Exciting electrons from the filled valence band to the empty conduction band causes an increase in electrical conductivity

for two
reasons:
1. The electrons in the previously vacant conduction band are free to migrate through the crystal in response to an applied electric
field.
2. Excitation of an electron from the valence band produces a “hole” in the valence band that is equivalent to a positive charge.
The hole in the valence band can migrate through the crystal in the direction opposite that of the electron in the conduction band
by means of a “bucket brigade” mechanism in which an adjacent electron fills the hole, thus generating a hole where the second
electron had been, and so forth.
Consequently, Si is a much better electrical conductor than diamond, and Ge is even better, although both are still much poorer
conductors than a typical metal (Figure 11.7.4).

Figure 11.7.4 : A Logarithmic Scale Illustrating the Enormous Range of Electrical Conductivities of Solids
Substances such as Si and Ge that have conductivities between those of metals and insulators are called semiconductors. Many
binary compounds of the main group elements exhibit semiconducting behavior similar to that of Si and Ge. For example, gallium
arsenide (GaAs) is isoelectronic with Ge and has the same crystalline structure, with alternating Ga and As atoms; not surprisingly,
it is also a semiconductor. The electronic structure of semiconductors is compared with the structures of metals and insulators in
Figure 11.7.5.

Figure 11.7.5 : A Comparison of the Key Features of the Band Structures of Metals, Semiconductors, and Insulators. Metallic
behavior can arise either from the presence of a single partially filled band or from two overlapping bands (one full and one
empty).

Temperature and Conductivity

Because thermal energy can excite electrons across the band gap in a semiconductor, increasing the temperature increases the
number of electrons that have sufficient kinetic energy to be promoted into the conduction band. The electrical conductivity of a
semiconductor therefore increases rapidly with increasing temperature, in contrast to the behavior of a purely metallic crystal. In a
metal, as an electron travels through the crystal in response to an applied electrical potential, it cannot travel very far before it
encounters and collides with a metal nucleus. The more often such encounters occur, the slower the net motion of the electron
through the crystal, and the lower the conductivity. As the temperature of the solid increases, the metal atoms in the lattice acquire
more and more kinetic energy. Because their positions are fixed in the lattice, however, the increased kinetic energy increases only

11.7.4 [Link]
the extent to which they vibrate about their fixed positions. At higher temperatures, therefore, the metal nuclei collide with the
mobile electrons more frequently and with greater energy, thus decreasing the conductivity. This effect is, however, substantially
smaller than the increase in conductivity with temperature exhibited by semiconductors. For example, the conductivity of a
tungsten wire decreases by a factor of only about two over the temperature range 750–1500 K, whereas the conductivity of silicon
increases approximately 100-fold over the same temperature range. These trends are illustrated in Figure 11.7.6.

Figure 11.7.6 : The Temperature Dependence of the Electrical Conductivity of a Metal versus a Semiconductor. The conductivity of
the metal (tungsten) decreases relatively slowly with increasing temperature, whereas the conductivity of the semiconductor
(silicon) increases much more rapidly.

n- and p-Type Semiconductors

Doping is a process used to tune the electrical properties of commercial semiconductors by deliberately introducing small amounts
of impurities. If an impurity contains more valence electrons than the atoms of the host lattice (e.g., when small amounts of a group
15 atom are introduced into a crystal of a group 14 element), then the doped solid has more electrons available to conduct current
than the pure host has. As shown in Figure 11.7.7a, adding an impurity such as phosphorus to a silicon crystal creates occasional
electron-rich sites in the lattice. The electronic energy of these sites lies between those of the filled valence band and the empty
conduction band but closer to the conduction band. Because the atoms that were introduced are surrounded by host atoms, and the
electrons associated with the impurity are close in energy to the conduction band, those extra electrons are relatively easily excited
into the empty conduction band of the host. Such a substance is called an n-type semiconductor, with the n indicating that the added
charge carriers are negative (they are electrons).

