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

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

electrons are removed from the thermoplastic rod, and it According to the electron sea model, all metals conduct
becomes positively charged, whereas the woolen cloth pulls electricity well because the outer electrons are free to move
away electrons from the rod and becomes negatively charged. through the lattice under the influence of an electric field.
This effect is not observed when a metal rod is rubbed against Metals are malleable and ductile because there are defects in
a woolen cloth. At the same time, students in high school or the solid state or one layer of atoms can slide over another
the first-year undergraduate level learn in chemistry that layer easily. However, some research has shown that this model
metallic crystals consist of “ions in a sea of electrons”. The “sea is not a correct description of metallic structure.5,6 It is fairly
of electrons” that bond the metallic ions together are free to obvious that the Drude theory of free electrons and the “ions
move around or become “delocalized”. Students may be in a sea of electrons” model provide similar depictions of
puzzled by these two pieces of inconsistent information metallic bonding.
because if the bonding electrons in metals are “free”, they Band Theory
should be easily transferred to a woolen cloth. In contrast, Band theory was developed to explain the mechanism of
experiments show that electrons in some covalently bonded electrical conduction.7 In classical physics, electrons in a solid
materials are much easier to remove. can have any energy value. The exclusion principle in quantum
Current Description of Metallic Structure and Bonding theory states that no two electrons in an atom can have the
In previous work,1,2 the “free electron” theory first proposed by same set of quantum numbers. This means that a maximum of
Paul Drude in 1900 was briefly described. In his theory,3 it was only two electrons can have the exact same energy value. On a
suggested that in crystalline solids, there can be electrons that very simplistic level, band theory, which is based on quantum
are free to move within the solid. The quantity or density of mechanics, states that when numerous atoms are being held
the free electrons depends on the material. In metals there are together in a crystal, the energy levels form a vast number of
usually between one and three free electrons per atom, which energy bands. Each band consists of many closely spaced
form an “electron gas” of independent particles surrounding discrete energy levels. The energy bands are separated by gaps
positive metal ions. When there is a current, the “free” in which there are no available energy levels. If energy in the
electrons are accelerated, but collisions with ions in the crystal form of an electric field is added to the electrons, those in
lattice slow them down. Even though Drude’s theory made a lower energy levels cannot accept the energy because they
tremendous contribution to the understanding of metallic cannot move into already occupied higher energy levels. Only
properties, as reported in earlier work,1,2 his theory is at odds electrons in the highest levels can accept energy, and they can
with some of the principles of physics.4 do so only if the energy is enough to raise them to slightly
Currently, the model of metallic bonding and structure
usually being taught in high school and in some university Received: April 4, 2018
undergraduate chemistry classes is the “ions in a sea of Revised: July 17, 2018
electrons” model. Occasionally, band theory is mentioned. In
© XXXX American Chemical Society and
Division of Chemical Education, Inc. A DOI: 10.1021/acs.jchemed.8b00239
J. Chem. Educ. XXXX, XXX, XXX−XXX
Journal of Chemical Education Article

