TRANSITON METAL CHEMISTRY

General Survey

One striking characteristic of the representative elements is that their chemistry changes
markedly across a given period as the number of valence electrons changes. The chemical
similarities occur mainly within the vertical groups. In contrast, the transition metals show great
similarities within a given period as well as within a given vertical group. This difference
occurs because the last electrons added for transition metals are inner electrons: d electrons for
the d-block transition metals and f electrons for the lanthanides and actinides. These inner d and f
electrons cannot participate as easily in bonding as can the valence s and p electrons. Thus the
chemistry of the transition elements is not affected as greatly by the gradual change in the
number of electrons as is the chemistry of the representative elements. Group designations are
traditionally given on the periodic table for the d-block transition metals. However, these
designations do not relate as directly to the chemical behavior of these elements as they do for
the representative elements, so we will not use them.

As a class, the transition metals behave as typical metals, possessing metallic luster and
relatively high electrical and thermal conductivities. Silver is the best conductor of heat and
electric current. However, copper is a close second, which explains copper’s wide use in the
electrical systems of homes and factories.
The above figure shows the position of the transition elements on the periodic table. The d-block
elements correspond to filling the 3d, 4d, 5d, or 6d orbitals. The inner transition metals
correspond to filling the 4f (lanthanides) or 5f (actinides) orbitals.

Despite their many similarities, the transition metals do vary considerably in certain properties.
For example:

 Tungsten has a high melting point and is used for filaments in light bulbs
 Mercury is a liquid
 Some transition metals such as iron and titanium are hard and strong and make very
useful structural materials
 Others such as copper, gold, and silver are relatively soft.

The chemical reactivity of the transition metals also varies significantly:

 Some react readily with oxygen to form oxides.

 Of these metals, some, such as chromium, nickel, and cobalt, form oxides that adhere
tightly to the metallic surface, protecting the metal from further oxidation.
 Others, such as iron, form oxides that scale off, constantly exposing new metal to the
corrosion process. On the other hand, the noble metals—primarily gold, silver, platinum,
and palladium—do not readily form oxides.

In forming ionic compounds with nonmetals, the transition metals exhibit several typical
characteristics:

 More than one oxidation state is often found. For example, iron combines with chlorine
to form FeCl2 and FeCl3.
 The cations are often complex ions, species where the transition metal ion is surrounded
by a certain number of ligands (molecules or ions that behave as Lewis bases). For
example, the compound [Co (NH3)6]Cl3 contains the Co(NH3)6 3+ cation and Cl – anions.

 Most compounds are colored, because the transition metal ion in the complex ion can
absorb visible light of specific wavelengths.
 Many compounds are paramagnetic (they contain unpaired electrons).
FIRST ROW TRANSITION METALS

They include: Sc, Ti V Cr, Mn, Fe, Co, Ni Cu and Zn. They are representative of the other
transition series and because they have great practical significance.

Electronic Configuration

The 3d orbitals begin to fill after the 4s orbital is complete, that is, after calcium ([Ar]4s2 ). The
first transition metal, scandium, has one electron in the 3d orbitals; the second, titanium, has two;
and the third, vanadium, has three. We would expect chromium, the fourth transition metal, to
have the electron configuration [Ar]4s23d4. However, the actual configuration is [Ar]4s13d5,
which shows a half-filled 4s orbital and a half filled set of 3d orbitals (one electron in each of the
five 3d orbitals). It is tempting to say that the configuration results because half-filled “shells”
are especially stable. Although there are some reasons to think that this explanation might be
valid, it is an oversimplification. For instance, tungsten, which is in the same vertical group as
chromium, has the configuration [Xe]6s24f145d4, where half-filled s and d shells are not found.
There are several similar cases.

Basically, the chromium configuration occurs because the energies of the 3d and 4s orbitals are
very similar for the first-row transition elements. When electrons are placed in a set of
degenerate orbitals, they first occupy each orbital singly to minimize electron repulsions. Since
the 4s and 3d orbitals are virtually degenerate in the chromium atom, we would expect the
following configuration:

since the second arrangement has greater electron–electron repulsions and thus a higher energy.