Figure 11.7.7 : Structures and Band Diagrams of n-Type and p-Type Semiconductors. (a) Doping silicon with a group 15 element
results in a new filled level between the valence and conduction bands of the host. (b) Doping silicon with a group 13 element
results in a new empty level between the valence and conduction bands of the host. In both cases, the effective band gap is
substantially decreased, and the electrical conductivity at a given temperature increases dramatically.
If the impurity atoms contain fewer valence electrons than the atoms of the host (e.g., when small amounts of a group 13 atom are
introduced into a crystal of a group 14 element), then the doped solid has fewer electrons than the pure host. Perhaps unexpectedly,
this also results in increased conductivity because the impurity atoms generate holes in the valence band. As shown in Figure
11.7.7 b, adding an impurity such as gallium to a silicon crystal creates isolated electron-deficient sites in the host lattice. The

electronic energy of these empty sites also lies between those of the filled valence band and the empty conduction band of the host
but much closer to the filled valence band. It is therefore relatively easy to excite electrons from the valence band of the host to the
isolated impurity atoms, thus forming holes in the valence band. This kind of substance is called a p-type semiconductor, with the p
standing for positive charge carrier (i.e., a hole). Holes in what was a filled band are just as effective as electrons in an empty band
at conducting electricity.

11.7.5 [Link]
The electrical conductivity of a semiconductor is roughly proportional to the number of charge carriers, so doping is a precise way
to adjust the conductivity of a semiconductor over a wide range. The entire semiconductor industry is built on methods for
preparing samples of Si, Ge, or GaAs doped with precise amounts of desired impurities and assembling silicon chips and other
complex devices with junctions between n- and p-type semiconductors in varying numbers and arrangements.
Because silicon does not stand up well to temperatures above approximately 100°C, scientists have been interested in developing
semiconductors made from diamonds, a more thermally stable material. A new method has been developed based on vapor
deposition, in which a gaseous mixture is heated to a high temperature to produce carbon that then condenses on a diamond kernel.
This is the same method now used to create cultured diamonds, which are indistinguishable from natural diamonds. The diamonds
are heated to more than 2000°C under high pressure to harden them even further. Doping the diamonds with boron has produced p-
type semiconductors, whereas doping them with boron and deuterium achieves n-type behavior. Because of their thermal stability,
diamond semiconductors have potential uses as microprocessors in high-voltage applications.

 Example 11.7.1

A crystalline solid has the following band structure, with the purple areas representing regions occupied by electrons. The
lower band is completely occupied by electrons, and the upper level is about one-third filled with electrons.

a. Predict the electrical properties of this solid.

b. What would happen to the electrical properties if all of the electrons were removed from the upper band? Would you use a
chemical oxidant or reductant to effect this change?
c. What would happen to the electrical properties if enough electrons were added to completely fill the upper band? Would
you use a chemical oxidant or reductant to effect this change?
Given: band structure
Asked for: variations in electrical properties with conditions
Strategy:
A. Based on the occupancy of the lower and upper bands, predict whether the substance will be an electrical conductor. Then
predict how its conductivity will change with temperature.
B. After all the electrons are removed from the upper band, predict how the band gap would affect the electrical properties of
the material. Determine whether you would use a chemical oxidant or reductant to remove electrons from the upper band.
C. Predict the effect of a filled upper band on the electrical properties of the solid. Then decide whether you would use an
oxidant or a reductant to fill the upper band.
Solution:
A. The material has a partially filled band, which is critical for metallic behavior. The solid will therefore behave like a metal,
with high electrical conductivity that decreases slightly with increasing temperature.
B. Removing all of the electrons from the partially filled upper band would create a solid with a filled lower band and an
empty upper band, separated by an energy gap. If the band gap is large, the material will be an electrical insulator. If the gap
is relatively small, the substance will be a semiconductor whose electrical conductivity increases rapidly with increasing
temperature. Removing the electrons would require an oxidant because oxidants accept electrons.
C. Adding enough electrons to completely fill the upper band would produce an electrical insulator. Without another empty
band relatively close in energy above the filled band, semiconductor behavior would be impossible. Adding electrons to the
solid would require a reductant because reductants are electron donors.

