The properties of elements

T he 9 - naturally occurring chem ical elem ents (90, in fact, because prom ethium and tech
netium are no longer found in their natural state on E arth) are com posed o f a nucleus
o f subatom ic nucleons orbited by negatively charged electrons. N ucleons are positively
charged protons and neutral neutrons. As an atom contains equal num bers o f protons and
electrons w ith equal but opposite charges, it carries no net electrical charge. T he m ass of a
proton is 1836 tim es that o f an electron. T he chem ical properties o f elem ents are largely,
although not entirely, determ ined by the w ay their outerm ost shells of electrons interact
w ith other elem ents. Ions are form ed w hen atom s capture surplus electrons to give nega
tively charged anions or w hen they shed electrons to give positively charged cations. An
atom m ay form several types o f ions. Iron, for exam ple, forms both ferric (Fe3+) ions and
ferrous (Fe- + ) ions, w hile it also occurs in the F e0 elem ental form.
A nuclide is an atom ic nucleus characterized by the num ber Z of its protons and the
num ber N o f its neutrons regardless o f its cloud of electrons. T he m ass num ber A is the
sum of the nucleons N + Z . D ifferent interactions act in the nucleus and explain its b in d
ing: the short-range (nuclear) strong force, the long-range electrom agnetic force, and the
m ysterious interm ediate w eak force. Two nuclides w ith the sam e num ber Z o f protons but
different num bers N o f neutrons w ill b e accom panied by the sam e suite o f electrons and
so have very sim ilar chem ical properties; they w ill be isotopes o f the sam e elem ent. The
chart o f the nuclides (Fig. 1.1) shows that in order to be stable, nuclides m ust contain a
specific proportion o f neutrons and protons. T he sem i-em pirical form ula for the energy of
a nucleus is:
E = aA - bA

-/3+ c (N -A Z }

- d

^AZ1/3n3

(1.1)

The properties of elem ents

Naturally abundant nuclide

Neutron-poor nuclides
(stable or long lived)
\
" Naturally rare or artificial nuclide
(short lived)
N
a
n
E

Z = N,

2
l

Neutron number, N
^ Figure 1.^ [

Chart of the nuclides (overview). The light stable elements have approximately the same number
Z of protons and number N of neutrons but the heavier stable elements deviate towards the
neutron-rich side according to (1.2): this relationship defines the valley of stability. Elements that
depart significantly from this rule are unstable (radioactive).

and this describes the so-called liquid drop m odel of the nucleus. T he constants a, b, c,
and d can be adjusted to fit laboratory data. As a first approxim ation, the volum e o f the
nucleus is proportional to A, its radius to A 1/3, and its surface area to A 2/3. T he first
term on the right-hand side expresses the volum e energy, w hich is proportional to the
num ber o f nucleons; the second term is the surface energy, w hich subtracts the unco m
pensated attraction of the nucleons located near the surface of the nucleus; the third term
expresses that, for a given A , the nuclear attraction betw een proton and neutron is slightly
stronger than p roton-proton and neu tro n -n eu tro n attraction; the fourth term accounts for
electrostatic energy w hich is inversely proportional to the distance betw een the neighbor
ing charges o f the protons. The locus o f m inim um energy, in the N , Z plot of Fig. 1.1,
w hich is know n as the valley o f stability, is obtained by m inim izing (1.1) w ith respect to
Z , and is conveniently represented by the equation:
2A
Z = -----------------TTT
4 + 0.031 A 2/3

(1.2)

For light elem ents (Z < 40), the term in A at the denom inator is very small, so Z & A /2
and therefore N & Z . A t higher m asses, electrostatic repulsion betw een protons gets
stronger and N > Z . O ne easily finds that for 238U, Z = 92 w hich is correct.
N uclei with N and Z too far from this valley o f stability are unstable and are said to be
radioactive. An isotope is radioactive if its nucleus undergoes spontaneous change such as
occurs, for instance, w hen alpha particles (two protons and two neutrons) or electrons are
em itted. It changes into a different isotope, referred to as radiogenic, by giving out energy,
usually in the form o f gam m a radiation, som e o f w hich is harm ful for hum ans. Several
internet sites provide tables o f all stable and radioactive nuclides. The vast m ajority of

1.1 The periodic table

natural isotopes o f naturally occurring elem ents are stable, i.e. the num ber o f their protons
and neutrons rem ains unchanged, sim ply because m ost radioactive isotopes have vanished
over the course o f geological tim e. They are therefore not a danger to people.

1.1 The periodic table

T he atom ic num ber o f an elem ent is equal to the num ber of its protons. We have seen before
that the atom s m ass num ber is equal to the num ber o f particles m aking up its nucleus. The
A vogadro num ber N is the num ber o f atom s contained in 12 g of the carbon-12 isotope.
T he atom ic mass o f an isotope is the w eight o f a num ber N o f atom s o f that isotope.
D im itri M endeleevs great discovery in 1871 was to dem onstrate the periodic character of
the properties o f elem ents w hen ordered by ascending atom ic num ber (Fig. 1.2). M elting
point, energy o f form ation, atom ic radius, and first ionization energy all vary periodically as
w e w ork through M endeleevs table. T he geochem ical properties o f elem ents are reflected
by their position in this table. T he alkali m etals (Li, N a, K, Rb, Cs), alkaline-earth m etals
(Be, M g, Ca, Sr, Ba), titanium group elem ents (Ti, Zr, Hf), but also the halogens (F, Cl,
Br, I), inert gases (He, N e, Ar, Kr, X e), rare-earths (lanthanides), or actinides (uranium
fam ily) all form groups sharing sim ilar chem ical properties; these properties are indeed
som etim es so sim ilar that it was long a challenge to isolate chem ically pure forms of
som e elem ents such as hafnium (Hf), w hich was only separated from zirconium (Zr) and
identified in 1922.

