Discussion

The transition elements are the series of elements that occupy the central part of the
periodic table, bridging the gap between the active s-block metals of groups 1A and 2A on the left
and the p-block metals, semimetals, and nonmetals of groups 3A–8A on the right (Figure 2.9.1).
In this region, the d and f subshells are gradually filled, thus, the transition elements are also called
the d-block elements. These elements readily give rise to ions with incompletely filled d subshells.
However, the Group 2B metals—Zn, Cd, and Hg—do not have this characteristic electron
configuration and so, although they are sometimes called transition metals, they really do not
belong in this category).
Each subshell consists of five orbitals and can accommodate 10 electrons, so each
transition series consists of 10 elements. The first series extends from scandium through zinc and
includes many familiar metals, such as chromium, iron, and copper. The second series runs from
yttrium through cadmium, and the third series runs from lutecium through mercury. In addition,
there is a fourth transition series made up of lawrencium through the recently discovered element
112, copernicium (Cn).
Tucked into the periodic table between barium (atomic number 56) and lutecium (atomic
number 71) are the lanthanides. In this series of 14 metallic elements, the seven orbitals are
progressively filled. Following radium (atomic number 88) is a second series of 14 elements, the
actinides, in which the subshell is progressively filled. The lanthanides and actinides together
comprise the f-block elements, or inner transition elements.
The transition metals iron and copper have been known since antiquity and have played an
important role in the development of civilization. Iron, the main constituent of steel, is still
important as a structural material. Worldwide production of steel was 1.22 billion metric tons in
2009. In newer technologies, other transition elements are useful. For example, the strong,
lightweight metal titanium is a major component in modern jet aircraft and is used in
manufacturing artificial joints and dental implants. Transition metals are also used as
heterogeneous catalysts in automobile catalytic converters and in the industrial synthesis of
essential chemicals such as sulfuric acid, nitric acid, and ammonia. The role of the transition
elements in living systems is equally important. Iron is present in biomolecules such as
hemoglobin, which transports oxygen from our lungs to other parts of the body. Cobalt is an
essential component of vitamin B12. Nickel, copper, and zinc are vital constituents of many
enzymes, the large protein molecules that catalyze biochemical reactions.
Figure 2.9.1 The transition elements are located in the central region of the periodic table.

Electron Configurations
From scandium across to copper, electrons are added to the 3d orbitals. Thus, the outer
electron configuration of scandium is 4s2 3d1 , that of titanium is 4s23d2 , and so on. The two
exceptions are chromium and copper, whose outer electron configurations are 4s13d5 and 4s13d10,
respectively. These irregularities are the result of the extra stability associated with half-filled
(decreases electron–electron repulsions) and completely filled 3d subshells. When the first-row
transition metals form cations, electrons are removed first from the 4s orbitals and then from the
3d orbitals. (This is the opposite of the order in which orbitals are filled in atoms.) For example,
the outer electron configuration of Fe2+ is 3d6 , not 4s23d4 .
In neutral molecules and complex anions, the metal atom usually has a positive oxidation
state. It therefore has a partial positive charge and a higher than that of the neutral atom. As a
result, the valence orbitals are again lower in energy than the valence orbital, and so all the metal’s
valence electrons occupy the orbitals. The metal atom in both VCl4 and MnO42-, for example, has
the valence configuration 3d1. Electron configurations and other properties for atoms and common
ions of first series transition elements are summarized in Table 2.9.1.
Historically, transition elements are placed in groups of the periodic table designated 1B–
8B because their valence electron configurations are similar to those of analogous elements in the
main groups 1A–8A. Thus, copper in group 1B and zinc in group 2B have valence electron
configurations similar to those of potassium in group 1A and calcium in group 2A. Similarly,
scandium in group 3B through iron in group 8B have the same number of valence electrons as the
-block elements aluminum in group 3A through argon in group 8A. Cobalt and nickel are also
assigned to group 8B although there are no main-group elements with 9 or 10 valence electrons.
Physical properties
The transition metals have several notable properties, including distinctive coloring,
formation of paramagnetic compounds, catalytic activity, and especially a great tendency to form
complex ions. Table 2.9.1 lists some of their properties.
Metallic Properties
All the transition elements are metals. Like the metals of groups 1A and 2A, the transition
metals are malleable, ductile, lustrous, and good conductors of heat and electricity. Silver has the
highest electrical conductivity of any element at room temperature, with copper a close second.
The transition metals are harder, have higher melting and boiling points, and are more dense than
the group 1A and 2A metals, largely because the sharing of d, as well as s, electrons results in
stronger bonding. From left to right across the first transition series, melting points increase from
for Sc to a maximum of for V in group 5B, then decrease to for Zn (Table 2.9.1). The second- and
third-series elements exhibit a similar maximum in melting point, but at group 6B rather than 5B:
for Mo and for W, the metal with the highest melting point. The melting points increase as the
number of unpaired electrons available for bonding increases and then decrease as the electrons
pair up and become less available for bonding. Zinc, in which all the and electrons are paired, has
a relatively low melting point and mercury is a liquid at room temperature.