11.7.6 [Link]
  Exercise 11.7.1

A substance has the following band structure, in which the lower band is half-filled with electrons (purple area) and the upper
band is empty.

a. Predict the electrical properties of the solid.

b. What would happen to the electrical properties if all of the electrons were removed from the lower band? Would you use a
chemical oxidant or reductant to effect this change?
c. What would happen to the electrical properties if enough electrons were added to completely fill the lower band? Would
you use a chemical oxidant or reductant to effect this change?
Answer:
a. The solid has a partially filled band, so it has the electrical properties of a conductor.
b. Removing all of the electrons from the lower band would produce an electrical insulator with two empty bands. An oxidant
is required.
c. Adding enough electrons to completely fill the lower level would result in an electrical insulator if the energy gap between
the upper and lower bands is relatively large, or a semiconductor if the band gap is relatively small. A reductant is required.

Metallic behavior requires a set of delocalized orbitals and a band of allowed energy levels that is partially occupied.
The electrical conductivity of a semiconductor increases with increasing temperature, whereas the electrical conductivity of
a metal decreases with increasing temperature.
n-Type semiconductors are negative charge carriers; the impurity has more valence electrons than the host. p-Type
semiconductors are positive charge carriers; the impurity has fewer valence electrons than the host.

Summary
Band theory assumes that the valence orbitals of the atoms in a solid interact to generate a set of molecular orbitals that extend
throughout the solid; the continuous set of allowed energy levels is an energy band. The difference in energy between the highest
and lowest allowed levels within a given band is the bandwidth, and the difference in energy between the highest level of one band
and the lowest level of the band above it is the band gap. If the width of adjacent bands is larger than the energy gap between them,
overlapping bands result, in which molecular orbitals derived from two or more kinds of valence orbitals have similar energies.
Metallic properties depend on a partially occupied band corresponding to a set of molecular orbitals that extend throughout the
solid to form a band of energy levels. If a solid has a filled valence band with a relatively low-lying empty band above it (a
conduction band), then electrons can be excited by thermal energy from the filled band into the vacant band where they can then
migrate through the crystal, resulting in electrical conductivity. Electrical insulators are poor conductors because their valence
bands are full. Semiconductors have electrical conductivities intermediate between those of insulators and metals. The electrical
conductivity of semiconductors increases rapidly with increasing temperature, whereas the electrical conductivity of metals
decreases slowly with increasing temperature. The properties of semiconductors can be modified by doping, or introducing
impurities. Adding an element with more valence electrons than the atoms of the host populates the conduction band, resulting in
an n-type semiconductor with increased electrical conductivity. Adding an element with fewer valence electrons than the atoms of
the host generates holes in the valence band, resulting in a p-type semiconductor that also exhibits increased electrical conductivity.

This page titled 11.7: Bonding in Metals is shared under a CC BY-NC-SA 3.0 license and was authored, remixed, and/or curated by Anonymous.

11.7.7 [Link]
11.8: Some Unresolved Issues

under construction
The breakdown of d-orbital hybridization
SF6 etc.

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11.8.1 [Link]
11.E: Chemical Bonding II: Additional Aspects (Exercises)

11.7 Bonding in Metals

Conceptual Problems
1. Can band theory be applied to metals with two electrons in their valence s orbitals? with no electrons in their valence s orbitals?
Why or why not?
2. Given a sample of a metal with 1020 atoms, how does the width of the band arising from p orbital interactions compare with the
width of the band arising from s orbital interactions? from d orbital interactions?
3. Diamond has one of the lowest electrical conductivities known. Based on this fact, do you expect diamond to be colored? Why?
How do you account for the fact that some diamonds are colored (such as “pink” diamond or “green” diamond)?
4. Why do silver halides, used in the photographic industry, have band gaps typical of semiconducting materials, whereas alkali
metal halides have very large band gaps?
5. As the ionic character of a compound increases, does its band gap increase or decrease? Why?
6. Why is silicon, rather than carbon or germanium, used in the semiconductor industry?
7. Carbon is an insulator, and silicon and germanium are semiconductors. Explain the relationship between the valence electron
configuration of each element and their band structures. Which will have the higher electrical conductivity at room temperature
—silicon or germanium?
8. How does doping affect the electrical conductivity of a semiconductor? Draw the effect of doping on the energy levels of the
valence band and the conduction band for both an n-type and a p-type semiconductor.