The only other unexpected configuration among the first-row transition metals is that of copper,
which is [Ar]4s13d10 rather than the expected [Ar]4s2 3d9. In contrast to the neutral transition
metals, where the 3d and 4s orbitals have very similar energies, the energy of the 3d orbitals in
transition metal ions is significantly less than that of the 4s orbital. This means that the
electrons remaining after the ion is formed occupy the 3d orbitals, since they are lower in energy.
First-row transition metal ions do not have 4s electrons. For example, manganese has the
configuration [Ar]4s23d5, while that of Mn2+ is [Ar]3d5. The neutral titanium atom has the
configuration [Ar]4s23d2, while that of Ti3+ is [Ar]3d1 .

Oxidation States and Ionization Energies

The transition metals can form a variety of ions by losing one or more electrons. First five metals
the maximum possible oxidation state corresponds to the loss of all the 4s and 3d electrons. For
example, the maximum oxidation state of chromium ([Ar]4s13d5) is 6. Toward the right end of
the period, the maximum oxidation states are not observed; in fact, the 2+ ions are the most
common. The higher oxidation states are not seen for these metals because the 3d orbitals
become lower in energy as the nuclear charge increases, and the electrons become
increasingly difficult to remove. Ionization energy increases gradually going from left to right
across the period. However, the third ionization energy (when an electron is removed from a 3d
orbital) increases faster than the first ionization energy, clear evidence of the significant decrease
in the energy of the 3d orbitals going across the period.

Standard Reduction Potential

When a metal acts as a reducing agent, the half-reaction is:

This is the reverse of the conventional listing for half-reactions in tables. Thus, to rank the
transition metals in order of reducing ability, the most positive potential is then the best reducing
agent. The transition metals are listed in order of reducing ability in the table below:

The reduction for hydrogen gives a zero potential for the process:

All the metals except copper can reduce Hions to hydrogen gas in 1 M aqueous solutions of
strong acid:

The reducing abilities of the first-row transition metals generally decrease going from left to
right across the period. Only chromium and zinc do not follow this trend.
Properties of 3d Transition Metals

 Scandium is a rare element that exists in compounds mainly in the +3 oxidation state—for
example, in ScCl3, Sc2O3, and Sc2(SO4)3. The chemistry of scandium strongly resembles that of
the lanthanides, with most of its compounds being colorless and diamagnetic. This is not
surprising; as the color and magnetism of transition metal compounds usually arise from the d
electrons on the metal ion, and Sc3+ has no d electrons. Scandium metal, which can be prepared
by electrolysis of molten ScCl3, is not widely used because of its rarity, but it is found in some
electronic devices, such as high-intensity lamps.
 Titanium is widely distributed in the earth’s crust (0.6% by mass). Because of its relatively low
density and high strength, titanium is an excellent structural material, especially in jet engines,
where light weight and stability at high temperatures are required. Nearly 5000 kg of titanium
alloys is used in each engine of a Boeing 747 jetliner. In addition, the resistance of titanium to
chemical attack makes it a useful material for pipes, pumps, and reaction vessels in the
chemical industry. Titanium dioxide, or more correctly, titanium(IV) oxide (TiO2), is a highly
opaque substance used as the white pigment in paper, paint, linoleum, plastics, synthetic fibers,
whitewall tires, and cosmetics (sunscreens, for example). Titanium (IV) oxide is widely
dispersed in nature, but the main ores are rutile (impure TiO2) and ilmenite (FeTiO3). Rutile is
processed by treatment with chlorine to form volatile TiCl4, which is separated from the
impurities and burned to form TiO2:

Ilmenite is treated with sulfuric acid to form a soluble sulfate:

When this aqueous mixture is allowed to stand, under vacuum, solid forms first and is removed.
The mixture is then heated, and the insoluble titanium (IV) oxide hydrate forms. The water of
hydration is driven off by heating to form pure TiO2:

In its compounds, titanium is most often found in the +4 oxidation state. Examples are TiO 2 and
TiCl4, the latter a colorless liquid (bp 137 degree Celsius) that fumes in moist air to produce
TiO2:

Titanium (III) compounds can be produced by reduction of the +4 state. In aqueous solution, Ti3+
exists as the purple Ti(H2O)6 3+ ion, which is slowly oxidized to titanium(IV) by air. Titanium
(II) is not stable in aqueous solution but does exist in the solid state in compounds such as TiO
and the dihalides of general formula TiX2

 Vanadium is widely spread throughout the earth’s crust (0.02% by mass). It is used mostly in
alloys with other metals such as iron (80% of vanadium is used in steel) and titanium.
Vanadium (V) oxide (V2O5) is used as an industrial catalyst in the production of materials such
as sulfuric acid. Pure vanadium can be obtained from the electrolytic reduction of fused salts,
such as VCl2, to produce a metal similar to titanium that is steel gray, hard, and corrosion
resistant. Often the pure element is not required for alloying. For example, ferrovanadium,
produced by the reduction of a mixture of V2O5 and Fe2O3 with aluminum, is added to iron to
form vanadium steel, a hard steel used for engine parts and axles.
 The principal oxidation state of vanadium is +5, found in compounds such as the orange V2O5
and the colorless VF5. The oxidation states from +5 to +2 all exist in aqueous solution.
 Although chromium is relatively rare, it is a very important industrial material. The chief ore of
chromium is chromite (FeCr2O4), which can be reduced by carbon to give ferrochrome

 Chromium commonly forms compounds in which it has the oxidation state +2, +3, or +6. The
Cr2+ (chromous) ion is a powerful reducing agent in aqueous solution. In fact, traces of O2 in
other gases can be removed by bubbling through a Cr2+ solution:

 The chromium(VI) species are excellent oxidizing agents, especially in acidic solution, where
chromium(VI) as the dichromate ion is reduced to the Cr3+ ion:

The oxidizing ability of the dichromate ion is strongly pH-dependent, increasing as [H+]
increases, as predicted by Le Châtelier’s principle. In basic solution, chromium(VI) exists as the
chromate ion, a much less powerful oxidizing agent:

Red chromium(VI) oxide (CrO3) dissolves in water to give a strongly acidic, red-orange solution:

Manganese is relatively abundant (0.1% of the earth’s crust), although no significant sources are
found in the United States. The most common use of manganese is in the production of an
especially hard steel used for rock crushers, bank vaults, and armor plate. One interesting source
of manganese is from manganese nodules found on the ocean floor. These roughly spherical
“rocks” contain mixtures of manganese and iron oxides as well as smaller amounts of other
metals such as cobalt, nickel, and copper. Apparently, the nodules were formed at least partly by
the action of marine organisms.

Manganese can exist in all oxidation states from +2 to +7, although +2 and +7 are the most
common. Manganese(II) forms an extensive series of salts with all the common anions. In
aqueous solution Mn2+ forms Mn(H2O)6 2–, which has a light pink color. Manganese (VII) is
found in the intensely purple permanganate ion (MnO4 –). Widely used as an analytical reagent in
acidic solution, the MnO4 – ion behaves as a strong oxidizing agent, with the manganese
becoming Mn2+

Some compounds of manganese in their common oxidation states are shown in the table below:

Iron is the most abundant heavy metal (4.7% of the earth’s crust) and the most important to our
civilization. It is a white, lustrous, not particularly hard metal that is very reactive toward
oxidizing agents. For example, in moist air it is rapidly oxidized by oxygen to form rust, a
mixture of iron oxides.

The chemistry of iron mainly involves its +2 and +3 oxidation states. Typical compounds are
shown in the table below. In aqueous solutions iron (II) salts are generally light green because of
the presence of Fe(H2O)6 2+. Although the Fe(H2O)63+ ion is colorless, aqueous solutions of
iron(III) salts are usually yellow to brown in color due to the presence of Fe(OH)(H2O)52+, which
results from the acidity of Fe(H2O)6 3+
Although cobalt is relatively rare, it is found in ores such as smaltite (CoAs2) and cobaltite
(CoAsS) in large enough concentrations to make its production economically feasible. Cobalt is
a hard, bluish white metal mainly used in alloys such as stainless steel and stellite, an alloy of
iron, copper, and tungsten that is used in surgical instruments.

