Article

Cite This: J. Chem. Educ. XXXX, XXX, XXX−XXX pubs.acs.org/jchemeduc

Is a Metal “Ions in a Sea of Delocalized Electrons?”

Peter F. Lang*
Birkbeck College, University of London, Malet Street, London WC1E 7HX, U.K.
*
S Supporting Information

ABSTRACT: This work outlines the inadequacies of the “ions in a sea of

electrons” model. Some general properties of metals are stated. A different
“soft/flexible” sphere model is described. The benefits of using this other
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model to account for metallic properties are discussed. Equations based on

the soft sphere model are used to calculate values of the enthalpies of
formation of the Mx+ ions and densities of the lanthanide elements to show
advantages of this model over the “electron sea” model. Values obtained from
the soft-sphere-derived equations are shown to agree well with observed ones.
KEYWORDS: Upper-Division Undergraduate, Inorganic Chemistry, Inquiry-Based/Discovery Learning, Metallic Bonding

■ INTRODUCTION
At the high school level, students in physics classes have either
carried experiments or have been shown that when a woolen
cloth is rubbed against a transparent thermoplastic rod
J. Chem. Educ.
the “electron sea” model, atoms in a metallic solid lose their
outer electrons and form a regular lattice of positive metallic
ions. The outer electrons do not “belong” to any atom but
form a pool or sea of delocalized electrons that are free and
move randomly throughout the fixed lattice of positive ions.

(Perspex or Plexiglas), both being covalently bonded materials,

electrons are removed from the thermoplastic rod, and it
becomes positively charged, whereas the woolen cloth pulls
away electrons from the rod and becomes negatively charged.
This effect is not observed when a metal rod is rubbed against
a woolen cloth. At the same time, students in high school or
the first-year undergraduate level learn in chemistry that
metallic crystals consist of “ions in a sea of electrons”. The “sea
of electrons” that bond the metallic ions together are free to
move around or become “delocalized”. Students may be
puzzled by these two pieces of inconsistent information
because if the bonding electrons in metals are “free”, they
should be easily transferred to a woolen cloth. In contrast,
experiments show that electrons in some covalently bonded
materials are much easier to remove.
Current Description of Metallic Structure and Bonding
In previous work,1,2 the “free electron” theory first proposed by
Paul Drude in 1900 was briefly described. In his theory,3 it was
suggested that in crystalline solids, there can be electrons that
are free to move within the solid. The quantity or density of
the free electrons depends on the material. In metals there are
usually between one and three free electrons per atom, which
form an “electron gas” of independent particles surrounding
positive metal ions. When there is a current, the “free”
electrons are accelerated, but collisions with ions in the crystal
lattice slow them down. Even though Drude’s theory made a
tremendous contribution to the understanding of metallic
properties, as reported in earlier work,1,2 his theory is at odds
with some of the principles of physics.4
Currently, the model of metallic bonding and structure
usually being taught in high school and in some university
undergraduate chemistry classes is the “ions in a sea of
electrons” model. Occasionally, band theory is mentioned. In
© XXXX American Chemical Society and
Division of Chemical Education, Inc.
According to the electron sea model, all metals conduct
electricity well because the outer electrons are free to move
through the lattice under the influence of an electric field.
Metals are malleable and ductile because there are defects in
the solid state or one layer of atoms can slide over another
layer easily. However, some research has shown that this model
is not a correct description of metallic structure.5,6 It is fairly
obvious that the Drude theory of free electrons and the “ions
in a sea of electrons” model provide similar depictions of
metallic bonding.
