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Transition elements:

The term transition metal (sometimes also called a transition element) has two possible meanings:

The IUPAC definition: states that a transition metal is "an element whose atom has an incomplete d sub-shell, or which can give rise to Cations with an incomplete d sub-shell." Group 12 elements are not transition metals in this definition. Some authors describe a "transition metal" as any element in the d-block of the periodic table, which includes groups 3 to 12 on the periodic table. All elements in the d-block are metals. In actual practice, the f-block is also included in the form of the lanthanide and actinide series.

Jensen has reviewed the history of the terms transition element (or metal) and dblock. The word transition was first used to describe the elements now known as the d-block by the English chemist Charles Bury in 1921, who referred to a transition series of elements during the change of an inner layer of electrons (for example n=3 in the 4th row of the periodic table) from a stable group of 8 to one of 18, or from 18 to 32.

[hide]v d e Periodic table H Li Be M Na g K Ca Rb Sr L a A Fr Ra c Cs Ba


Alkali metals

B C

N O F S

He Ne

Al Si P S T V c i Z N Y r b L H T u f a L R D r f b Cr M o W Sg M F C n e o R R Tc u h O Re Ir s B H M h s t N i P d C u A g A Pt u D R s g Z n C d H g C n

Cl Ar

Ga Ge As Se Br Kr In Sn Sb Te I Xe

C e T h

P N P S Eu r d m m P N A U Pu a p m

G d C m

T D H T Er b y o m B F M Cf Es k m d

Y b N o

Tl Pb Bi Po At Rn Uu Uu Uu Uu Uu Uu t q p h s o
Unknown chem. properties

Alkaline Transition Other earth Lanthanides Actinides metals metals metals

Metalloids

Other Noble Halogens nonmetals gases

Electronic configuration:
Electronic configuration of first series of d-block elements For first series (Sc z=21) to (Zn Sc (z=21): 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 2 2 6 2 6 Ti (z=22) : 1s , 2s , 2p , 3s , 3p , 4s2, 2 2 6 2 6 V (z=23) : 1s , 2s , 2p , 3s , 3p , 4s2, 2 2 6 2 6 1 Cr (z=24) : 1s , 2s , 2p , 3s , 3p , 4s , Mn (z=25) : 1s2, 2s2, 2p6, 3s2, 3p6, 4s2 Fe (z=26) : 1s2, 2s2, 2p6, 3s2, 3p6, 4s2 2 2 6 2 6 Co (z=27) : 1s , 2s , 2p , 3s , 3p , 4s2 2 2 6 2 6 Ni (z=28) : 1s , 2s , 2p , 3s , 3p , 4s2 2 2 6 2 6 Cu (z=29) : 1s , 2s , 2p , 3s , 3p , 4s1 2 2 6 2 6 2 10 Zn (z=30) : 1s , 2s , 2p , 3s , 3p , 4s ,3d . z=30) 3d1. 3d2. 3d3. 3d5. ,3d5. ,3d6. ,3d7. ,3d8. ,3d10.

Classification
In the d-block the atoms of the elements have between 1 and 10 d electrons.
Group 3 4 Ti 22 Zr 40 5 V 23 Nb 41 6 Cr 24 7 8 9 Co 27 10 Ni 28 Pd 46 Pt 78 11 Cu 29 12 Zn 30

Period 4 Sc 21 Period 5 Y 39 Period 6 * 5771

Mn 25 Fe 26

Mo 42 Tc 43 W 74 Re 75

Ru 44 Rh 45 Os 76 Ir 77

Ag 47 Cd 48 Au 79 Hg 80

Hf 72 Ta 73

Period 7 ** 89103 Rf 104 Db 105 Sg 106 Bh 107 Hs 108 Mt 109 Ds 110 Rg 111 Cn 112

Typical and non-typical transition elements :