II

III

IV

VI

VII

VIII

H
Li

Be

Na

Mg

Al

Ca

Sc

Ti

Rb

Sr

Zr

Cs

Ba La*

Hf

11
19

37
55
87

Fr

12

20

21

38

39

56
88

57

22
40
72

24

25

26

27

28

29

30

31

Si

14

15

32

33

16

34

F
Cl

17
35

10

Ne

18

Ar

36

Co

Ni

Cu

Zn

Ga

Ge

As

Se

Br

Kr

Nb

Mo (Tc) Ru

Rh

Pd

Ag

Cd

In

Sn

Sb

Te

Xe

Ta

Ir

Pt

Au

Hg

Tl

Pb

Bi

Po

At

73

42
74

Mn

Fe

41

Cr

43
75

Re

44
76

<s

45
77

46

78

47
79

48
80

49
81

50
82

51
83

52
84

5:
85

54
86

Rn

89

Ra Ac**
57

*Lanthanides

La

**Actinides

Ac

89

- <3
[ Figure 1.2^

23

13

He

58

Ce
90

Th

Siderophile

59

Pr
91

Pa

60

61

62

Nd (Pm) Sm
92

93

Np

63

Eu

64

Gd

65

Tb

66

Dy

67

Ho

68

Er

69

Tm

70

Yb

71

Lu

94

Pu

| Cu | Chalcophile

| Rb | Lithophile

Atmophile

Mendeleev's periodic table of the elements and their geochemical classification after
Goldschmidt. The elements in parentheses do not occur naturally on Earth. The atomic number
of each element is given. Roman numerals over columns indicate groups.

The properties of elem ents

<&
*
f (examples)
^ Figure 1.3[

Examples of orbital geometry. Shown here are the surfaces of maximum probability of electron
localization around the nucleus corresponding to various orbitals. s, p, d, f are the quantum
numbers. Note the two types of d orbitals. Drawn using Orbital Viewer (Dave Manthey).
It is therefore very im portant to understand how elem ents are ordered in the periodic
table. Put simply, an atom can be represented as a point-like nucleus containing the mass
and charge o f the nuclear particles and by m ass-less electrons orbiting this point. T he heavy
nucleus is norm ally assum ed to b e im m une to fluctuations in the m ore volatile electron
clouds and is treated as stationary (B orn-O ppenheim er approxim ation). Q uantum m echan
ics requires the different forms o f electron energy to be distributed discretely, i.e. at separate
energy levels. It also requires that the different form s o f m om entum b e quantized, not only
the linear form o f gas m olecules bouncing around in a box, but also the angular m om entum
of the electrons on their atom ic orbitals and around their spin axis. T he angular m om entum
L plays the sam e role w ith respect to angular velocity w as linear m om entum p = m v
plays w ith linear velocity v: the fam iliar expression defining the linear kinetic energy as
p - / - m becom es L - / - 1 for rotational kinetic energy, w ith the m om ent of inertia I playing
for rotational energy the role o f m ass m for linear translation.
T he H eisenberg principle states that the uncertainty o f the position and the velocity of
a particle vary inversely to one another and therefore prevents the exact calculation of
electron orbits around the nucleus. An orbital is a com plex function used by quantum
m echanics to describe the probability of the presence o f an electron around the nucleus but
it is often reduced to a three-dim ensional surface m eant to represent the locus of m axim um
probability. It is denoted (Fig. 1.3) by a set o f integers know n as quantum num bers. T he
four levels o f quantization are as follows:
1. T he first (principal) quantum num ber n characterizes the total energy level of the elec
tron and can take positive values 1, - , 3, . . . It defines the m ain electron shells, w hich
are som etim es represented by the letters K, L, M , . . .
- . The second (orbital) quantum num ber l characterizes the total orbital angular m om en
tum L of the electron; it ranges from 0 to n - 1 and defines the num ber o f lobes o f the
orbitals o f each shell, w hich are usually designated by the letters s, p, d, f.

1.1 The periodic table

Table 1.1 Electronic configuration of the light elements

Quantum numbers
Element

I
VIII
I
II
III
IV
V
VI
VII
VIII
I

1
1
2
2
2
2
2
2
2
2
3

0
0
0
0
1
1
1
1
1
1
0

0
0
0
0
-1
-1
0
0
+1
+1
0

+ 1/2
-1 /2
+ 1/2
-1 /2
+ 1/2
-1 /2
+ 1/2
-1 /2
+ 1/2
-1 /2
+ 1/2

Configuration
1s1
1s2 = [He]
[He] 2s1
[He] 2s2
[He] 2s2 2p1
[He] 2s2 2p2
[He] 2s2 2p3
[He] 2s2 2p4
[He] 2s2 2p5
[He] 2s2 2p6 = [Ne]
s
3
e]
e[
N

H
He
Li
Be
B
C
N
O
F
Ne
Na

Group

3. T he third (m agnetic) quantum num ber m (0, 1 , . . . , l ) gives the part L z o f the angular
m om ent w hich points along the rotation axis; it defines the shape o f the orbital.
4. T he fourth quantum num ber s describes the m om entum associated w ith the spin of the
electron and gives the direction o f spin o f the electron around its own axis relative to its
orbital m ovem ent.
T he Pauli exclusion principle states that no two electrons can have the sam e quantum
num bers.
T he periodic table can be constructed by assigning a unique set o f quantum num bers to
each elem ent (Table 1.1) and the filling o f the successive orbitals can now proceed from
low er to higher energy levels until the num ber o f electrons m atches the num ber of protons
in the nucleus. This holds for n , by definition, but also for l because of the electrostatic
screening by electrons on low er orbitals (see below ): for exam ple, orbital 2p is filled after
orbital 2s. T he filling order is show n in Fig. 1.4 and can b e exactly m atched w ith the
periodic table.
A num ber o f Internet sites provide detailed periodic classifications, o f w hich I
can recom m end http://w w w .w ebelem ents.com /, w hile D ave M antheys excellent site
http://w w w .orbitals.com /orb/ov.htm provides softw are to create very professionally drawn
orbital pictures (Fig. 1.3).
In the periodic table, groups I (alkali m etals) and II (alkaline-earth m etals) correspond
to the filling o f s orbitals, and groups III to V III to that o f the p orbitals. T he interm edi
ate groups (transition elem ents such as iron and platinum ) differ in the occupation o f their
d orbitals. W hen occupied, these d orbitals are norm ally closer to the nucleus than the s
orbitals of the next shell out. O ccupation o f the orbitals is noted n x 1, w here x represents
the type o f orbital (s, p, d, f), n its principal quantum num ber and i the num ber o f electrons
it contains. M ost elem ents o f the first series (e.g. V, Cr, M n, Fe, Co, N i, Cu, Zn) have an
electron form ula o f the type [Ne]3s2 3p6 3d1 4 s2, w here [Ne] represents the fully occupied

10

The properties of elem ents

l= 0
^ Figure 1.4[

The filling order of the lowest orbitals of the elements in the periodic table. The vertical scale
shows the energy levels.