Band Theory
Band theory was developed to explain the mechanism of
electrical conduction.7 In classical physics, electrons in a solid
can have any energy value. The exclusion principle in quantum
theory states that no two electrons in an atom can have the
same set of quantum numbers. This means that a maximum of
only two electrons can have the exact same energy value. On a
very simplistic level, band theory, which is based on quantum
mechanics, states that when numerous atoms are being held
together in a crystal, the energy levels form a vast number of
energy bands. Each band consists of many closely spaced
discrete energy levels. The energy bands are separated by gaps
in which there are no available energy levels. If energy in the
form of an electric field is added to the electrons, those in
lower energy levels cannot accept the energy because they
cannot move into already occupied higher energy levels. Only
electrons in the highest levels can accept energy, and they can
do so only if the energy is enough to raise them to slightly
Received: April 4, 2018
Revised: July 17, 2018
A DOI: 10.1021/acs.jchemed.8b00239
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Journal of Chemical Education
higher unoccupied levels. In conductors, the highest-energy
band (the conduction hand) is only partly occupied, so
random movement of electrons that are in the highest band is
allowed. When there is a potential difference between the ends
of such a solid (e.g., a metal wire), these electrons can freely
move down the potential gradient, forming an electric current.
In insulators, there is a large energy gap between the highest
occupied band and the next empty energy band. Since the
highest band is fully occupied in an insulator, electrons cannot
move across the solid to create a current. Electrons are unable
to jump into the next energy level because the energy gap to
the next higher level is too great. Band theory clarifies the
mechanism of electrical conduction precisely, but it does not
describe other metallic properties that can be explained by the
soft sphere model, so it will not be discussed further in this
work.
Diverse Properties of Metals
Before the alternative model of metallic bonding is defined, it is
useful to go through some of the general properties of metals
to provide an appreciation that metals possess a wide range of
attributes and can be vastly different from each other. All of the
properties given below are well-known properties of metals and
are similarly described in many textbooks. In the solid state,
nearly all metals possess a body-centered cubic (bcc),
hexagonal close-packed (hcp) or cubic close-packed (ccp)
structure. A few metals possess complex structures (e.g., the
crystal structure of manganese is not easily described), and
they are too complicated to be discussed here. Metals are good
conductors of heat, sound, and electricity and most are
malleable and ductile. It is not correct to say that metals in
general are hard and strong materials with high melting points
and high densities.
All of the alkali metals are soft and have low densities and
low melting points. Most binary alkali metal salts can be
considered to be fully ionic,8 with lithium hydride being a
notable exception. The lithium ion is very small, and the
nuclear charge tends to distort the electron density
surrounding the hydride ion; a detailed study has shown that
it is more covalent than ionic.9 Alkaline-earth metals are fairly
soft and compared with alkali metals have higher melting
points and densities. The majority of binary alkaline-earth
metal salts can also be described as ionic but may show some
covalent character. Most metals in the p block have melting
points similar to those of the alkaline-earth metals. Excluding
aluminum, they have slightly higher densities, and their binary
salts display more covalent character. Some p-block metals
have multiple oxidation states. Unlike s- and p-block elements,
transition elements and the lanthanides do not show any
characteristic patterns in their first and second ionization
energies. It is useful to note that d and f electrons behave
differently from s and p electrons, as shown, for example, in the
study of their ionization energies.10,11 Densities, melting
points, and oxidation states of transition metals have much
wider ranges than those of the s- and p-block metals.
Metals in the d block (except zinc, cadmium, and mercury)
have melting points ranging from 920 to >3400 °C. They also
exhibit a large range of densities, from 3 to 22.6 g/cm3.
Osmium, iridium, and platinum possess the highest densities of
all natural occurring elements. Transition elements have
variable oxidation states that may be as high as 8+. Some
transition metals are very good heterogeneous catalysts.
Transition metals also exhibit a wide range of coefficients of
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expansion and electrical conductivities. The three metals with
the highest electrical conductivities are copper, silver, and gold
(all being transition metals). Most lanthanides, on the other
hand, have a common oxidation state of 3+, but they can also
possess other oxidation states. All lanthanides have high
melting points and fairly high densities (ranging from 5.2 to
9.8 g/cm3).