Table 2.9.1 Selected properties of first-series transition elements

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Atomic Radii and Densities
From left to right across a transition series, the atomic radii decrease, at first markedly and
then more gradually after group 6B. Toward the end of each series, the radii increase again (Figure
2.9.2). The decrease in radii with increasing atomic number occurs because the added electrons
only partially shield the added nuclear charge. As a result, the effective nuclear charge, Zeff,
increases. With increasing Zeff, the electrons are more strongly attracted to the nucleus and atomic
size decreases. The upturn in radii toward the end of each series is probably due to more effective
shielding and increasing electron–electron repulsion as double occupation of the orbitals is
completed. In contrast to the large variation in radii for main-group elements, all transition metal
atoms have quite similar radii, which accounts for their ability to blend together in forming alloys
such as brass (mostly copper and zinc).
The atomic radii of the second- and third-series transition elements from group 4B on are
nearly identical, though we would expect an increase in size on adding an entire principal quantum
shell of electrons. The small sizes of the third-series atoms are associated with what is called the
lanthanide contraction, the general decrease in atomic radii of the f-block lanthanide elements
between the second and third transition series (Figure 2.9.3).
The lanthanide contraction is due to the increase in effective nuclear charge with
increasing atomic number as the subshell is filled. By the end of the lanthanides, the size decreases
due to a larger almost exactly compensates for the expected size increase due to an added quantum
shell of electrons. Consequently, atoms of the third transition series have radii very similar to those
of the second transition series.
The densities of the transition metals are inversely related to their atomic radii (Figure
2.9.4). The densities initially increase from left to right across each transition series and then
decrease toward the end of each series. Because the second- and third-series elements have nearly
the same atomic volume, the much heavier third series elements have unusually high densities: for
osmium and iridium, the most dense elements.

Figure 2.9.2 Trends in metallic radii (rmetal) across the three rows of s- and d-block metals
K to Zn, Rb to Cd, and Cs to Hg (Housecroft, ).
 Figure 2.9.3. Atomic radii (in pm) of the lanthanide elements.

Figure 2.9.4 Relative densities of the transition metals.

Ionization Energies and Oxidation Potentials

Ionization energies generally increase from left to right across a transition series, though
there are some irregularities, for the atoms of the first transition series (Figure 2.9.5). The general
trend correlates with an increase in effective nuclear charge and a decrease in atomic radius.
 Figure 2.9.5. Variation of the
first, second, and third ionization
energies for the first-row
transition metals.

Table 2.9.2 lists standard potentials for oxidation of first-series transition metals. Except
for copper, all the Eo values are positive, which means that the solid metal is oxidized to its aqueous
cation more readily than H2 gas is oxidized to H+(aq).

In other words, the first-series metals, except for copper, are stronger reducing agents than H2 gas
and can therefore be oxidized by the H+(aq) ion in acids like HCl that lack an oxidizing anion:

Oxidation of copper requires a stronger oxidizing agent, such as HNO3.