The elements of groups 411 are now generally recognized as transition metals, as are Sc and Y in Group 3. For the elements La-Lu and Ac-Lr and also for Group 12, different sets of definitions are used by different authors. Many chemistry textbooks and printed periodic tables classify La and Ac as Group 3 elements and transition metals, since their atomic ground-state configurations are s2d1 like Sc and Y. The elements Ce-Lu are considered as the lanthanide series (or lanthanoid according to IUPAC) and Th-Lr as the actinide series. The two series together are classified as f-block elements, or (in older sources) as inner transition elements.
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Some inorganic chemistry textbooks include La with the lanthanides and Ac with the actinides .This classification is based on similarities in chemical behavior, and defines 15 elements in each of the two series even though they correspond to the filling of an f subshell which can only contain 14 electrons. A third classification defines the f-block elements as La-Yb and Ac-No, while placing Lu and Lr in Group 3. This is based on the aufbau principle (or Modeling rule) for filling electron subshells, in which 4f is filled before 5d (and 5f before 6d), so that the f subshell is actually full at Yb (and No) while Lu (and Lr) has an [ ] s2f14d1 configuration. However La and Ac are exceptions to the Aufbau principle with electron configuration [ ] s2d1 (not [ ] s2f1 as the aufbau principle predicts) so it is not clear from atomic electron configurations whether La or Lu (Ac or Lr) should be considered a transition metal. Zinc, cadmium, and mercury are sometimes not classified as transition metals as they have the electronic configuration [ ] d10s2, with no incomplete d shell. In the oxidation state +2 the ions have the electronic configuration [ ] d10. While these elements can exist in the +1 oxidation state, as in the diatomic ion Hg2+ 2, there are no unpaired electrons because of the formation of a covalent bond between the two atoms of the dimer.

Post transition metals:


The group 12 elements Zn, Cd and Hg may be classed as post-transition metals in this case. However, it is often convenient to include these elements in a discussion of the transition elements

Characteristic properties
There are a number of properties shared by the transition elements that are not found in other elements, which results from the partially filled d shell. These include The formation of compounds whose color is due to dd electronic transitions, The formation of compounds in many oxidation states, due to the relatively low reactivity of unpaired d electrons.

The formation of many paramagnetic compounds due to the presence of unpaired d electrons. A few compounds of main group elements are also paramagnetic (e.g. nitric oxide, oxygen)

Energy Difference:
Here the inner d orbital has more energy than the valence-shell s orbital. In divalent and trivalent ions of the transition metals, the situation is reversed such that the s electrons have higher energy. Consequently, an ion such as Fe2+ has no s electrons: it has the electronic configuration [Ar] 3d6 as compared with the configuration of the atom, [Ar] 4s23d6
Colored compounds:

From left to right, aqueous solutions of: K2Cr2O7 (orange); K2CrO4 (yellow); CuSO4 (blue); KMnO4 (purple). Color in transition-series metal compounds is generally due to electronic transitions of two principal types. Charge transfer transitions. An electron may jump from a predominantly ligand orbital to a predominantly metal orbital, giving rise to a ligand-to-metal chargetransfer (LMCT) transition. These can most easily occur when the metal is in a high oxidation state. For example, the color of chromate, dichromate and permanganate ions is due to LMCT transitions. Another example is that mercuric iodide, HgI2, is red because of a LMCT transition. A metal-to ligand charge transfer (MLCT) transition will be most likely when the metal is in a low oxidation state and the ligand is easily reduced. d-d transitions: An electron jumps from one d-orbital to another. In complexes of the transition metals the d orbitals do not all have the same energy. The pattern of splitting of the d orbitals can be calculated using crystal field theory. The extent of the splitting depends on the particular metal, its oxidation state and the nature of the ligands.
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Color Except zinc all the transition metals complex ions are colorless due to presence of unpaired electrons. The color of ions can be explained on the basis of "Crystal field theory". According to this theory, the bonding between ligands and a metal ion is electrostatic. The ligands surrounding the metal ion and create an electrostatic field around its d-orbitals. This field split '5' degenerated d -orbitals in to two sets of different energies. (i) A high energy pair (e.g.) of dx2-dy2 and dz2. (ii) A low energy trio (t2g) of dxy, dyz, dzx.

In many cases difference of energy between two sets 'e.g.' and 't2g' is equivalent to a wavelength in the visible region. Thus absorbing visible light, an electron may be able to move from lower energy set t2g to higher energy set e.g. In doing so, some of the component wavelength of white light is removed, so the remaining component wavelength of light reflected or transmitted shows the colour. For example: Cu+2 (blue), V+3 (green), Co+2 (pink), Fe+2 (green), Fe+3 (yellow), Ti+3 (purple).

Oxidation states:
As stated earlier, most of the d-block elements exist in several oxidation states - for example, the oxidation number of iron can be 0, +2, +3 and +6. The widest range of oxidation numbers is for manganese, which has a lowest oxidation number of 0 and a highest oxidation number of +7. There are general tendencies concerning the oxidation numbers: (a) The 1st and last elements, scandium and zinc, have only 1 oxidation number.