The bond dissociation energy of a Cl−Cl bond is 242.4 kJ/
mol, and the first ionization energy of cesium is 375.7 kJ/
mol.12 Values of the work function of some metals, related to
the phenomenon of the photoelectric effect, such as that of
ruthenium at 454.5 kJ/mol and rhodium at 480.5 kJ/mol,12 are
higher than some bond energies and ionization energies, such
as the examples given above, and this can be confusing to some
chemistry students who have been taught that electrons in a
metal are “delocalized” and free to move around. There are no
observable trends in many metallic properties such as electrical
conductance or density. It is evident that the “ions in a sea of
electrons” model is unable to explain many of the large
differences in properties among metals, and a better model is
needed.
■ THE SOFT/FLEXIBLE SPHERE MODEL OF
METALLIC STRUCTURE AND BONDING
The soft/flexible sphere model was created some time ago to
derive equations that can replicate observed internuclear
separations of ionic crystals and covalently bonded molecules
in both the gaseous and solid states.1,13 The details given below
provide some of the important features of the soft sphere
model that have been published previously.1,2,8,18 Earlier work
has shown that for any particular coordination number, only a
small number of group 1 and group 2 ions behave like fairly
hard spheres1 and that many other ions do not resemble hard
spheres at all. Internuclear separations of ionic and covalent
solids calculated from soft-sphere-derived radii and from a
series of simple equations derived from the model produced
very good agreement with observed values for binary
compounds.1,8,13
An atom is often portrayed as a sphere, and in the soft
sphere model, as discussed in prior work,1 atoms and ions are
regarded as compressible spheres. In an atom, in general, the
electron density is concentrated in the space near the nucleus
and decreases as the distance from the nucleus increases.
However, in a metal crystal, there are small pockets or regions
of electron density that are isolated from the main body of
electron density and occupy spaces directly in between
individual atoms of the crystal. A simple way of representing
the situation is to consider a proportion of the outermost
electrons as being detached or separated from the metal atom.
However, they are neither exactly “free” nor completely
“delocalized”. Although it is not strictly correct to describe
individual electrons as being detached and occupying fixed or
exact positions because of quantum-mechanical principles,14
for the sake of simplicity the term “detached electron(s)” will
be used in the rest of this work. Figure 1 illustrates the
midpoint sites occurring between one ion in the middle layer
and the ions in the top and bottom layers in part of an hcp
crystal structure. Readers not acquainted with crystal structures
can familiarize themselves with this topic by reading, for
example, Structural Inorganic Chemistry by A. F. Wells15 or any
introductory text in crystallography.
Each crystal structure has a different number of equivalent
positions midway or at the midpoint between the atom(s)/
J. Chem. Educ. XXXX, XXX, XXX−XXX
Journal of Chemical Education
Figure 1. Section of a hexagonal unit cell with one ion in the middle
layer. The sites between the ion in the middle layer and atoms in the
upper and lower layers that can be occupied by detached electrons are
shown.
ion(s) and nearest neighboring ions. Thus, depending on
which structure a metal possesses, the possible number of
outermost electrons detached from each individual metal atom
can range from zero to a maximum of six (see below). Table 1
Table 1. Crystal Structures of Metals and Maximum
Possible Numbers of Detached Electrons
Crystal Number of Nearest Maximum Number of Detached
Structure Neighbors Per Atom Electrons Per Atom
hcp 12 6 maintains that outer electrons of metal atoms form a pool or
bcc 8 4
ccp 12 6
lists for each crystal structure the number of nearest neighbors
(which is equal to the number of sites available for occupation
by detached electrons) and the maximum number of detached
electrons per atom that can occur.