higher unoccupied levels. In conductors, the highest-energy expansion and electrical conductivities. The three metals with
band (the conduction hand) is only partly occupied, so the highest electrical conductivities are copper, silver, and gold
random movement of electrons that are in the highest band is (all being transition metals). Most lanthanides, on the other
allowed. When there is a potential difference between the ends hand, have a common oxidation state of 3+, but they can also
of such a solid (e.g., a metal wire), these electrons can freely possess other oxidation states. All lanthanides have high
move down the potential gradient, forming an electric current. melting points and fairly high densities (ranging from 5.2 to
In insulators, there is a large energy gap between the highest 9.8 g/cm3).
occupied band and the next empty energy band. Since the The bond dissociation energy of a Cl−Cl bond is 242.4 kJ/
highest band is fully occupied in an insulator, electrons cannot mol, and the first ionization energy of cesium is 375.7 kJ/
move across the solid to create a current. Electrons are unable mol.12 Values of the work function of some metals, related to
to jump into the next energy level because the energy gap to the phenomenon of the photoelectric effect, such as that of
the next higher level is too great. Band theory clarifies the ruthenium at 454.5 kJ/mol and rhodium at 480.5 kJ/mol,12 are
mechanism of electrical conduction precisely, but it does not higher than some bond energies and ionization energies, such
describe other metallic properties that can be explained by the as the examples given above, and this can be confusing to some
soft sphere model, so it will not be discussed further in this chemistry students who have been taught that electrons in a
work. metal are “delocalized” and free to move around. There are no
observable trends in many metallic properties such as electrical
Diverse Properties of Metals
conductance or density. It is evident that the “ions in a sea of
Before the alternative model of metallic bonding is defined, it is electrons” model is unable to explain many of the large
useful to go through some of the general properties of metals differences in properties among metals, and a better model is
to provide an appreciation that metals possess a wide range of needed.
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,
■ THE SOFT/FLEXIBLE SPHERE MODEL OF
METALLIC STRUCTURE AND BONDING
nearly all metals possess a body-centered cubic (bcc), The soft/flexible sphere model was created some time ago to
hexagonal close-packed (hcp) or cubic close-packed (ccp) derive equations that can replicate observed internuclear
structure. A few metals possess complex structures (e.g., the separations of ionic crystals and covalently bonded molecules
crystal structure of manganese is not easily described), and in both the gaseous and solid states.1,13 The details given below
they are too complicated to be discussed here. Metals are good provide some of the important features of the soft sphere
conductors of heat, sound, and electricity and most are model that have been published previously.1,2,8,18 Earlier work
malleable and ductile. It is not correct to say that metals in has shown that for any particular coordination number, only a
general are hard and strong materials with high melting points small number of group 1 and group 2 ions behave like fairly
and high densities. hard spheres1 and that many other ions do not resemble hard
All of the alkali metals are soft and have low densities and spheres at all. Internuclear separations of ionic and covalent
low melting points. Most binary alkali metal salts can be solids calculated from soft-sphere-derived radii and from a
considered to be fully ionic,8 with lithium hydride being a series of simple equations derived from the model produced
notable exception. The lithium ion is very small, and the very good agreement with observed values for binary
nuclear charge tends to distort the electron density compounds.1,8,13
surrounding the hydride ion; a detailed study has shown that An atom is often portrayed as a sphere, and in the soft
it is more covalent than ionic.9 Alkaline-earth metals are fairly sphere model, as discussed in prior work,1 atoms and ions are
soft and compared with alkali metals have higher melting regarded as compressible spheres. In an atom, in general, the
points and densities. The majority of binary alkaline-earth electron density is concentrated in the space near the nucleus
metal salts can also be described as ionic but may show some and decreases as the distance from the nucleus increases.
covalent character. Most metals in the p block have melting However, in a metal crystal, there are small pockets or regions
points similar to those of the alkaline-earth metals. Excluding of electron density that are isolated from the main body of
aluminum, they have slightly higher densities, and their binary electron density and occupy spaces directly in between
salts display more covalent character. Some p-block metals individual atoms of the crystal. A simple way of representing
have multiple oxidation states. Unlike s- and p-block elements, the situation is to consider a proportion of the outermost
transition elements and the lanthanides do not show any electrons as being detached or separated from the metal atom.
characteristic patterns in their first and second ionization However, they are neither exactly “free” nor completely
energies. It is useful to note that d and f electrons behave “delocalized”. Although it is not strictly correct to describe
differently from s and p electrons, as shown, for example, in the individual electrons as being detached and occupying fixed or
study of their ionization energies.10,11 Densities, melting exact positions because of quantum-mechanical principles,14
points, and oxidation states of transition metals have much for the sake of simplicity the term “detached electron(s)” will
wider ranges than those of the s- and p-block metals. be used in the rest of this work. Figure 1 illustrates the
Metals in the d block (except zinc, cadmium, and mercury) midpoint sites occurring between one ion in the middle layer
have melting points ranging from 920 to >3400 °C. They also and the ions in the top and bottom layers in part of an hcp
exhibit a large range of densities, from 3 to 22.6 g/cm3. crystal structure. Readers not acquainted with crystal structures
Osmium, iridium, and platinum possess the highest densities of can familiarize themselves with this topic by reading, for
all natural occurring elements. Transition elements have example, Structural Inorganic Chemistry by A. F. Wells15 or any
variable oxidation states that may be as high as 8+. Some introductory text in crystallography.
transition metals are very good heterogeneous catalysts. Each crystal structure has a different number of equivalent
Transition metals also exhibit a wide range of coefficients of positions midway or at the midpoint between the atom(s)/
B DOI: 10.1021/acs.jchemed.8b00239
J. Chem. Educ. XXXX, XXX, XXX−XXX
Journal of Chemical Education Article