The standard potential for the oxidation of a metal is a composite property that depends on
for the sublimation of the metal, the ionization energies of the metal atom, and for the hydration
of the metal ion:

Nevertheless, the general trend in the values shown in Table 2.9.2 correlates with the general trend
in the ionization energies in Table 2.9.1. The ease of oxidation of the metal decreases as the
ionization energies increase across the transition series from Sc to Zn. (Only Mn and Zn deviate
from the trend of decreasing values.) Thus, the so-called early transition metals, those on the left
side of the d-block (Sc through Mn), are oxidized most easily and are the strongest reducing agents.
Table 2.9.2 Standard potentials for oxidation of first-series transition metals
_____________________________________________________________________________

______________________________________________________________________________

The reactivity of the metals

In general, the metals are moderately reactive and combine to give binary compounds when
heated with dioxygen, sulfur or the halogens, product stoichiometry depending, in part, on the
available oxidation states. Combination with H 2, B, C or N2 may lead to interstitial hydrides,
borides, carbides or nitrides.

Most d-block metals should, on thermodynamic grounds, liberate H2 from acids but, in
practice, many do not since they are passivated by a thin surface coating of oxide or by having a
high dihydrogen overpotential, or both. Silver, gold and mercury (i.e. late, second and third row
metals) are, even in the thermodynamic sense, the least reactive metals known. For example, gold
is not oxidized by atmospheric O2 or attacked by acids, except by a 3 :1 mixture of concentrated
HCl and HNO3 (aqua regia).

Color
The colors of d-block metal compounds are a characteristic feature of species with ground
state electronic configurations other than d0 and d10. For example, [Cr(OH2)6]2+ is sky-blue,
[Mn(OH2)6]2+ very pale pink, [Co(OH2)6]2+ pink, [MnO4]- intense purple and [CoCl4]2- dark blue.
In contrast, complexes of Sc(III) (d0) or Zn(II) (d10) are colorless unless the ligands contain a
chromophore that absorbs in the visible region.
Many of the observed colors are of low intensity and is consistent with the color originating
from electronic ‘d–d’ transitions. For an isolated gas phase ion, such transitions are forbidden by
the Laporte selection rule, l= +1 (where l is the orbital quantum number). The pale colors
observed in complexes indicate that the probability of a transition occurring is low. Table 2.9.3
shows relationships between the wavelength of light absorbed and observed colors.
Species such as [MnO4]- have intense colors of a different origin, namely charge transfer
absorptions or emissions. The latter are not subject to Laporte selection rule and are always more
intense than electronic transitions between different d orbitals.
Paramagnetism
The occurrence of paramagnetic compounds of d-block metals is common and arises from
the presence of unpaired electrons.
Complex formation
d-block metal ions readily form complexes, with complex formation often being
accompanied by a change in color and sometimes a change in the intensity of color. The effect of
adding concentrated HCl to aqueous cobalt(II) ions is shown below:

Table 2.9.3. The visible part of the electromagnetic spectrum.

Variable oxidation states

Most d-block metals exhibit variable oxidation states. For example, manganese in group
7B shows oxidation states of +2 in Mn2+(aq), +3 in Mn(OH)3(s), +4 in MnO2(s), +6 in MnO42-(aq)
(manganate ion), and +7 in MnO4-(aq) (permanganate ion) (Figs 2.9.6 & 2.9.7). Exceptions are in
Groups 3B and 12B as illustrated in Table 2.9.5. In Group 12B, the +1 oxidation state is found for
species containing (or formally containing) the [M2]2+ unit. This is extremely common for Hg, but
is rare for Zn and Cd. Metals that display the greatest number of different oxidation states occur
in or near the middle of a d-block row.
The common oxidation states for each element include +2, +3, or both. The +3 oxidation
states are more stable at the beginning of the series, whereas toward the end the +2 oxidation states
are more stable. The reason for this trend can be understood by examining the ionization energy.
In general, the ionization energies increase gradually from left to right. However, the third
ionization energy (when an electron is removed from the 3d orbital) increases more rapidly than
the first and second ionization energies (Figure 2.9.4). Because it takes more energy to remove the
third electron from the metals near the end of the row than from those near the beginning, the
metals near the end tend to form M2+ ions rather than M3+ ions. The highest oxidation state for a
transition metal is +7, for manganese (4s23d5). For elements to the right of Mn (Fe to Cu), oxidation
numbers are lower. Transition metals usually exhibit their highest oxidation states in compounds
with very electronegative elements such as oxygen and fluorine—for example, V2O5, CrO3, and
Mn2O7.