In any crystal with an hcp or ccp structure of atoms of the
same element, each atom has a coordination number of 12
(i.e., 12 nearest neighbors), but in a bcc structure, each atom
has only eight nearest neighbors. Examples of hcp structures
include titanium and zirconium, and the soft sphere model
assumes that both have two detached electrons. Since there are
six atoms in each complete hexagonal unit and each atom has
two detached electrons, at any one time only one-third of the
12 sites in a unit cell are occupied. A second example of metals
with a different structure is provided by vanadium and
niobium. Both have the bcc structure, and there are two
atoms in each complete bcc unit cell. The model assumes that
each atom has three detached electrons, which means that at
any one time only three-quarters of the eight midpoint sites are
occupied. The detached electrons can move at random from
one site to another within the unit cell. The de Broglie
relationship,16 which was discussed in previous work,1 shows
that the electron wavelength is directly proportional to its
speed, and the speed v is a function of the electrostatic
attraction between the electron and the nucleus and the
distance from the nucleus. A “detached” electron is equally
attracted by two positive ions in opposite directions and hence
moves or vibrates within the midpoint site with an orbital
radius r equal to [e] (the radius of the electron “cloud”), where
2πr is the de Broglie wavelength. The maximum number of
detached electrons per atom has to be less than or equal to half
the number of available sites in a unit cell. For example, a metal
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with the bcc structure has only eight nearest neighbors, and
therefore, each atom in the unit cell can have a maximum of
only four detached electrons and a minimum of one detached
electron (or half an electron in the case that only one of the
two atoms has an electron detached and occupying a midpoint
site). As already mentioned in earlier work,17 the model also
assumes that only a very small proportion of electrons in any
atom take part in current flow when a potential difference
exists across the metal solid, or else numerous “free” electrons
will collide with each other, releasing energy in the process and
causing the temperature of the solid to increase rapidly. Some
further details of the model are given in previous work.2,18
This model is much more useful than the electron sea model
because it can account for many characteristics of metals as
discussed below. Properties of transition metals such as
densities, work functions, lattice energies of binary oxides
and ionic salts, electrical resistivities, coefficients of expansion,
and enthalpies of formation of Mx+ ions can be calculated using
equations derived from this model. Previous work has shown
that values calculated from these equations agree very well with
observed values.1,2,17,18
Comparison between the “Ions in a Sea of Electrons” and
Soft Sphere Models
The merits of the electron sea and soft sphere models have
been compared previously.1,2,17,18 The mains points are
detailed here to help the reader to differentiate between the
usefulness of the two models. The “electron sea” model
sea of delocalized electrons that are free and move randomly
throughout the metallic solid. Naturally one may expect that
when a metal is under pressure with shorter interatomic
distances, the widths of the valence and conduction bands
should increase and lead to more “free-electron-like behavior”.
The electrons in the electron sea should be forced closer
together, and the conductivity should improve. Second, since
the metal ions are surrounded by free electrons, there should
be free electrons on the metal surface that can be removed very
easily. As revealed by experimental research,6 under high
pressure the electrical conductivity in a metal decreases, and it
has been shown that when a metal is under very high pressure,
the resistance of the metal increases drastically and it acts more
like an insulator6 than a conductor of electricity. Additionally,
photoelectric effect experiments have shown without doubt
that it is not easy to remove electrons from a metal surface, and
the work functions of some metals are higher than some
ionization energies, as shown by the examples given above.
These behaviors are not easily explained by the “electron sea”
model. Nevertheless, the soft-sphere model can accounted for
them. When a metal is under pressure, the shape and size of
the unit cell changes. This reduces the volume of the site(s)
occupied by the detached electron(s), and if the volume is
reduced sufficiently it can no longer be occupied. When the
shape of the unit cell changes, the distances between some of
the “midpoint sites” may increase to such an extent that the
detached electrons occupying those sites may no longer be able
to move from one site to the next. When there are no vacant
sites and the space between the ions under pressure becomes
too small to facilitate electron movement or the electrons
cannot move between sites in neighboring unit cells, the metal
becomes a virtual insulator. As shown in Figure 2, under high
pressure the shape of the unit cell is changed, there is less space
J. Chem. Educ. XXXX, XXX, XXX−XXX
Journal of Chemical Education
in some of the vacant sites, and the distances between some
sites have become greater.8
Figure 2. Unit cells under pressure.