Answers
3. The low electrical conductivity of diamond implies a very large band gap, corresponding to the energy of a photon of ultraviolet
light rather than visible light. Consequently, diamond should be colorless. Pink or green diamonds contain small amounts of
highly colored impurities that are responsible for their color.
4. -
5. As the ionic character of a compound increases, the band gap will also increase due to a decrease in orbital overlap. Remember
that overlap is greatest for orbitals of the same energy, and that the difference in energy between orbitals on adjacent atoms
increases as the difference in electronegativity between the atoms increases. Thus, large differences in electronegativity increase
the ionic character, decrease the orbital overlap, and increase the band gap.

Numerical Problems
1. Of Ca, N, B, and Ge, which will convert pure silicon into a p-type semiconductor when doping? Explain your reasoning.
2. Of Ga, Si, Br, and P, which will convert pure germanium into an n-type semiconductor when doping? Explain your reasoning.

11.E: Chemical Bonding II: Additional Aspects (Exercises) is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or
curated by LibreTexts.

11.E.1 [Link]
 CHAPTER OVERVIEW

12: Intermolecular Forces: Liquids And Solids

Petrucci: General Chemistry

Principles and Modern Applications
I II III IV V VI VII VIII IX X XI XII XIII XIV XV XVI XVII XVIII XIX XX
XXI XXII XXIII XXIV XXV XXVI XXVII XXVIII

Template:HideTOC
12.1: Intermolecular Forces
12.2: Some Properties of Liquids
12.3: Some Properties of Solids
12.4: Phase Diagrams
12.5: Network Covalent Solids and Ionic Solids
12.6: Crystal Structures
12.7: Energy Changes in the Formation of Ionic Crystals

12: Intermolecular Forces: Liquids And Solids is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.

1
12.1: Intermolecular Forces
 Learning Objectives
To describe the intermolecular forces in liquids.

The properties of liquids are intermediate between those of gases and solids, but are more similar to solids. In contrast to
intramolecular forces, such as the covalent bonds that hold atoms together in molecules and polyatomic ions, intermolecular forces
hold molecules together in a liquid or solid. Intermolecular forces are generally much weaker than covalent bonds. For example, it
requires 927 kJ to overcome the intramolecular forces and break both O–H bonds in 1 mol of water, but it takes only about 41 kJ to
overcome the intermolecular attractions and convert 1 mol of liquid water to water vapor at 100°C. (Despite this seemingly low
value, the intermolecular forces in liquid water are among the strongest such forces known!) Given the large difference in the
strengths of intra- and intermolecular forces, changes between the solid, liquid, and gaseous states almost invariably occur for
molecular substances without breaking covalent bonds.

The properties of liquids are intermediate between those of gases and solids, but are more
similar to solids.
Intermolecular forces determine bulk properties, such as the melting points of solids and the boiling points of liquids. Liquids boil
when the molecules have enough thermal energy to overcome the intermolecular attractive forces that hold them together, thereby
forming bubbles of vapor within the liquid. Similarly, solids melt when the molecules acquire enough thermal energy to overcome
the intermolecular forces that lock them into place in the solid.
Intermolecular forces are electrostatic in nature; that is, they arise from the interaction between positively and negatively charged
species. Like covalent and ionic bonds, intermolecular interactions are the sum of both attractive and repulsive components.
Because electrostatic interactions fall off rapidly with increasing distance between molecules, intermolecular interactions are most
important for solids and liquids, where the molecules are close together. These interactions become important for gases only at very
high pressures, where they are responsible for the observed deviations from the ideal gas law at high pressures.
In this section, we explicitly consider three kinds of intermolecular interactions. There are two additional types of electrostatic
interaction that you are already familiar with: the ion–ion interactions that are responsible for ionic bonding, and the ion–dipole
interactions that occur when ionic substances dissolve in a polar substance such as water. The first two are often described
collectively as van der Waals forces.

Dipole–Dipole Interactions
Polar covalent bonds behave as if the bonded atoms have localized fractional charges that are equal but opposite (i.e., the two
bonded atoms generate a dipole). If the structure of a molecule is such that the individual bond dipoles do not cancel one another,
then the molecule has a net dipole moment. Molecules with net dipole moments tend to align themselves so that the positive end of
one dipole is near the negative end of another and vice versa, as shown in Figure 12.1.1a.