Nucleus
^ Figure 1.5[

|nner electron
cloud

Shielding of the nuclear charge by the cloud of electrons orbiting between the outer electrons
and the nucleus.

orbitals o f a neon atom; and their divalent ions, such as F e2+ and C u2+, have a configura
tion [Ne]3s2 3p6 3d1. T hese transition elem ents differ only by the num ber i of electrons in
orbital 3d but have an identical outer electron shell 4s, w hich explains w hy their chem ical
properties are so similar. This phenom enon is further am plified in the rare-earths (or lan
thanides), such as L a and Ce (shell 4 f ), and the actinides ( 5 f ), such as U and Th, w here
the s and p orbitals of the external shells are identical.
S im ple rules hold for the prediction o f atom ic radii. First, the potential energy and atom ic
radius increase w ith n and therefore down each colum n o f the periodic table. Second,
the atom ic radius decreases across each row. This is due to the reduction o f electrostatic
attraction of the outer electrons by the cloud o f the inner electrons (Fig. 1.5), a phenom enon
know n as shielding. For the lanthanides and the actinides, the f electrons on their m ultilobate orbitals leave som e parts o f the nucleus exposed (Fig. 1.3) and therefore do not
screen the increasing charge o f the nucleus as efficiently as the m ore sm oothly shaped
low er-order orbitals. As a result, their atom ic radii decrease sm oothly w ith their increasing
atom ic num ber, a phenom enon know n as lanthanide (and actinide) contraction.

11

1.2 Chemical bonding

Triangular
(e.g. CO3, BO3)

Octahedral
(e.g. Fe2+, Mg2+, Ca2+)
^ Figure 1.6[

Tetrahedral
(e.g. SiO4, AlO4)

Dodecahedral
(e.g. K+)

The main ion coordination systems in naturally occurring minerals: triangular (three closest
neighbors), tetrahedral (4), octahedral ( 6 ), and dodecahedral (12) coordination.
The energy stored in silicates as chem ical bonds depends on the nature o f the cations
and the crystal sites accom m odating them . D epending on their ionic radius, cations m ay
occupy sites o f varying size and the num ber o f oxygen neighbors w ith w hich they bond
(coordination num ber) increases w ith the size o f the site. Carbon and boron atom s com bine
w ith oxygen in a triangular arrangem ent (i.e. threefold coordination, Fig. 1.6), w hile silicon
and alum inum atom s com bine w ith oxygen to form a tetrahedron (fourfold coordination).
However, m edium -sized cations, such as F e2+, M g2+, or C a2+, w ill take up vacant octa
hedral sites (sixfold coordination) betw een SiO 4 tetrahedra w hile the biggest ions, such
as K + or O H

hydroxyl anions, require the m ost spacious sites, norm ally o f tw elvefold

coordination.

1.2 Chemical bonding

A tom s and ions com bine to form m atter in its solid, liquid, or gaseous states. The
im portance of occupation of the outer electron shell can b e illustrated by com paring the
interaction betw een two atom s o f helium , w here two electrons occupy orbital 1s, with
the interaction betw een two hydrogen atom s, each w ith a single electron only. W hen the
tw o helium atom s com e close together and their electron clouds interpenetrate, one atom s
electrons cannot be accom m odated by the orbital o f the other as this w ould infringe the
Pauli exclusion principle. They m ust therefore ju m p to the 2s orbital, at a cost in energy that
penalizes the form ation o f such bonds. Two hydrogen atom s, however, can lend one another

12

The properties of elem ents

a 1s electron. T he resulting electron configuration is m ore advantageous than that of iso

lated hydrogen atom s and thus chem ical bonding is favored. This is the essence of P aulings
valence bond theory, w hich, however, fell into disfavor for its inability to explain the spec
troscopic properties o f substances. In contrast, the crystal field theory sees fully ionized
cations, such as N a+ or C a2+ being hosted in sites defined by negatively charged lig
ands such as the silicate netw ork: the bond is assum ed to b e fully electrostatic. A lthough
the valence theory accounts for m any properties of the transition elem ents, it is now also
considered as largely obsolete.
T he dual character o f m ost chem ical bonds is accounted for by the concept o f m olecular
orbitals: w hen atom s and ions com e close to each other, their individual electronic orbitals
m erge into collective orbitals, w hich, however, in general rem ain difficult to calculate. The
type of chem ical bonding is determ ined by the probability of the presence o f the electron
next to one of the bound nuclei, w hich is exactly w hat the m olecular orbitals are m eant to
describe. If the electron is transferred perm anently, ionic bonding has occurred: a sodium
atom in the presence o f a chlorine atom w ill give up its isolated 3s electron because their
outer shells w ill then be com pletely occupied, w ith sodium configured like neon and chlo
rine like argon. T he ions form ed in this way, noted as N a+ and C l- , are particularly stable;
their outer electron shell is largely spherical and these ions act like electrically charged
spheres m utually attracted by their electrostatic fields to form ionic com pounds such as
table salt, N aC l. Conversely, w hen the num ber o f electrons that can b e exchanged fails to
fill the outer shells of the tw o partners, a covalent bond is form ed. Two hydrogen atoms
lend one another their m issing electron but m ust share the two 1s electrons over tim e by
form ing hybrid orbitals o f com plex geom etry thereby allow ing them to fill the outer shell
of both atoms.
T he transition elem ents (V, Fe, Cu, Zn, etc.) are particularly sensitive to their crystalline
environm ent. T hey differ from each other by a different filling of their d orbital (Fig. 1.3).
Two o f these orbitals, called eg, have their lobes lying along the axes o f rectangular coor
dinates, w hile three orbitals, called t2g, lie in each plane defined by two axes but w ith their
lobes sticking out in betw een the axes. In the m ost com m on octahedral sites occupied by
transition elem ents in silicates, w ith an oxygen atom at each apex along the axes, an elec
tron occupying a t2g orbital feels the repulsion by the electrons from the oxygen ions, the
so-called crystal field, m uch less than an electron occupying an eg orbital (Fig. 1.7). C all
ing A the crystal field stabilization energy (CSFE), i.e. the difference in bonding energy
betw een t2g and eg, the energy shift o f the three t2g orbitals is - 2 A /5 , w hile the shift for
the two eg orbitals is + 3 A /5 , thereby ensuring that the m ean energy shift w ith respect to
a spherical environm ent is zero (Fig. 1.8).
L et us now give exam ples o f how these concepts are relevant to the energetics o f elem ent
partitioning in crystallographic sites:

1. Trivalent chrom ium ion C r3+ has electronic form ula [Ar]3d3 4 s0 ([Ar] stands for the
orbital filling o f argon) in an octahedral site. O ne electron on each t2g orbital gives this
ion a bonding energy o f 3 x ( - 2 A / 5 ) = - 6 A / 5 . In spite of a charge at odds w ith the
m ajor cations, such a large value m akes C r3+ an elem ent abundant in som e F e-M g
m inerals, m ost conspicuously pyroxene.