Another argument saying that metals are malleable and
ductile because of defects in the solid state cannot be correct.
Many solids, both ionic and covalent, including nonmetallic
solids such as silicon and sulfur, contain solid-state defects but
are not malleable or ductile.1 It is also said that metals are
malleable because one layer of atoms can easily slide over the
next layer. If this is the case, it will only create a kink2 in the
metal and not a smooth bend. In addition, if a layer can easily
slide over the next layer, the bonds holding the two layers are
not very strong, and the metal will lack tensile or compressive
strength. In the soft sphere model, most of the time not all of
the available sites are occupied by electrons, and when a metal
is twisted or bent, electrons can move from one site to another
within a unit cell, allowing the shape of the metal to change
without any bonds being broken. The detached electrons can
move around different sites inside a unit cell. As discussed
above and in previous work1,2,17,18), only some of those sites
are occupied at any one time. In the solid state, a metal crystal
is divided into numerous “microsegments” or “domains”
limited by imperfections in the solid state. A flow of electrons
along any particular direction will be limited to flow within the
domains. Since all of the unit cells in a metal sample are
identical and there are vacant sites that can promote the
movement of electrons, a very small voltage will initiate current
flow along the metal solid.
By definition, a catalyst is a material that increases the rate of
a chemical reaction but does not directly take part in the
reaction and is not used up. It can do this by providing a
different and easier path for the reactants to react. Again, the
electron sea model cannot show why some metals are good
heterogeneous catalysts. In the soft sphere model, detached
electrons only occupy sites within the unit cell, and there are
very few detached electrons on the surface of a metal. When
reactants move toward the metal they are adsorbed onto the
metal surface by electrostatic forces. This creates new “unit
cells” between the reactant surfaces and the metal surface that
allow electrons to flow from the reactants to the surface of the
metal or from the metal surface to the reactants.2 This allows
the movement of electrons between the different reactants and
enables bonds in the reactants to be broken and new bonds to
be formed. Hence, a new and possibly more energetically
favorable route is provided for the necessary reaction,
increasing the reaction rate.
If metal solids were just ions surrounded by free electrons, it
would be quite logical to expect that there should be some
easily observable trends in the properties of metals, including
transition metals, like densities, coefficients of expansion,
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electrical resistivities, etc. However, there are little or no visible
trends at all. In contrast, simple formulas derived from the soft
sphere model are capable of calculating values such as
densities, coefficients of expansion, electrical resistivities,
work functions, and enthalpies of formation of the Mx+ ions
of transition metals and lattice energies of ionic metal
compounds. Prior work has clearly established that values
calculated using expressions derived from the soft sphere
concept show good agreement with observed values,2,17,18 but
the same cannot be said of the “ions in a sea of electrons”
model.
Examples of Values Calculated by “Soft Sphere” Equations
Compared to Observed Values
The results from previous work1,2,17,18 compare calculated and
observed values of characteristics of main-group and transition
metals. A lengthy duplication of the outcome is not included
here. Instead, two examples comparing calculated and
observed values involving lanthanide elements are detailed
below to illustrate the simplicity and usefulness of the
equations.