(b) All the elements except zinc can have oxidation number +3 (c) All the elements except scandium can have oxidation number +2 (d) From scandium to manganese, the highest oxidation number = the number of 4s electrons + the number of 3d electrons (e) From manganese to zinc, low oxidation numbers are common.

Examples of variable oxidation states in the transition metals: Iron Iron has two common oxidation states (+2 and +3) in, for example, Fe2+ and Fe3+. It also has a less common +6 oxidation state in the ferrate (VI) ion, FeO42-. Manganese Manganese has a very wide range of oxidation states in its compounds. For example: +2 +3 +4 +6 in Mn2+ in Mn2O3 in MnO2 in MnO42-

The molecules or ions surrounding the central metal ion are called ligands. Ionic compounds are mostly formed with oxidation states +2 and +3. In aqueous solution the ions are hydrated by (usually) six water molecules arranged octahedrally.
Magnetism

Transition metal compounds are paramagnetic when they have one or more unpaired d electrons. In octahedral complexes with between four and seven d electrons both high spin and low spin states are possible. Tetrahedral transition metal complexes such as [FeCl4]2 are high spin because the crystal field splitting is small so that the energy to be gained by virtue of the electrons being in lower energy orbitals is always less than the energy needed to pair up the spins. Some compounds are diamagnetic. These include octahedral, low-spin, d6 and squareplanar d8 complexes. In these cases, crystal field splitting is such that all the electrons are paired up. Ferromagnetism occurs when individual atoms are paramagnetic and the spin vectors are aligned parallel to each other in a crystalline material. Metallic iron and the alloy alnico are examples of ferromagnetic materials involving transition metals. Anti-ferromagnetism is another example of a magnetic property arising from a particular alignment of individual spins in the solid state.
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Diamagnetic, Paramagnetic, and Ferromagnetic Materials:


When a material is placed within a magnetic field, the magnetic forces of the material's electrons will be affected. This effect is known as Faraday's Law of Magnetic Induction. However, materials can react quite differently to the presence of an external magnetic field. This reaction is dependent on a number of factors, such as the atomic and molecular structure of the material, and the net magnetic field associated with the atoms. The magnetic moments associated with atoms have three origins. These are the electron motion, the change in motion caused by an external magnetic field, and the spin of the electrons. In most atoms, electrons occur in pairs. Electrons in a pair spin in opposite directions. So, when electrons are paired together, their opposite spins cause their magnetic fields to cancel each other. Therefore, no net magnetic field exists. Alternately, materials with some unpaired electrons will have a net magnetic field and will react more to an external field. Most materials can be classified as diamagnetic, paramagnetic or ferromagnetic. Diamagnetic materials have a weak, negative susceptibility to magnetic fields. Diamagnetic materials are slightly repelled by a magnetic field and the material does not retain the magnetic properties when the external field is removed. In diamagnetic materials all the electron are paired so there is no permanent net magnetic moment per atom. Diamagnetic properties arise from the realignment of the electron paths under the influence of an external magnetic field. Most elements in the periodic table, including copper, silver, and gold, are diamagnetic. Paramagnetic materials have a small, positive susceptibility to magnetic fields. These materials are slightly attracted by a magnetic field and the material does not retain the magnetic properties when the external field is removed. Paramagnetic properties are due to the presence of some unpaired electrons, and from the realignment of the electron paths caused by the external magnetic field. Paramagnetic materials include magnesium, molybdenum, lithium, and tantalum. Ferromagnetic materials have a large, positive susceptibility to an external magnetic field. They exhibit a strong attraction to magnetic fields and are able to
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retain their magnetic properties after the external field has been removed. Ferromagnetic materials have some unpaired electrons so their atoms have a net magnetic moment. They get their strong magnetic properties due to the presence of magnetic domains. In these domains, large numbers of atom's moments (1012 to 1015) are aligned parallel so that the magnetic force within the domain is strong. When a ferromagnetic material is in the unmagnitized state, the domains are nearly randomly organized and the net magnetic field for the part as a whole is zero. When a magnetizing force is applied, the domains become aligned to produce a strong magnetic field within the part. Iron, nickel, and cobalt are examples of ferromagnetic materials. Components with these materials are commonly inspected using the magnetic particle method.