13

^ Figure 1.^ [

1.2 Chemical bonding

Crystal field effect on a transition element, such as Fe, Mn, Cr, in octahedral coordination. Six
oxygen atoms form the apexes of the octahedron. The t2g orbitals of the transition element lie
between the oxygen atoms, while the eg orbitals point toward them. The filling of an eg orbital
by electrons therefore has to overcome excess repulsion energy compared with a t2g orbital.

eg
+34/5

Spherical
field

-24/5
---- T
--------- f2g
Octahedral
field

No field

^ Figure 1.8[

Splitting of the d energy levels in the octahedral site of (Fig. 1.7). If the ion is inserted into a
spherical site, the repulsion to overcome is symmetric for the electrons on all the d orbitals. In an
octahedral site, which is particularly common in silicate rocks, the two eg orbitals are subjected to
stronger repulsion than the three t2g orbitals. For the same overall interaction energy, and a
difference A in bonding energy between t2g and eg (the crystal field stabilization energy), the
energy shift of the t2g orbitals is - 2 A /5 , while the shift for the eg orbitals is + 3 A /5 . In a
tetrahedral site, the situation would be reversed.

2. F errous iron F e2+ has electronic form ula [Ar]3d6 4 s0. O nce the low est three t2g orbitals
are occupied by one electron each, there are two options: (i) if A is less than the rep u l
sive energy o f electron-electron pairing, the next electron w ill fit an upper eg orbital or,
(ii) if A is large, it w ill pair w ith an electron on the t2g orbital. Two F e2+ configurations
are therefore possible in each case (Fig. 1.9) w hich receive their denom ination from
the w ay electronic spins add up. T he m ost abundant iron in the m antle corresponds to
the sm all A case and is referred to as high-spin Fe. T he energy gain due to crystal

14

The properties of elem ents

High-spin Fe2+

^ Figure 1.^ [

Two electronic configurations for the same ion Fe2+ with 6 d electrons. When the crystal field is
strong, the energy gap A between the t2g and eg orbitals increases, and the six electrons fill the
three t2g orbitals. This is the low-spin configuration. When the crystal field is weak, the energy
cost of pairing electrons dominates and two electrons move to the upper eg orbitals. This is the
low-spin configuration. Only some ions of transition elements show such a dual configuration.
field is 4 x ( - 2 A /5 ) + 2 x (3 A /5 ) = - 2 A / 5 . Conversely, the large A case (full t2g)
is referred to as low -spin F e and has a crystal field effect o f - 1 2 A /5 .
3. F or divalent nickel N i2+ ([A r]3d8 4 s0), the configuration is unique: the three t2g orbitals
are fully occupied, w hile each o f the eg orbitals hosts one electron. T he energy gain
is 6 x ( - 2 A / 5 ) + 2 x (3A /5 ) = - 6 A / 5 ; N i2+ therefore snuggles in octahedral sites
and is notably enriched in F e-M g silicates such as olivine and pyroxenes.
4. T he com m on high-spin M n2+ ([A r]3d54 s0) as w ell as Z n2+ ([A r]3d104 s0) have sym
m etrical orbital configurations and therefore no energy gain: in general, they show little
preference betw een silicate m inerals or betw een silicates and m elts.
T he effect of the crystal field is essentially sym m etrical w hen these ions occur in tetrahedral
coordination.
In solutions, transition-elem ent com pounds form by interaction betw een a ligand and
a cation, w hich is the basis of Lew is acid -b ase theory. Typical of such interaction is
hydration, e.g. for Zn
Z n2+ + H 2O ^

Z n2+ (O H )

+ H+

(1.3)

15

1.3 States of matter and the atomic environment of elements

w hich shows the strong attraction o f the Z n2+ cation for the lone electron pair carried
by the oxygen. W ater acts as the donor and Z n2+ is the acceptor. T he reaction results
in the liberation o f a proton, w hich justifies the fact that Z n2+ is referred to as a Lew is
acid and w ater as a Lew is base. In general, a species donating a pair o f electrons is a
Lew is base, w hereas a species accepting this pair is a Lew is acid. T he variable hardness
of Lew is acids, not to be confused w ith their strength that m easures the energy o f the
proton bond, helps us to understand the direction of inorganic and organic reactions. Ions
are separated into hard Class a (groups I and II o f the periodic table plus the lightest
transition elem ents), soft Class b (the upper right o f the periodic table), and borderline
(Fe2+ , C u2+ , Z n2+ , Pb2+ ) elem ents as a function o f their affinity for lone electron pairs.
W hy this additional criterion is im portant can b e illustrated w ith the follow ing reaction:
CoCl4- + 6 H 2 O ^

Co (H 2 O ) 6+ + 4 C l-

(1.4)

A dding the Lew is acid C a2+, w hich is a harder acceptor than C o2+ and therefore strongly
binds to w ater m olecules, displaces the reaction to the left and gives the strong blue color
of the chloride to the solution. In contrast, adding Z n 2+ , w hich is a softer Lew is acid than
C o2+, pushes the reaction to the right and shows the p ink color o f the hydroxide. Such
reactions are essential to account for the role o f m etals w ith respect to organic ligands.
Pressure is especially im portant in the environm ent of ions. O xygen is m ore com press
ible than sm aller ions and, w ith its cation coordination num ber increasing, it plays an
essential role. Thus, at depths o f m ore than 660 km, pressure levels in the low er m antle
are such that silicon coordination shifts from fourfold to sixfold thereby prom oting the
com pact stacking o f oxygen atom s. Likew ise, under conditions o f the low erm ost m an
tle, site distortion becom es im portant and som e m inerals such as oxides show a transition
from high-spin to low -spin iron. It rem ains, however, a real challenge to predict w ith full
accuracy the chem ical properties o f elem ents at very great depths.