Figure 12.1.1 : Attractive and Repulsive Dipole–Dipole Interactions. (a and b) Molecular orientations in which the positive end of
one dipole (δ+) is near the negative end of another (δ−) (and vice versa) produce attractive interactions. (c and d) Molecular
orientations that juxtapose the positive or negative ends of the dipoles on adjacent molecules produce repulsive interactions. (CC
BY-SA-NC; anonymous)
These arrangements are more stable than arrangements in which two positive or two negative ends are adjacent (Figure 12.1.1c).
Hence dipole–dipole interactions, such as those in Figure 12.1.1b, are attractive intermolecular interactions, whereas those in
Figure 12.1.1d are repulsive intermolecular interactions. Because molecules in a liquid move freely and continuously, molecules

12.1.1 [Link]
always experience both attractive and repulsive dipole–dipole interactions simultaneously, as shown in Figure 12.1.2. On average,
however, the attractive interactions dominate.

Figure 12.1.2 : Both attractive and repulsive dipole–dipole interactions occur in a liquid sample with many molecules. (CC BY-SA-
NC; anonymous)
The green arrows pointing towards each other represent attraction. The gray arrows pointing away from each other represent
repulsion
Because each end of a dipole possesses only a fraction of the charge of an electron, dipole–dipole interactions are substantially
weaker than the interactions between two ions, each of which has a charge of at least ±1, or between a dipole and an ion, in which
one of the species has at least a full positive or negative charge. In addition, the attractive interaction between dipoles falls off
much more rapidly with increasing distance than do the ion–ion interactions. Recall that the attractive energy between two ions is
proportional to 1/r, where r is the distance between the ions. Doubling the distance (r → 2r) decreases the attractive energy by one-
half. In contrast, the energy of the interaction of two dipoles is proportional to 1/r3, so doubling the distance between the dipoles
decreases the strength of the interaction by 23, or 8-fold. Thus a substance such as HCl, which is partially held together by dipole–
dipole interactions, is a gas at room temperature and 1 atm pressure. Conversely, NaCl, which is held together by interionic
interactions, is a high-melting-point solid. Within a series of compounds of similar molar mass, the strength of the intermolecular
interactions increases as the dipole moment of the molecules increases, as shown in Table 12.1.1.
Table 12.1.1 : Relationships Between the Dipole Moment and the Boiling Point for Organic Compounds of Similar Molar Mass
Compound Molar Mass (g/mol) Dipole Moment (D) Boiling Point (K)

C3H6 (cyclopropane) 42 0 240

CH3OCH3 (dimethyl ether) 46 1.30 248

CH3CN (acetonitrile) 41 3.9 355

The attractive energy between two ions is proportional to 1/r, whereas the attractive
energy between two dipoles is proportional to 1/r6.

12.1.2 [Link]
 Dipole Intermolecular Force

Video Discussing Dipole Intermolecular Forces. Source: Dipole Intermolecular Force, YouTube(opens in new window) [[Link]]

 Example 12.1.1

Arrange ethyl methyl ether (CH3OCH2CH3), 2-methylpropane [isobutane, (CH3)2CHCH3], and acetone (CH3COCH3) in order
of increasing boiling points. Their structures are as follows:

Given: compounds.
Asked for: order of increasing boiling points.

Strategy:
Compare the molar masses and the polarities of the compounds. Compounds with higher molar masses and that are polar will
have the highest boiling points.

Solution:
The three compounds have essentially the same molar mass (58–60 g/mol), so we must look at differences in polarity to predict
the strength of the intermolecular dipole–dipole interactions and thus the boiling points of the compounds.
The first compound, 2-methylpropane, contains only C–H bonds, which are not very polar because C and H have similar
electronegativities. It should therefore have a very small (but nonzero) dipole moment and a very low boiling point.
Ethyl methyl ether has a structure similar to H2O; it contains two polar C–O single bonds oriented at about a 109° angle to
each other, in addition to relatively nonpolar C–H bonds. As a result, the C–O bond dipoles partially reinforce one another and
generate a significant dipole moment that should give a moderately high boiling point.
Acetone contains a polar C=O double bond oriented at about 120° to two methyl groups with nonpolar C–H bonds. The C–O
bond dipole therefore corresponds to the molecular dipole, which should result in both a rather large dipole moment and a high
boiling point.
Thus we predict the following order of boiling points:

2-methylpropane < ethyl methyl ether < acetone

12.1.3 [Link]