Catalytic Properties

The transition metals and their compounds are known for their homogeneous and heterogeneous catalytic activity. This activity is ascribed to their ability to adopt multiple oxidation states and to form complexes. Vanadium(V) oxide (in the contact process), finely divided iron (in the Haber process), and nickel (in Catalytic hydrogenation) are some of the examples. Catalysts at a solid surface involve the formation of bonds between reactant molecules and atoms of the surface of the catalyst (first row transition metals utilize 3d and 4s electrons for bonding). This has the effect of increasing the concentration of the reactants at the catalyst surface and also weakening of the bonds in the reacting molecules (the activation energy is lowering). Also because the transition metal ions can change their oxidation states, they become more effective as catalysts. Transition metals as catalysts: Iron in the Haber -Process The Haber- Process combines the hydrogen and nitrogen to make ammonia using an iron catalyst.

Nickel in the hydrogenation of C=C bonds This reaction is at the heart of the manufacture of margarine from vegetable oils.
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However, the simplest example is the reaction between ethene and hydrogen in the presence of a nickel catalyst.

Transition metal compounds as catalysts Vanadium (V) oxide in the Contact Process: At the heart of the Contact Process is a reaction which converts sulphur dioxide into sulphur trioxide. Sulphur dioxide gas is passed together with air (as a source of oxygen) over a solid vanadium (V) oxide catalyst.

Iron ions in the reaction between persulphate ions and iodide ions: Persulphate ions (peroxodisulphate ions), S2O82-, are very powerful oxidising agents. Iodide ions are very easily oxidised to iodine. And yet the reaction between them in solution in water is very slow. The reaction is catalysed by the presence of either iron(II) or iron(III) ions.

Other properties:

As implied by the name, all transition metals are metals and conductors of electricity. In general transition metals possess a high density and high melting points and boiling points. These properties are due to metallic bonding by delocalized d electrons, leading to cohesion which increases with the number of shared electrons. However the group 12 metals have much lower melting and boiling points since their full d subshells prevent dd bonding. In fact mercury has a melting point of 39 C and is a liquid at room temperature.

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Many transition metals can be bound to a variety of ligands.


General Reactivity:

These elements have d electrons in their valence shells, and this gives them different characteristics to other metals in the periodic table. They each exist in several oxidation states except scandium and zinc; many of their compounds are coloured; and they readily form complexes by acting as Lewis acids.
Occurrence and Extraction:

The first six elements, scandium to iron, occur mainly as the oxides in various mineral deposits. The most abundant of these is iron, found chiefly in magnetite and haematite, both commonly known as iron ore. The remaining of the elements occurs mainly as sulfides such as zinc blende. Each element is extracted from the appropriate mineral by various extraction methods. The extraction of iron, however, is of immense importance as steel basically a mixture of iron and carbon - is used in greater quantities world-wide than any other metal. Steel is produced from iron ore in two main stages: (1) A blast furnace produces impure iron from iron ore (2) The impure iron is then purified and alloyed with other metals to produce steel.
Physical Properties:

All these elements are hard, rigid and have good thermal and electrical conductivities. They have high melting and boiling points.
Chemical Properties:

The chemistry of the d-block elements is governed by the fact that most exhibit several oxidation numbers. This is because the energies of all the d electrons are very similar. The d electrons also confer properties on these elements not found elsewhere: - They easily form complexes - Their complexes are often colored - Some complexes are paramagnetic
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- They make good catalysts. The chemical properties of these elements and their many complexes are extensive, and not suitable for further study here.
Industrial Information:

The d-block elements are used in many thousands of applications. Iron is the most widely used element because it is converted to steel, which consists of iron with 0.2 - 1.7% carbon. The addition of carbon hardens the iron and gives it better resistance to corrosion. Special steels can be prepared by the addition of small quantities of other elements - stainless steel contains 18% chromium and 8% nickel. Iron and steel are extensively used in our society. Other important uses of some of these elements include titanium in aircraft and spaceship manufacture. Titanium is less dense than other d-block elements, and this lightness, coupled with its extra hardness, make it more suitable than aluminium in high-flying aircraft and space vessels. Chromium is often used for electroplating, and alloyed with nickel to make nichrome - used in electrical components as its electrical resistance hardly varies with temperature. Copper is used as protective sheeting as it is more resistant to oxidation than other elements. The green patina that forms on exposure to air is copper (II) carbonate, sulfate or chloride. Copper is also used in electrical cables. Zinc is used in protecting steel by galvanising, and in alloys, eg brass (copper and zinc).

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