1.3 States of matter and the atomic environment of elements

Bonds form ed by condensed m aterials are generally m ore com plex than those form ed by
gases. In silicates, w hich are so im portant to our understanding o f geological phenom ena,
a sm all silicon (or possibly alum inum ) atom (Fig. 1.10) lies at the center o f a tetrahedron
of four oxygen atoms. As in carbon chem istry, SiO 4 tetrahedra m ay polym erize to varying
degrees by sharing one or m ore oxygens at their apexes. T he S i-O bond is a quite strongly
covalent one. O ther elem ents, such as M g, Fe, or N a, m ay b e accom m odated w ithin the
silicate fram ew ork in their ionic form s M g 2+, F e2+, Na+.
T he m any crystallized silicate and alum ino-silicate structures are classified according to
the pattern form ed by their tetrahedra. T he m ost im portant ones in geology are:
1. Isolated-tetrahedra silicates: the m ost com m on m inerals in this fam ily are the var
ious sorts o f olivine, such as forsterite M g 2 SiO 4 , and o f garnet, such as pyrope
M g 3 A l 2 (SiO 4 )3 .

16

The properties of elem ents

O
Si

O
O
O
. Si
O

^ Figure 1.1p|

\O

Si
O

SiO4 tetrahedra, which are the building blocks of silicate structures and their polymerization.
Aluminum similarly forms AlO4 tetrahedra.

2. Single-chain silicates: these are the pyroxenes, w hich fall into two groups w ith two
different crystallographic system s; orthopyroxenes, such as enstatite M g 2Si2O 6, and
clinopyroxenes, such as diopside C aM gS i2O 6.
3. D ouble-chain silicates: am phiboles, such as trem olite C a2M g5Si8O 22(O H )2 or h o rn
blende C a2M g4A l2Si7O 22(O H )2. T he form ation o f these hydroxylated m inerals
requires som e degree o f w ater pressure.
4. Sheet silicates: m icas and clay m inerals usually containing alum inum , potassium , and
sm aller ions such as F e2+ and M g2+. A distinction is draw n betw een di-octahedral m icas
like m uscovite (com m on w hite m ica) K 2A l6Si6O 20(O H )4 and tri-octahedral m icas like
biotite (ordinary black m ica) K 2M g 6A l2Si6O 20(O H )4, the difference being the propor
tions o f 2 + and 3 + cations and therefore site occupancy. This fam ily is extrem ely
diverse.
5. Fram ew ork silicates: these silicates are interconnected at each o f their apexes. This
fam ily includes quartz SiO 2 and the feldspars, the m ost im portant o f w hich are albite
N aA lS i3O 8, anorthite C aA l2Si2O 8, and the various potassium feldspars w hose form ula
is K A lSi 3 O 8.
O ther significant m inerals include iron oxides and titanium oxides, w hich are com m only
cubic ionic solids such as m agnetite F e 3 O 4 and ilm enite FeTiO3. C orundum is the oxide of
alum inum A l 2 O 3 . C alcium carbonate (calcite, aragonite) and m agnesium carbonate (m ag
nesite), form ed by stacking o f C a2+ or M g2+ ions, contain sm all carbonate groupings
CO 32 - able to rotate around the axis o f symmetry.
T he m inerals cited above are only exam ples, albeit im portant ones, but alone they fail to
provide a sufficiently precise representation of the chem ical diversity of rocks. E lem ents
are located w ithin m inerals at sites characterized by the num ber o f oxygen atom s that they
have as their im m ediate neighbors. We have already com e across the tetravalent silicon
ion Si4+ (i.e. carrying four positive charges) at a tetrahedral site and said that it could be
replaced by the trivalent alum inum ion Al3+. E lectrical neutrality is m aintained through
paired substitutions such as A l3+A l3+ substituting for Si4+M g2+. Such substitution is p o s
sible and even com m onplace in pyroxenes, am phiboles, m icas, and feldspars as the two
ions have sim ilar ionic radii (0.39 and 0.26 A, respectively) and sim ilar electrical charges.

17

1.4 Geochemical classifications

Likew ise, M g2+ ions (0.72 A) located at octahedral sites o f naturally occurring olivine,
i.e. those surrounded by six oxygen atom s, are com m only replaced by F e2+ ions (0.61 A)
or N i2+ ions (0.69 A). Ions o f the rare-earth elem ent family, such as the Y b3+ ytterbium
ion (0.99 A), m ay substitute for the C a2+ ion ( 1 .0 0 A) in clinopyroxenes or am phiboles.
As these continuous substitution phenom ena are analogous to those w hereby various ions
co-exist in aqueous solutions, the term solid solution is used.
N ot all solid solutions are possible. T he larger ions, such as the alkali m etals (K+, R b+ )
or the alkaline-earth m etals (Sr2+, B a2+ ) o f the higher periods, have ionic radii that are too
big for them to fit readily into the com m on silicate m inerals. Ions w ith different charges
m anage to substitute for m ajor ions if the electrical im balance can be offset locally: a
(Ca 2+ ) 2 pair m ay thus be replaced by a Y b 3+ N a+ pair in a clinopyroxene, w hereas its
replacem ent by a Th4+ thorium ion requires the form ation o f a defect w ith a h igh energy
cost. Ions that carry too high a charge or w hose ionic radius is too sm all or too large are
rejected by the lattice of essential m inerals and concentrate either in accessory m inerals,
such as the phosphates or titanates, or in poorly characterized phases in grain fractures
and interstices. T hese outcasts are term ed incom patible elem ents. However, this is a re l
ative concept: potassium and barium are incom patible in the feldspar-free m antle; yet, in
the continental crust, w here feldspar is abundant, K and B a are com patible. T he volatile
elem ents and com pounds, such as the rare gases, water, and carbon dioxide, call for som e
attention. As long as no gas phase is present, i.e. as long as the concentration o f one o f the
m ost abundant volatiles in the solid or liquid in question does not exceed saturation level,
they behave like any other elem ent w ith varying levels of com patibility. In the absence of
vapor, for exam ple, the inert gases such as helium or argon need not be classified separately
from the other trace elem ents.

