and crystallizes in a body centered cubic unit cell.
Calculate
the density of gold. (17.79 g/cc)
9. Barium metal has a density of 3.50 g / cm3 and an atomic radius of 220 pm. In what type
of cubic unit cell does Barium crystallize ? (bcc)
10. The salt CuI was studied and the following facts were obtained:
a) The I- ions form a cubic close packed array.
b) The Cu+ ions are in cavities that give rise to a coordination number of 4.
a. What type of cavities in the I- array do the Cu+ ions occupy ? What fraction of these
cavities are occupied by the Cu+ ions?
b. The arrangement of layers of I- ions is described by the letter sequence __________ .
c. In forming the particular lattice the third layer of I- ions will cover what type of cavity?
d. What is the coordination number of I-?
e. If the coordination number of Cu+ had been 6, what type of cavity would it occupy in the
I- array? What would be the coordination number I- under these conditions?
f. Of the two types of cavities in the I- array, ______________ is the larger and ___________

20
 is the more numerous one.
g.Per unit cell, there are ________ I- ions and _________ Cu+ ions.

11. Shown below is a representation of the first two layers in a close packed array. (The solid
circles are in the first layer.)

a. Two types of cavities exist in this lattice. Identify several of these using "O' for octahedral
and "T" for tetrahedral.
b. Over what type of cavity would the third layer be located if the lattice were cubic ? If the
lattice were hexagonal close packed?
12. The usual geometric picture drawn of the octahedral arrangement of six groups about a central
point is shown below. For one of the octahedral holes in the above diagram, label the
surrounding spheres a, b, c, d, e,and f to indicate how they fit the drawing below.
e

b hole d

21
13. Consider the following substances in their solid state.
NO2 N2 CaO Cu SiO2
Listed below are a number of statements. By each statement write the formula of the above
substance that is best described by the statement.
a. Is a good conductor in the liquid state but not in the solid state.
b. Has the lowest melting point.
c. Has the highest melting point.
d. At any particular temperature will have the highest vapor pressure.
e. Crystal lattice is stabilized by dipole and London forces only.
f. Lattice points occupied by ions.
g. Crystal lattice stabilized by covalent bonds.

14. The mineral perovskite has a structure in which Ca2+ ions occupy the corners of a cubic unit
cell, O2- ions are in the centers of each of the faces, and a Ti4+ is at the center of the cell.
What is the formula of perovskite.

15. On the folowing page is a phase diagram for a hypothetical substance.

a. On the diagram label the regions in which the solid, liquid, and vapor phases would be
stable.
b. Give the temperature and pressure of the triple point.
c. Which line represents a plot of the sublimation pressure of the solid as a function of
temperature ?
d. Which line represents a plot of the vapor pressure of the liquid as a function of temperature ?
e. What is the normal boiling point of the substance ?
f. Suppose you have a sample of this substance at 0.8 atm and 20 °C. Describe what would
happen if you heated the substance to 120 °C at a constant pressure of 0.8 atm. Give the
temperatures of any phase changes that may occur during the heating process.
g. Do the same as in (f) when the pressure is 0.4 atm.
h. Which would be greater, the density of the solid or the density of the liquid? Justify your
answer.

22
 C

1.0
B
Pressure, atm

0.5
O

20 40 60 80 100 120
Temperature, o C

Answers 10-16

10. a. Tetrahedral b. abcabcabc... c. Octahedral d. 4 e. Octahedral, 6 f. Octahedral,

Tetrahedra; g. 4,4
11. a. see notes. b. Octahedral. Tetrahedral.
13. a. CaO b. N2 c. SiO2 d. N2 e. NO2 f. CaO & Cu g. SiO2
14. CaTiO3
15. b. triple point: 32 °C & 0.5 atm c. AO d. OB e. 120 °C f. melts at 32 °C, boils at 96 °C
g. sublimes at 23 °C h. dsolid = dliquid since OC is essentially vertical.

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