For any specific metal, the number of detached electrons per
atom, x, is dependent on the electron configuration and the
crystal structure. Defects in the solid state may cause the
number of detached electrons to change from the expected
value by up to ±1 depending on the surroundings. The size
and volume of the metallic ion in the solid state are determined
by mainly two factors. The first is the number of detached
electrons, because the fewer the number of electrons detached,
the larger will be the radius of the ion. The second is the
number of electrons in the electron shells or orbitals nearest in
energy to the electron orbitals from which electrons are
detached. According to prior work,17 in the case of lanthanum,
the number of electrons relevant to the size and volume of the
lanthanum atom is n = 16 (the sum of 4d10/2, 5s2 5p6, 6s2, and
5d1) and for the 4f series, n is the sum of 4d10/2, 5s2, 5p6, 6s2,
and the number of 4f electrons in the neutral atom. For
instance, there are two detached electrons per atom for cerium,
so (n − x)/n = 16/18. The atomic volume17 of any lanthanide,
Vc, can be obtained from the following expression:
Vc = kn[(n − x)/n]3 (I)
In eq I, kn is a constant and is equal to the volume of a
hypothetical atom at the start of a series with zero relevant
electrons in that series; kn is also depends on the number of
electron shells or principal quantum number.
For the 4f series, kn is equal to 46 Å3 (where 1 Å = 10−10 m
or 10−8 cm) and is equal to the volume of the hypothetical
atom at the start of the series with no f electrons. Since density
is mass per unit volume, the density D of any lanthanide
element can then be calculated from eq II:]
D = ks/{kn[(n − x)/n]3 } (II)
where ks is the mass number of the atom multiplied by the
unified atomic mass unit (1.66 × 10−24 g).
In Table 2, densities calculated using eq II and observed
values are shown. The model assumes that europium has only
0.5 detached electrons, which means that at any one time only
one electron is detached between two atoms. Most of the
values agree to over 90%, and just over half the values agree to
95% or better.
Some lanthanides possess more than one crystal structure at
room temperature, and some of the structures are distorted. A
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Journal of Chemical Education Article

ji H zyij M
k−1 y
zi 1 y0.33333
E F = R jjj 0 zzzjjjj k −a1.3333 zzzzjjj zzz
j Ma z X
Table 2. Calculated and Observed Densities

k {k { k {
∑ Q i2
Density (g/cm3) 2 (III)
Atom Number of Detached Electrons Calculated Observed
La 1
/2 6.08 6.15 As described in prior work,17 in eq III, R is the Rydberg
Ce 2 7.36 6.77 constant for infinite mass (for this calculation expressed in kJ/
Pr 2 7.24 6.77 mol rather than wavenumbers); H0 is the classical Bohr radius;
Nd 2 7.27 7.04 Ma is the size of the cation, which can be obtained by an
Pm 2 7.16 7.26 equation derived from the soft sphere model;17 X is the size of
Sm 2 7.33 7.52 the negative charge, in this case given by the electron orbital
Eu 1
/2 5.88 5.24 radius r, where 2πr is the de Broglie wavelength; and ∑Qi2 is
Gd 3 8.63 7.90 the sum of the squares of the charges on all of the ions. The
Tb 3 8.56 8.23 higher the charge on the Mx+ ions, the greater is the number of
Dy 3 8.61 8.55 electrons that must be removed from the overlap region. This
Ho 3 8.59 8.80 means that the higher the value of x, the greater is the energy
Er 3 8.59 9.07 required to separate the electrons from the atom. The Rydberg
Tm 3 9.35 9.32 constant is the amount of energy needed to remove an electron
Yb 1 6.94 6.90 from a species the size of a hydrogen atom, and it is multiplied
Lu 3 8.66 9.84 by the distance ratio (H0/Ma) since the greater the size, the
lower is the energy needed to remove the electron. The ratio
(Mak−1/Xk−1.3333) gives an approximation of the overlap and is
multiplied by an approximation factor of (1/2)0.33333.