1.4 Geochemical classifications

T here are m any w ays to arrange elem ents by their geochem ical properties. Such practice,
reducing as it does the w ide diversity of behavior of elem ents to lim ited ranges o f behavior,
m ight be thought pointless, but it does provide an overview o f their chem ical proper
ties. The m ost w idespread classification is probably that of V ictor G oldschm idt (Fig. 1.2).
G oldschm idts schem e rests on the observation by B erzelius, a Sw edish eighteenth-century
chem ist, that som e elem ents tend to form oxides or carbonates w hereas others form
sulfides. T he lithophile elem ents (Na, K, Si, Al, Ti, M g, Ca) generally concentrate in
the rock-form ing m inerals o f the crust and m antle; the siderophile elem ents (Fe, Co,
N i, Pt, Re, Os) have an affinity for iron and therefore concentrate in the E arth s core;
the chalcophile elem ents (Cu, Ag, Zn, Pb, S) readily form sulfides; the atm ophile ele
m ents (O, N, H, and the inert gases) concentrate in the atm osphere. Certain elem ents
in each group tend to be volatile; K is a m ore volatile lithophile than either M g or Ti
(see C hapter 12). R efractory elem ents such as M g or C r tend to concentrate in solid
residues.

18

The properties of elem ents

[ Figure 1.111

Plot of the electrostatic potential (charge/ionic radius) vs. ionic radius for different metallic ions.
Ionic radii are given in A (10- 10m). The curves of constant charge (1+ to 5+) are also shown. The
roman numerals refer to coordination numbers. This plot is useful for the identification of groups
of elements with coherent geochemical behavior: network-forming elements, high-field-strength
elements (HFSE), and large-ion lithophile elements (LILE).

T he ratio o f the charge to the radius o f an ion defines its electrostatic potential, i.e. its
ability to m odify the electrostatic field in w hich adjacent ions are bathing. This potential
defines a large num ber of the properties associated w ith each elem ent, such as its tendency
to attract bond electrons (electronegativity) or to form com pounds such as oxo-anions and
hydrates. Plotting this potential vs. the ionic radius itself, w hich is a m easure o f the io n s
ability to fit specific sites in m inerals, is particularly inform ative of the geochem ical p ro p
erties o f a particular ion (Fig. 1.11). L arge ions carrying w eak charges (K, Rb, Cs, Ba) are
accom m odated w ith difficulty by the m ain m inerals of the m antle, except for K -feldspars,
and so are concentrated in the continental crust. They are know n as large-ion lithophile
elem ents (LILE). Sm all ions carrying strong charges (Zr, N b, Th, U ) develop intense elec
trostatic fields (high-field-strength elem ents, H FSE), hence they do not readily substitute
for the m ajor elem ents in ordinary m inerals. Relative positions in the periodic table rem ain,
however, essential, and elem ents in the sam e colum n share com m on geochem ical proper
ties, as is the case of the alkali m etals (Na, K, Cs), alkaline-earth m etals (Mg, Ca, Sr),
halogens (F, Cl, Br), or transition elem ents o f the sam e row.

19

1.5 The different reservoirs and their compositions

1.5 The different reservoirs and their compositions

In solids, elem ents are sequestered in m inerals, m inerals assem ble as rocks, and rocks
constitute the m ain geodynam ic units o f the m antle and the crust. Som e elem ents occur
in particularly large abundances in seaw ater or in the atm osphere (H, O, N, Ar). Terres
trial rocks fall into three m ain categories: igneous rocks, such as basalts and granites,
produced by m agm atic processes, i.e. from the m elting of rocks; sedim entary rocks,
form ed by the accum ulation of clastic and biological particles or by chem ical p recipi
tation on the floors of the oceans and other bodies o f water; and m etam orphic rocks,
produced by firing existing rocks at high tem perature, under pressure, and, for m ost
o f them , in the presence o f aqueous or carbonic fluids. E xtra-terrestrial rocks cannot
be classified in quite the sam e way. Igneous rocks occur on the M oon, m ost probably
on M ars, and as m eteorites (achondrites). A nother type o f m eteorite, know n as a chondrite, has no terrestrial equivalent. C hondrites w ere form ed by condensation of gases from
the solar nebula and by droplets of silicate liquids called chondrules, from w hich their
nam e is derived. M etam orphic transform ations m ay affect planetary rocks and m eteorites
as well.
A reservoir is a loosely defined term referring to a very large body o f rock (m antle,
crust), w ater (ocean), or gas (atm osphere) w hose m ean com position stands in sharp co n
trast to the com position o f other reservoirs. It m ay contain a variety of com ponents, but
its com position is norm ally very different from the com position o f com ponents present in
other reservoirs: for instance, the Si-rich rocks m aking up the continental-crust reservoir
are easily differentiated from the M g-rich rocks m aking up the m antle. A reservoir m ay be
spatially continuous (e.g. the ocean) or scattered over large distances in the E arth (e.g. recy
cled oceanic crust in the deep m antle). T he m ost abundant chem ical elem ents in each o f the
m ain terrestrial reservoirs are listed in A ppendix A . However, a clearer understanding of
these chem ical distributions requires som e idea of w hich m inerals contain these elem ents
(see next chapter). O xygen is found ju st about everyw here, w hereas silicon is confined to
the silicates, w hich are by far the m ost abundant m inerals. T he silicon content of m inerals
is a particularly significant param eter because the SiO 2 (silica) concentration is a m easure
o f the acidity of rocks: this obsolete term , w hich dates from the days w hen silicates w ere
view ed as silicic acid salts, still pervades the literature. T he silica concentration o f m iner
als increases from olivine, pyroxene, am phibole, and m ica through to feldspar and quartz.
M agnesium and iron are particularly abundant in olivine, in pyroxene o f igneous rocks,
in am phibole, and in the sheet m inerals (biotite, chlorite, and serpentine) of m etam orphic
rocks. A felsic (acidic) rock, such as a granite or a rhyolite, is rich in silicon and poor in
m agnesium and iron; a mafic rock, the archetype o f w hich is basalt, has a high M g and
F e content. C alcium is found, above all, in igneous pyroxene and calcitic feldspar (plagioclase), in sedim entary carbonate, and in m etam orphic am phibole. A lum inum has m any
carriers: in igneous rocks it is located, by increasing order o f pressure, in plagioclase, spinel
(oxides), and garnet; it concentrates in the clay m inerals o f sedim entary rocks and in m ica
o f m etam orphic rocks (biotite and m uscovite). Potassium and sodium are scarcely found
outside m ica and feldspar.