The chemistry of cobalt involves mainly its +2 and +3 oxidation states, although compounds
containing cobalt in the 0, +1, or +4 oxidation state are known. Aqueous solutions of cobalt (II)
salts contain the Co(H2O)6 2+ ion, which has a characteristic rose color. Cobalt forms a wide
variety of coordination compounds.

Nickel, which ranks twenty-fourth in elemental abundance in the earth’s crust, is found in ores,
where it is combined mainly with arsenic, antimony, and sulfur. Nickel metal, a silvery white
substance with high electrical and thermal conductivities, is quite resistant to corrosion and is
often used for plating more active metals. Nickel is also widely used in the production of alloys
such as steel.
Nickel in compounds is almost exclusively in the +2 oxidation state. Aqueous solutions of nickel
(II) salts contain the Ni(H2O)6 2+ ion, which has a characteristic emerald green color.

Copper, widely distributed in nature in ores containing sulfides, arsenides, chlorides, and
carbonates, is valued for its high electrical conductivity and its resistance to corrosion. It is
widely used for plumbing, and 50% of all copper produced annually is used for electrical
applications. Copper is a major constituent in several well-known alloys. Although copper is not
highly reactive (it will not reduce H+to H2, for example), the reddish metal does slowly corrode
in air, producing the characteristic green patina consisting of basic copper sulfate.

The chemistry of copper principally involves the +2 oxidation state, but many compounds
containing copper (I) are also known. Aqueous solutions of copper (II) salts are a characteristic
bright blue color due to the presence of the Cu(H2O)6 2+ ion. Although trace amounts of copper
are essential for life, copper in large amounts is quite toxic; copper salts are used to kill bacteria,
fungi, and algae. For example, paints containing copper are used on ship hulls to prevent fouling
by marine organisms.

Widely dispersed in the earth’s crust, zinc is mainly refined from sphalerite (ZnS), which often
occurs with galena (PbS). Zinc is a white, lustrous, very active metal that behaves as an excellent
reducing agent and tarnishes rapidly. About 90% of the zinc produced is used for galvanizing
steel. Zinc forms colorless salts in the +2 oxidation state.
THE ELEMENTS

The two terms d-block metal and transition metal are often used interchangeably; however,
they do not mean the same thing. The name transition metal originally derived from the fact that
their chemical properties were transitional between those of the s and p blocks. Now, however,
the IUPAC definition of a transition element is that it is an element that has an incomplete d
subshell in either the neutral atom or its ions. Thus the Group 12 elements (Zn, Cd, Hg) are
members of the d block but are not transition elements. In the following discussion, it will be
convenient to refer to each row of the d block as a series, with the 3d series the first row of the
block (Period 4), the 4d series the second row (Period 5), and so on. It will prove important to
note the intrusion of the f block, the inner transition elements, the lanthanoids, into the 5d series.
Elements towards the left of the d block are often referred to as early and those towards the right
are referred to as late.

Occurrence and Recovery

Key point: Chemically soft members of the block occur as sulfide minerals and are partially
oxidized to obtain the metal; the more electropositive ‘hard’ metals occur as oxides and are
extracted by reduction.

The elements on the left of the 3d series occur in nature primarily as metal oxides or as metal
cations in combination with oxoanions. Of these elements, titanium ores are the most difficult to
reduce, and the element is widely produced by heating TiO2 with chlorine and carbon to produce
TiCl4, which is then reduced by molten magnesium at about 1000ºC in an inert-gas atmosphere.