few lanthanides have slightly more complex forms and not In eq III, the sum of the squares of the charges includes the
simple close-packed structures. charge on the positive ion, Q, and the number of electrons
The enthalpy of formation of a metal ion Mx+ is the sum of being removed from the atom, Qe, which is equivalent to the
the enthalpy of formation of the atom (i.e., the enthalpy of charge of the ion. ∑Qi2 is then the sum of the squares of the
atomization) and the ionization energies of M to M+, M+ to charges on the positive ions and the electrons removed. For
M2+, etc., up to and including M(x−1)+ to Mx+, and this is not example, for Ce4+, Q2 of the positive ion is 16 since each ion
easily calculated by a single simple equation. Nonetheless, has a +4 charge. However, Qe2 of the outermost electrons to be
enthalpies of formation of the transition metal Mx+ ions can be removed is only 1.333 since at any given time only 2/6 (or 1/3)
replicated by a simple soft sphere equation.17 In this work, of the available midpoint sites are occupied by detached
lanthanide Mx+ ions are calculated using a slightly modified electrons and (1 × 1/3 + 1 × 1/3 + 1 × 1/3 + 1 × 1/3) = 1.333.
version of an equation derived from the soft sphere model to Hence, ∑Qi2 of the positive and negative charges is equal to 16
calculate lattice energies. + 1.333 = 17.333 or Q2 + keQe2, where ke is 1/3. As a further
Lattice energies of ionic compounds can normally evaluated example, for Eu3+, Q2 of the positive ion is 9 since each ion has
by the Born−Haber cycle. The lattice energies of mainly ionic a +3 charge. However, Qe2 of the outermost electrons to be
compounds are also calculated to a fairly good degree of removed is only 1.5 since at any given time only half of the
accuracy by the Born−Lande/Born−Mayer and Kapustinskii available midpoint sites are occupied by (three) detached
equations. Lattice energies of alkali metal halides obtained electrons and (1 + 1 + 1) × 1/2 = 1.5. Hence, ∑Qi2 of the
from these equations tend to agree to within a few percent of positive and negative charges is equal to 9 + 1.5 or Q2 + keQe2,
the experimental results,19 but for transition metal compounds where ke is 1/2.
the agreement between the calculated and observed values is The cell constants of the particular crystal structure are used
often poor and can have differences approaching 20% or to work out the soft sphere radii of the positive ions so that the
more.1,20 enthalpy of formation of a metal Mx+ can be calculated using
The soft sphere model suggests that when two or more ions eq III. Where the atom solidifies in more than one crystal
of a compound form part of a crystal lattice, they are deformed structure, only one is chosen to calculate the radius and only
and overlap each other.1,8 Therefore, the lattice energy is the one common oxidation state is used (to work out ∑Qi2) for
energy required to overcome this deformation or inter- the calculation.
penetration of the ions and can be approximated as the energy Table 3 shows the observed and calculated enthalpies of
required to remove the electron(s) bonding the ions in the formation for Mx+ ions in the lanthanide series. A common
overlap space. The lattice energy can be calculated if the oxidation state of 3+ is used throughout the series except for
relative sizes and degrees of deformation of the ions are known, cerium and praseodymium, which are 4+, and samarium, which
provided that the energy to remove an electron (dissociate) is 2+. Values of X used in the above calculations are kept the
from a standard species is known. same as those used in calculating values of transition metal
A very simple expression has been derived from the soft ions. X and k of course can be different for lanthanides, and
sphere model to calculate lattice energies of group 1 and group different values of X or k may improve the agreement with
2 salts.8 The results produced replicated values of lattice observed values. However, to be consistent and maintain
energies obtained from the Born−Haber cycle very closely. simplicity, they are not changed. Two thirds of the results
The original equation was changed slightly and then used to agree with the observed values to 90% or better even though
calculate enthalpies of formation, EF, of Mx+ ions of transition the crystal structures of some of the lanthanides are not perfect
metals. The values calculated by this equation for transition simple close-packed structures21 and some have more than one
metal ions Mx+ give good agreement with observed values.17 structure. For example, samarium possesses two structures,
The equation is reproduced here as follows: rhombohedral and hexagonal. The value of the enthalpy for
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Table 3. Enthalpies of Formation of Mx+ work functions, densities, metallic (internuclear separation)
and ionic radii, enthalpies of formation of usually the most
EF (kJ/mol)
stable Mx+ ions, electrical resistivities, and coefficients of
Ion Mx+ Crystal Structure Calculated Observed expansion. This model can also explain other behavior such as
La3+ hcp 4027 3887 why some transition metals are good heterogeneous catalysts
Ce4+ ccp 7519 7500 and why metals are malleable and ductile. There is very strong
Pr4+ ccp 7568 7750 evidence that the soft sphere model of metallic structure and
Nd3+ hcp 3252 4028 bonding is a much more appropriate physical representation of
Pm3+ hcp 3274 4043 metals than the “ions in a sea of electrons” model. It is more
Sm2+ hcp 1528 1819 suited to explaining metallic characteristics to undergraduate
Eu3+ bcc 4285 4212 level chemistry classes, and a scheme for introducing the
Gd3+ hcp 4555 4148 concept and making use of it in a chemistry class is provided in
Tb3+ hcp 4597 4180 the Supporting Information.