20

The properties of elem ents

W hen rock m elts, som e elem ents (Na, K, Al, Ca, Si) are fusible, w hereas others (Mg
and to a lesser extent Fe) are m ore refractory; m agm atic m elting therefore contributes to
geochem ical fractionation am ong reservoirs. In the sam e way, som e elem ents (Na, K, Ca,
M g) are m ore soluble in w ater than others, inducing further geochem ical fractionation
during erosion and sedim entation.
W hen the com position of the m antle is com pared w ith that o f the Earth as a w hole
it can be seen to have a high refractory-elem ent content, especially o f M g and Cr, and
a low er content o f fusible elem ents, especially N a, K, Al, Ca, and Si, dem onstrating its
residual character w ith regard to m elting. As m ight be expected, olivine and pyroxene
are predom inant in the m ineralogy o f the upper mantle: peridotite is the ubiquitous rock
form ing the upper m antle. T he continental crust, on the other hand, is enriched in fusible
elem ents (accom m odated m ainly in feldspar, quartz, and clay m inerals) and exhibits a m elt
liquid character in contrast to the residual m antle. T he oceans are obviously enriched
in soluble N a, K, and C a cations and anions (C l- , SO4- ), w hile elem ents that are both
insoluble and fusible (Si, Fe, and Al) accum ulate in clastic sedim entary rocks (clays).
T he com position o f the Sun, the E arth s crust and m antle, etc., is given in A ppendix A .
It is not always easy to determ ine these com positions; w hile observation o f the solar spec
trum and analysis o f m eteorites, o f seawater, and o f river w ater yield data that can be
tabulated fairly directly, determ ining the com position o f the E arth s crust calls for discus
sion o f the nature of the low er crust, the low er m antle, the core, and o f the Earth as a whole.
The m echanism s responsible for form ing these m ajor, but not directly observable, geolog
ical reservoirs m ust therefore b e reasonably w ell understood b efore their com positions can
be estim ated. This w ill be covered briefly in Chapters 11 and 12.

1.6 The nucleus and radioactivity

A lthough the forces holding the nucleus together are extrem ely pow erful, observation
shows that som e nuclei are unstable, i.e. radioactive. R adioactivity is a property of
the nucleus and involves gigantic energies of the order o f a few M eV per nucleon
(1 eV /m olecule = 1.6 x 10-19 x 6.022 x 1023 = 96.5 kJ m o l- 1 ) (Table 1.2). T he tem
peratures, w hich are a m easurem ent o f atom ic and m olecular excitation, required to break
a nuclear bond are orders o f m agnitude higher than those required to exchange electrons
(chem ical reactions) or even to rem ove an electron from an atom ic orbital (ionization
energy) and only occur in stellar interiors like that o f the Sun. T hese enorm ous energies
explain the extrem e efficiency o f nuclear energy w ith respect to any other alternative energy
form. N uclear bonds are not dependent on the atom s electron suite and therefore not on
any chem ical reaction or m ineralogical phase change w hich take place at m uch low er ener
gies: rem oving the first electron from an atom typically requires only a few eV per atom
(ionization potential). M ineralogical, tem perature, and pressure processes involve even
sm aller energies. R adioactivity is therefore independent o f the chem ical and m ineralogical
environm ent of the elem ent, o f tem perature and o f pressure, w hich affects only the electron
shells. F or exam ple, the rubidium -87 or uranium -238 decay probability per unit o f tim e is

21

1.6 The nucleus and radioactivity

Table 1.2 The molar energy scale of different physical and chemical processes
Strength
(kJ mol- 1)

6 x 106
6
4.1
4.2 x 10-5

5.8 x 108
580
393.5
0.040

T
(

Nuclear
Electronic
Chemical2
Kinetic3

Strength
(eV/molecule)

Bond

7.0 x 1010
69 800
47 400
0.5

1 Equivalent temperature (energy per mol/gas constant).

2 Combustion of one mole (12 grams) of carbon in oxygen.
3 One mole of air (22.4 liters at ambient pressure) at 60 km h- 1.

the sam e in the ocean or in a lake, in granite or lim estone, in the E arth s crust or low er m an
tle, on the M oon or on M ars, etc. This probability has not varied m easurably over the course
o f geological tim e. T he rem arkable consistency o f radioactive isotopic chronom eters of
diverse geologic and planetary objects obtained by using different radioactive isotopes d is
pels any doubt about the validity o f nuclear clocks. T he extrem e tem perature conditions
found in m assive stars provide a few exceptions to this rule, but these are of no practical
relevance to our Solar System .
T here are a num ber o f decay processes:
1. T he a (alpha) process, w hich is the em ission o f a helium nucleus (two protons and two
neutrons), is com m on at high m ass. T he nucleons (positively charged protons and neu
tral neutrons) are held together by the short-range attractive strong force. This force is
essentially restricted to adjacent nucleons and therefore varies linearly w ith their n um
ber. In contrast, the electrom agnetic force, w hich tends to pry the positively charged
protons apart, is w eaker but acts over a broader range, so that it involves the entire
nucleus. It varies w ith the total num ber o f proton pairs and therefore w ith the squared
num ber o f protons. O verall, for the heavier nuclei, the repulsive force therefore tends
to com pensate the attractive force and the m ean energy holding the particles together
decreases. A heavy nucleus becom e knobby and w obbly and som e parts tend to detach.
T he a (alpha) process occurs w hen the sum of the m asses o f the daughter nuclide and
the a particle is less than the mass of the parent nuclide. It is a consequence of a quantum
property o f nuclear particles know n as the tunnel effect: although the potential barrier
opposing the ejection o f an a particle is m uch greater than the energy gain resulting
from separation, there is a non-zero probability that an ejection w ill occur. For exam ple
147Sm ^ 143N d + a .
2. The p - (beta m inus) process involves the em ission o f an electron by the parent nucleus.
In a vacuum , a free neutron does not survive m ore than 15 m inutes before it turns into
a proton and an electron. A neutron bound in a nucleus is definitely m ore stable but,
as indicated above, the low er energy o f the p ro to n -n eu tro n interaction w ith respect to
that o f sim ilar nucleons favors a nucleus w ith an equal num ber o f protons and neutrons.
W hen N > Z , this condition is violated, and excess energy is released by converting a