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
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 discussed below. Properties of transition metals such as
upper and lower layers that can be occupied by detached electrons are densities, work functions, lattice energies of binary oxides
shown. and ionic salts, electrical resistivities, coefficients of expansion,
and enthalpies of formation of Mx+ ions can be calculated using
ion(s) and nearest neighboring ions. Thus, depending on equations derived from this model. Previous work has shown
which structure a metal possesses, the possible number of that values calculated from these equations agree very well with
outermost electrons detached from each individual metal atom observed values.1,2,17,18
can range from zero to a maximum of six (see below). Table 1 Comparison between the “Ions in a Sea of Electrons” and
Soft Sphere Models
Table 1. Crystal Structures of Metals and Maximum
Possible Numbers of Detached Electrons The merits of the electron sea and soft sphere models have
been compared previously.1,2,17,18 The mains points are
Crystal Number of Nearest Maximum Number of Detached detailed here to help the reader to differentiate between the
Structure Neighbors Per Atom Electrons Per Atom
usefulness of the two models. The “electron sea” model
hcp 12 6 maintains that outer electrons of metal atoms form a pool or
bcc 8 4 sea of delocalized electrons that are free and move randomly
ccp 12 6
throughout the metallic solid. Naturally one may expect that
when a metal is under pressure with shorter interatomic
lists for each crystal structure the number of nearest neighbors distances, the widths of the valence and conduction bands
(which is equal to the number of sites available for occupation should increase and lead to more “free-electron-like behavior”.
by detached electrons) and the maximum number of detached The electrons in the electron sea should be forced closer
electrons per atom that can occur. together, and the conductivity should improve. Second, since
In any crystal with an hcp or ccp structure of atoms of the the metal ions are surrounded by free electrons, there should
same element, each atom has a coordination number of 12 be free electrons on the metal surface that can be removed very
(i.e., 12 nearest neighbors), but in a bcc structure, each atom easily. As revealed by experimental research,6 under high
has only eight nearest neighbors. Examples of hcp structures pressure the electrical conductivity in a metal decreases, and it
include titanium and zirconium, and the soft sphere model has been shown that when a metal is under very high pressure,
assumes that both have two detached electrons. Since there are the resistance of the metal increases drastically and it acts more
six atoms in each complete hexagonal unit and each atom has
like an insulator6 than a conductor of electricity. Additionally,
two detached electrons, at any one time only one-third of the
photoelectric effect experiments have shown without doubt
12 sites in a unit cell are occupied. A second example of metals
that it is not easy to remove electrons from a metal surface, and
with a different structure is provided by vanadium and
niobium. Both have the bcc structure, and there are two the work functions of some metals are higher than some
atoms in each complete bcc unit cell. The model assumes that ionization energies, as shown by the examples given above.
each atom has three detached electrons, which means that at These behaviors are not easily explained by the “electron sea”
any one time only three-quarters of the eight midpoint sites are model. Nevertheless, the soft-sphere model can accounted for
occupied. The detached electrons can move at random from them. When a metal is under pressure, the shape and size of
one site to another within the unit cell. The de Broglie the unit cell changes. This reduces the volume of the site(s)
relationship,16 which was discussed in previous work,1 shows occupied by the detached electron(s), and if the volume is
that the electron wavelength is directly proportional to its reduced sufficiently it can no longer be occupied. When the
speed, and the speed v is a function of the electrostatic shape of the unit cell changes, the distances between some of
attraction between the electron and the nucleus and the the “midpoint sites” may increase to such an extent that the
distance from the nucleus. A “detached” electron is equally detached electrons occupying those sites may no longer be able
attracted by two positive ions in opposite directions and hence to move from one site to the next. When there are no vacant
moves or vibrates within the midpoint site with an orbital sites and the space between the ions under pressure becomes
radius r equal to [e] (the radius of the electron “cloud”), where too small to facilitate electron movement or the electrons
2πr is the de Broglie wavelength. The maximum number of cannot move between sites in neighboring unit cells, the metal
detached electrons per atom has to be less than or equal to half becomes a virtual insulator. As shown in Figure 2, under high
the number of available sites in a unit cell. For example, a metal pressure the shape of the unit cell is changed, there is less space
C DOI: 10.1021/acs.jchemed.8b00239
J. Chem. Educ. XXXX, XXX, XXX−XXX
Journal of Chemical Education Article