Dy3+
Ho3+
Er3+
hcp
hcp
hcp
4606
4632
4649
4189
4224
4252
■
*
ASSOCIATED CONTENT
S Supporting Information
Tm3+ hcp 4667 4277
Yb3+ ccp 4079 4348
The Supporting Information is available on the ACS
Lu3+ hcp 4692 4315
Publications website at DOI: 10.1021/acs.jchemed.8b00239.
Scheme showing how the soft/flexible sphere model can
2+ 2+ be introduced to explain properties of metals in a
Sm shown in Table 3 was calculated assuming that Sm has
a hexagonal structure. There is no attempt to estimate the chemistry class (PDF, DOC)

■
measure of uncertainty to be used because experimental
uncertainty has not be provided for all the values published in AUTHOR INFORMATION
the literature that are used in the calculation.
The data given in the CRC Handbook12 or in The Structures Corresponding Author
of the Elements21 are reliable, but they are still compared to *E-mail: p.f.lang@gmail.com.
values provided by other publications such as the Journal of ORCID
Physical and Chemical Reference Data and Crystal Data
Determinative Tables.22 In the majority of cases, the data Peter F. Lang: 0000-0002-8530-5422
shown in different publications are either identical or very Notes
similar. The author declares no competing financial interest.
Values of ionic radii, bond lengths, work functions,
enthalpies of formation of Mx+, coefficients of expansion of
transition metals, etc., calculated from expressions derived
■ ACKNOWLEDGMENTS
I thank Professor C. D. Flint for helpful discussions and advice.

■
from the soft sphere model in the vast majority of cases show
very good agreement with observed values. They are not listed REFERENCES
here and can be found in prior work.1,2,8,17,18

■
CONCLUSION AND FINAL COMMENTS
Chemistry at the high school level is sometimes a bit
confusing, such as the case of the meaning of van der Waals
forces.23 At university, undergraduates are sometimes taught
ideas that are not very useful or reliable. For example, the
radius ratio rules printed in many textbooks are not
dependable and often fail to confirm the true structure of
inorganic compounds. They have been described in a
university textbook as “more in the spirit of a first guess
than a predictive tool”.24 The “ions in a sea of electrons”
model, developed at a time before many sophisticated
experiments were made possible to test it, has been shown
to be inadequate. Evidently, it cannot clarify many of the
properties of the transition metals, nor can it be used to derive
equations that can calculate values of metallic or ionic radii or
enthalpies of formation of Mx+ ions. Band theory provides a
correct theoretical interpretation of electrical conductivity but
is not concerned with other metallic properties. The soft/
flexible sphere model provides a good alternative that can
account for many metallic properties. Second, for students that
are not familiar with crystal structures and crystallography, this
is a good opportunity to introduce them to the topic.
Equations deduced from the soft sphere model produce
good agreement between calculated and observed values of
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