The oxides of Cr, Mn, and Fe are reduced with carbon, a much cheaper reagent. To the right of
Fe in the 3d series, Co, Ni, Cu, and Zn occur mainly as sulfides and arsenides, which is
consistent with the increasingly soft Lewis acid character of their dipositive ions. Sulfide ores are
usually roasted in air either to the metal directly (for example, Ni) or to an oxide that is
subsequently reduced (for example, Zn). Copper is used in large quantities for electrical
conductors; electrolysis is used to refine crude copper to achieve the high purity needed for high
electrical conductivity. The difficulty of reducing the early 4d and 5d metals Mo and W is
apparent from the table below. It reflects the tendency of these elements to have stable high
oxidation states.

The platinum metals (Ru and Os, Rh and Ir, and Pd and Pt), which are found at the lower right of
the d block, occur as sulfide and arsenide ores, usually in association with larger quantities of
Cu, Ni, and Co. They are collected from the sludge that forms during the electrolytic refinement
of copper and nickel.

Gold (and to some extent silver) is found in its elemental form

Physical properties

Key points: The properties of the d metals are largely derived from their electronic structure,
with the strength of metallic bonding peaking at Group 6; the lanthanide contraction is
responsible for some of the anomalous behaviour of the metals in the 5d series.

The d block of the periodic table contains the metals most important to modern society:

 It contains the immensely strong and light titanium, the major components of most steels (Fe,
Cr, Mn, Mo)
 The highly electrically conducting copper
 The malleable gold and platinum
 The very dense osmium and iridium.

To a large extent these properties derive from the nature of the metallic bonding that binds the
atoms together.
Metallic bonding introduces the concept of band structure. Generally speaking, the same band
structure is present for all the d-block metals and arises from the overlap of the (n+1) s orbitals to
give an s band and of the nd orbitals to give a d band. The principal differences between the
metals is the number of electrons available to occupy these bands: Ti (3d24s2 ) has four bonding
electrons, V (3d34s2 ) five, Cr (3d54s1) six, and so on. The lower, net bonding region of the
valence band is therefore progressively filled with electrons on going to the right across the
block, which results in stronger bonding, until around Group 7 (at Mn, Tc, Re) when the
electrons begin to populate the upper, net antibonding part of the band. This trend in bonding
strength is reflected in the increase in melting point from the low-melting alkali metals
(effectively only one bonding electron for each atom, resulting in melting points typically less
than 100ºC) up to Cr, and its decline thereafter to the low-melting Group 12 metals (mercury
being a liquid at room temperature). The strength of metallic bonding in tungsten is such that its
melting point (3410ºC) is exceeded by only one other element, carbon.

The radii of d-metal ions depend on the effective charge of the nucleus, and ionic radii generally
decrease on moving to the right as the atomic number increases. The radius of the metal atoms in
the solid element is determined by a combination of the strength of the metallic bonding and the
size of the ions. Thus, the separations of the centres of the atoms in the solid generally follow a
similar pattern to the melting points: they decrease to the middle of the d block, followed by an
increase back up to Group 12, with the smallest separations occurring in and near Groups 7 and
8.

The atomic radii of the elements in the 5d series (Hf, Ta, W…….) are not much bigger than
those of their 4d-series congeners (Zr, Nb, Mo,...). In fact, the atomic radius of Hf is smaller than
that of Zr even though it appears in a later period. To understand this anomaly, we need to
consider the effect of the lanthanoids (the first row of the f block). The intervention of the
lanthanoid elements in Period 6 corresponds to the occupation of the poorly shielding 4f orbitals.
Because the atomic number has increased by 32 between Zr in Period 5 and its congener Hf in
Period 6 without a corresponding increase in shielding, the overall effect is that the atomic radii
of the 5d-series elements are much smaller than expected. This reduction in radius is the
lanthanide contraction

The lanthanide contraction also affects the ionization energies of the 5d-series elements, making
them higher than expected on the basis of a straightforward extrapolation. Some of the metals—
specifically Au, Pt, Ir, and Os—have such high ionization energies that they are unreactive under
normal condition.

Atomic mass increases with atomic number, and the combination of this increase with the
changes in the radii of the metal atoms in the metal lattice means that the mass densities of the
elements reach a peak with Ir (density 22.65 g cm/3).
Trends in chemical properties