in some of the vacant sites, and the distances between some electrical resistivities, etc. However, there are little or no visible
sites have become greater.8 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
Figure 2. Unit cells under pressure. 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
Another argument saying that metals are malleable and here. Instead, two examples comparing calculated and
ductile because of defects in the solid state cannot be correct. observed values involving lanthanide elements are detailed
Many solids, both ionic and covalent, including nonmetallic below to illustrate the simplicity and usefulness of the
solids such as silicon and sulfur, contain solid-state defects but equations.
are not malleable or ductile.1 It is also said that metals are For any specific metal, the number of detached electrons per
malleable because one layer of atoms can easily slide over the atom, x, is dependent on the electron configuration and the
next layer. If this is the case, it will only create a kink2 in the crystal structure. Defects in the solid state may cause the
metal and not a smooth bend. In addition, if a layer can easily number of detached electrons to change from the expected
slide over the next layer, the bonds holding the two layers are value by up to ±1 depending on the surroundings. The size
not very strong, and the metal will lack tensile or compressive and volume of the metallic ion in the solid state are determined
strength. In the soft sphere model, most of the time not all of by mainly two factors. The first is the number of detached
the available sites are occupied by electrons, and when a metal electrons, because the fewer the number of electrons detached,
is twisted or bent, electrons can move from one site to another the larger will be the radius of the ion. The second is the
within a unit cell, allowing the shape of the metal to change number of electrons in the electron shells or orbitals nearest in
without any bonds being broken. The detached electrons can energy to the electron orbitals from which electrons are
move around different sites inside a unit cell. As discussed detached. According to prior work,17 in the case of lanthanum,
above and in previous work1,2,17,18), only some of those sites the number of electrons relevant to the size and volume of the
are occupied at any one time. In the solid state, a metal crystal lanthanum atom is n = 16 (the sum of 4d10/2, 5s2 5p6, 6s2, and
is divided into numerous “microsegments” or “domains” 5d1) and for the 4f series, n is the sum of 4d10/2, 5s2, 5p6, 6s2,
limited by imperfections in the solid state. A flow of electrons and the number of 4f electrons in the neutral atom. For
along any particular direction will be limited to flow within the instance, there are two detached electrons per atom for cerium,
domains. Since all of the unit cells in a metal sample are so (n − x)/n = 16/18. The atomic volume17 of any lanthanide,
identical and there are vacant sites that can promote the Vc, can be obtained from the following expression:
movement of electrons, a very small voltage will initiate current
flow along the metal solid. Vc = kn[(n − x)/n]3 (I)
By definition, a catalyst is a material that increases the rate of
a chemical reaction but does not directly take part in the In eq I, kn is a constant and is equal to the volume of a
reaction and is not used up. It can do this by providing a hypothetical atom at the start of a series with zero relevant
different and easier path for the reactants to react. Again, the electrons in that series; kn is also depends on the number of
electron sea model cannot show why some metals are good electron shells or principal quantum number.
heterogeneous catalysts. In the soft sphere model, detached For the 4f series, kn is equal to 46 Å3 (where 1 Å = 10−10 m
electrons only occupy sites within the unit cell, and there are or 10−8 cm) and is equal to the volume of the hypothetical
very few detached electrons on the surface of a metal. When atom at the start of the series with no f electrons. Since density
reactants move toward the metal they are adsorbed onto the is mass per unit volume, the density D of any lanthanide
metal surface by electrostatic forces. This creates new “unit element can then be calculated from eq II:]
cells” between the reactant surfaces and the metal surface that D = ks/{kn[(n − x)/n]3 } (II)
allow electrons to flow from the reactants to the surface of the
metal or from the metal surface to the reactants.2 This allows where ks is the mass number of the atom multiplied by the
the movement of electrons between the different reactants and unified atomic mass unit (1.66 × 10−24 g).
enables bonds in the reactants to be broken and new bonds to In Table 2, densities calculated using eq II and observed
be formed. Hence, a new and possibly more energetically values are shown. The model assumes that europium has only
favorable route is provided for the necessary reaction, 0.5 detached electrons, which means that at any one time only
increasing the reaction rate. one electron is detached between two atoms. Most of the
If metal solids were just ions surrounded by free electrons, it values agree to over 90%, and just over half the values agree to
would be quite logical to expect that there should be some 95% or better.
easily observable trends in the properties of metals, including Some lanthanides possess more than one crystal structure at
transition metals, like densities, coefficients of expansion, room temperature, and some of the structures are distorted. A
D DOI: 10.1021/acs.jchemed.8b00239
J. Chem. Educ. XXXX, XXX, XXX−XXX
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
E DOI: 10.1021/acs.jchemed.8b00239
J. Chem. Educ. XXXX, XXX, XXX−XXX
Journal of Chemical Education Article

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

■
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