Chemistry of Selected Transition Elements

Chromium
Chromium, which gets its name from the Greek word for color (chroma), is obtained from
the ore chromite, a mixed metal oxide with the formula , or Reduction of chromite with carbon
gives the alloy ferrochrome, which is used to make stainless steel, a hard, corrosion-resistant steel
that contains up to 30% chromium.

Pure chromium is obtained by reducing chromium(III) oxide with aluminum:

In addition to its use in making steels, chromium is widely used to electroplate metallic
objects with an attractive, protective coating. Chromium is hard and lustrous, takes a high polish,
and resists corrosion because an invisible, microscopic film of chromium(III) oxide shields the
surface from further oxidation. The aqueous solution chemistry of chromium can be systematized
according to its oxidation states and the species that exist under acidic and basic conditions (Table
2.9.6). The common oxidation states are +2, +3, and +6, with the +3 state the most stable.
Table 2.9.5. Oxidation states of the d-block metals; the most stable states are marked in blue.
Tabulation of zero oxidation states refers to their appearance in compounds of the metal. In
organometallic compounds, oxidation states of less than zero are encountered (see Chapter 23).
An oxidation state enclosed in [ ] is rare.

Figure 2.9.6 Common oxidation

states for first-series transition
elements. The states encountered
most frequently are shown in red.
Most transition elements have
more than one common oxidation
state.
 Figure 2.9.7 Oxidation states of
manganese.

Chromium metal reacts with aqueous acids in the absence of oxygen to give Cr(aq)2+, the
beautiful blue chromium(II) (chromous) ion, in which Cr 2+ is bound to six water molecules,
Cr(H2O)62+ (Figure 2.9.8a):

In air, the reaction of chromium metal with acids yields chromium(III) because chromium(II) is
rapidly oxidized by atmospheric oxygen:

Although the Cr(H2O)63+ ion is violet, chromium(III) solutions are often green because anions
replace some of the bound water molecules to give green complex ions such as Cr(H2O)5Cl2+ and
Cr(H2O)4Cl22+ (Figure 2.9.8b).
In basic solution, chromium(III) precipitates as chromium(III) hydroxide, a pale
green solid that dissolves both in acid and in excess base (Figure 2.9.9):

This behavior is typical of amphoteric metal hydroxides.

Table 2.9.6 Chromium species in common oxidation states
________________________________________________________________________

Figure 2.9.8 Reaction of

chromium metal with aqueous
acids.

Figure 2.9.9 Amphoteric behavior

of chromium(III) hydroxide.
 In contrast to the amphoteric Cr(OH)3, chromium(II) hydroxide is a typical basic
hydroxide. It dissolves in acid but not in excess base. Conversely, the chromium(VI) compound,
CrO2(OH)2 , is a strong acid (chromic acid, H2CrO4). Acid strength increases with increasing
polarity of the O-H bonds, which increases, in turn, with increasing oxidation number of the
chromium atom.

In the +6 oxidation state, the most important solution species are the yellow chromate ion,
CrO4 and the orange dichromate ion Cr2O72-. These ions are interconverted by the rapid
-2

equilibrium reaction

Because the equilibrium constant is about 1014, CrO4-2 ions predominate in basic solutions and
Cr2O72-ions predominate in acidic solutions (Figure 2.9.10). The ion is tetrahedral, and the ion has
a structure in which two ions share a common oxygen atom. The ion is a powerful oxidizing agent
in acidic solution and is widely used as an oxidant in analytical chemistry.