22

The properties of elem ents

neutron into a proton and an electron. This process calls for a special type o f force, the
w eak interaction, w hich is analogous to electrom agnetic forces but, as reflected by its
nam e, m uch weaker. This interaction is o f little relevance to our fam iliar environm ent
and is difficult to explain simply. T he continuous distribution of electron energy em itted
during this process cast doubt on the quantification o f nuclear energy until it was shown
that there was a particle o f zero m ass, a neutrino, that practically does not interact with
the m atter through w hich it passes, but w hich can carry considerable energy. C ollaps
ing stars lose energy through neutrino em ission. For exam ple, 87Rb ^ 87Sr + |3- + V,
w here p - is the electron and V an antineutrino. B eta-m inus radioactivity is a com m on
process w hen the nucleus has a high neutron/proton ratio. A sym m etrical process of p+
(beta plus) positron em ission (particle w ith the sam e m ass as an electron but of opposite
charge) takes place w hen the nucleus has a high proton/neutron ratio (N < Z ), a situa
tion rarely found for natural nuclides, w hich, as w e w ill learn later in C hapter 12, form
in neutron-rich environm ents.
3. C apture o f an electron o f the K shell is a less frequent process, and was identified by
von W eizsacker during his investigation o f excess argon-40 in the E arth s atm osphere.
For exam ple, 40K + e - ^

40Ar. E lectron capture affects the nuclide in m uch the sam e

w ay as positron em ission does.

4. Spontaneous fission o f som e heavy atom s like uranium -238 or plutonium -244 is a rather
rare and very slow process; it forms the basis o f the fission-track dating m ethod.
A nuclide m ay be unstable w ith respect to two decay processes sim ultaneously and the
probabilities o f decom position by each process are additive. For exam ple, potassium -40
(40K) decays dually into 40C a by p - em ission and into 40A r by electron capture; this is
know n as a branched m ode o f radioactive decay.

Exercises

1. G ive the first three quantum num bers o f an electron in a 3p orbital.

2. F ind the electronic form ula of the elem ents K, Hf, and F. C om pare the orbital elec
tronic configuration for K and Rb (s block), H f and Zr (d block), F and Cl (p block).
For each elem ent, w hich ionic configuration should b e the m ost stable?
3. Plot the ionic radius and the first ionization energy as a function o f the num ber Z of
protons.
4. W hich ion of N a+ , K + , R b+ , M g2+ , C a2+ has the sm allest radius? W hy?
5. W hy is the ionic radius o f Yb (0.99 A) sm aller than that of L a (1.16 A)?
6. C alculate the crystal field stabilization energy (CFSE) in units o f A for the com m on
ions Sc3+ , Ti4+ , V 5+ , C r3+ , M n 2+ , F e2+ , C o2+ , N i2+ , C u2+ , and Z n2+ in octahedral
vs. tetrahedral environm ents in high-spin configuration.
7. The PetD B database (http://w w w .petdb.org/) collects geochem ical data on m id-ocean
ridge basalts (M O RB). Table 1.3 gives the concentrations o f the transition elem ents
o f the first row in som e glassy sam ples from the E ast Pacific R ise (EPR) and also the

23

Exercises

Table 1.3 Concentrations of transition elem ents of the first row in some glassy samples from the East Pacific
Rise (EPR) and also the mean value of these concentrations calculated in MORB from a much larger set of
samples. Data in ppm except for TiO2, MnO, and FeO, which are given in weight%
Sample

Sc

TiO2

Cr

MnO

FeO

Co

Ni

2.07
2.27
3.21
1.77
2.08
0.96
1.34

176
385
361
308
277
180
207

5.99
23.4
81.7
161
204
383
665

0.22

11.8

0.22

12.7
15.3

0.21

10.8

0.17
0.13
0.17

10.2

26.6
41.0
44.1
43.6
38.1
32.4
33.7

8.5
9.2

26.8
46.3
45.8
45.8
45.4
45.3
52.7

33.5
72.7
64.4
104
145
632

Mean EPR

38.7

1.90

270

199

0.20

10.8

43.7

84.4

74.4

94.1

1
2

3
4
5
6

0.25

10.6

Cu

Zn

45.9
74.9
74.3
86.8

131
114
115
92.4

72.7
93.4
81.2

50.5
68.4

88.2

m ean value o f these concentrations calculated in M O RB from a m uch larger set of

sam ples. N orm alize the data for each sam ple to the m ean value, plot the norm alized
values against the atom ic num ber, and use the results from the previous exercise to
infer w hether fractionation is due to the precipitation o f m inerals in w hich these ele
m ents are in octahedral sites (e.g. olivine, pyroxene) or to m inerals in w hich they could
also reside in tetrahedral sites (oxides).
8. T he platinum -group elem ents (PG E) consist o f the follow ing transition elem ents: Ru
(44), Rh (45), Pd (46), Os (76), Ir (77), and Pt (78) w ith their proton num bers given in
parentheses. D iscuss how to apply the crystal field theory to these elem ents and decide
w hat you need to know to understand their crystal chemistry.
9. L et the length of a polyhedron edge b e a and the radius o f the circum scribed sphere
b e R. For a tetrahedron it can b e shown that R = (1 /4 ) a V 6 , w hile for an octahedron
R = (1 /2 )a V 2 . T he ionic radius o f O 2 - is 1.4 A. C alculate the radius of the cations
that closely fit in a tetrahedral or octahedral site. C om pare w ith a table of ionic radii
(e.g. http://w w w .w ebelem ents.com ).
10. U sing the data listed in Table 1.4, draw a sem i-logarithm ic plot o f the com position of:
(i) ordinary chondrites norm alized to CI carbonaceous chondrites for decreasing
50 percent condensation tem perature
(ii) continental crust norm alized to the B SE or prim itive m antle by decreasing values
o f the norm alized value
(iii) the prim itive m antle norm alized first to CI carbonaceous chondrites, then to
ordinary chondrites using the sam e order
(iv) a H aw aiian basalt and a m id-ocean ridge basalt norm alized to prim itive m antle
using the sam e order.
11. U sing the first plot of the previous exercise, try to evaluate the condensation tem pera
ture o f the elem ents for w hich this param eter is m issing.
12. U sing all the plots and a periodic table, find w hich group o f elem ents trivalent yttrium
(Y) is hom ologous to. Then do the sam e for thorium (Th) and uranium (U).