Figure 2.9.10 Conversion of the

yellow CrO42-(aq) ion to the orange
Cr2O7 2-(aq) ion
Iron
Iron, the fourth most abundant element in the Earth’s crust at 5.6% by mass, is immensely
important both in human civilization and in living systems. Because iron is relatively soft and
easily corroded, it is combined with carbon and other metals, such as vanadium, chromium, and
manganese, to make steel alloys that are harder and less reactive than pure iron. Iron is obtained
from its most important ores, hematite Fe2O3 and magnetite, Fe3O4 by reduction with coke in a
blast furnace. In living systems, iron is an essential constituent of numerous biomolecules. The
body of a healthy human adult contains about 4 g of iron, 65% of which is present in the oxygen-
carrying protein hemoglobin.
The most common oxidation states of iron are +2 (ferrous) and +3 (ferric). When iron metal
reacts in the absence of air with an acid such as HCl, which lacks an oxidizing anion, the product
is the light green iron(II) ion, Fe(H2O)6 2+ :

The oxidation stops at the iron(II) stage because the standard potential for oxidation of the iron(II)
ion is negative:

In air, the iron(II) ion is slowly oxidized by atmospheric oxygen to the iron(III) ion, Fe(H2O)63+ :

When iron is treated with an acid that has an oxidizing anion—for example, dilute nitric acid—the
metal is oxidized directly to iron(III):

The addition of a base to iron(III) solutions precipitates the gelatinous, red-brown hydrous oxide,
Fe2O3 xH2O , usually written as Fe(OH)3 (Figure 2.9.11):
 Figure 2.9.11 When dilute NaOH is added to a
solution of iron(III) sulfate, Fe2(SO4)3 , a
gelatinous, red-brown precipitate of Fe(OH)3
forms.

Because is very insoluble (Ksp = 2.6 x 10-39) , it forms as soon as the pH rises above pH 2. The
red-brown rust stains that you’ve seen in sinks and bathtubs are due to air oxidation of in hard
water followed by deposition of hydrous iron(III) oxide. Unlike Cr(OH)3, Fe(OH)3 is not
appreciably amphoteric. It dissolves in acid, but not in excess base.

Copper
Copper, a reddish metal, is a relatively rare element, accounting for only 0.0068% of the
Earth’s crust by mass. Like the other group 1B elements silver and gold, copper is found in nature
in the elemental state. Copper’s most important ores are sulfides, such as chalcopyrite, CuFeS2. In
a multistep process, copper sulfides are concentrated, separated from iron, and converted to molten
copper(I) sulfide, which is then reduced to elemental copper by blowing air through the hot liquid:

The product, containing about 99% copper, is purified by electrolysis. Because of its high electrical
conductivity and negative oxidation potential, copper is widely used to make electrical wiring and
corrosion-resistant water pipes. Copper is also used in coins and is combined with other metals to
make alloys such as brass (mostly copper and zinc) and bronze (mostly copper and tin). Though
less reactive than other first-series transition metals, copper is oxidized on prolonged exposure to
O2, CO2, and water in moist air, forming basic copper(II) carbonate, Cu2(OH)2CO3. Subsequent
reaction with dilute H2SO4 in acid rain then forms Cu2(OH)2SO4, the green patina seen on bronze
monuments.

In its compounds, copper exists in two common oxidation states, +1 (cuprous) and +2
(cupric). Because Eo for the Cu+/Cu2+ half-reaction is less negative than that for theCu/Cu+ half-
reaction, any oxidizing agent strong enough to oxidize copper to the copper(I) ion is also able to
oxidize the copper(I) ion to the copper(II) ion.

Dilute nitric acid, for example, oxidizes copper to the oxidation state:

It follows from the values that can disproportionate, oxidizing and reducing itself:

The positive E value for the disproportionation corresponds to a large equilibrium constant,
indicating that the reaction proceeds far toward completion:
Thus, the copper(I) ion is not an important species in aqueous solution, though copper(I) does exist
in solid compounds such as CuCl. In the presence of Cl- ions, the disproportionation equilibrium
is reversed because precipitation of the insoluble, white copper(I) chloride drives the following
reaction to the right:

The more common +2 oxidation state is found in the blue aqueous ion, , and in numerous
solid compounds and complex ions. The addition of base (aqueous ammonia) to a solution of a
copper(II) salt gives a blue precipitate of copper(II) hydroxide, which dissolves in excess aqueous
ammonia, yielding the dark blue complex ion Cu(NH3)42+ (Figure 20.12):

Figure 2.9.12. Reactions of with aqueous ammonia.

Assignment: Read Chapters 20-22. HOUSECROFT & SHARPE (2012). d-block metal
chemistry.