Introduction

5/7/2013

Introduction
The position of the d-block elements in the PT is as shown above. They are called the d-block elements because electrons are being added to the d-subshells. The elements with proton number 21 (Sc) to 30 (Zn) are known as the first d-block elements.

5/7/2013

Electronic Configuration
The electronic configuration of calcium (proton number 20), the element prior to scandium is: 1s22s22p63s23p64s2 or [Ar]4s2. Note that, the last two electrons of the calcium atom are filled into the 4s orbital instead of the 3d orbital. This is because, in an isolated atom (without any electrons), the 4s sub-shell has a lower energy than the 3d sub-shell. Hence, electrons must first fill the 4s orbital before filling the 3d orbitals. However, once electrons are filled into the 3d orbital, the order is reversed. The 3d orbitals now have lower energy than the 4s orbital. Hence, the e.c of Sc (proton number=21) is [Ar]3d14s2 and not [Ar]4s23d1
5/7/2013 3

Electronic Configuration
*

5/7/2013

Electronic Configuration
The e.c for the first transition series (from Sc to Zn) is given in the table below. *

5/7/2013

Electronic Configuration
Note that the e.c of Cr is not [Ar]3d44s2 as expected. This is because the configuration of [Ar]3d54s1 is energetically more stable as all the five 3d sub-shells are completely half-filled. * Similarly, the e.c of copper is not [Ar]3d94s2 as expected. This is because the configuration of [Ar]3d104s1 is energetically more stable as all the five 3d sub-shells are completely filled. *
5/7/2013 6

Electronic Configuration
The e.c of the first transition series can be represented as [Ar]3dx4sy, where x has one of the values one to ten (except 4 and 9) and y is two in all cases except Cr and Cu where its value is one. The e.c of the d-block elements is different from that of the Period 3 elements as shown below: *

5/7/2013

Electronic Configuration
In the Period 3 elements, each additional electron goes into the outer sub-shell, while for the d-block elements, each additional electron goes into the inner sub-shell. The inner sub-shells of the Period 3 elements are all fully filled, while the outer sub-shells of the d-block elements are not.

5/7/2013

Transition Elements
Transition element is defined as an element that can form one or more stable ions with an incomplete subshell of d-electrons. Hence, Sc and Zn are not transition elements (even though they are d-block elements). The only stable ion of Sc is Sc3+ ([Ar]3d04s0) where the 3d orbitals are empty. Zn forms only the Zn2+ ion ([Ar]3d104s0) where the 3d orbitals are fully filled. Hence, the first transition series actually runs from Ti (proton number 22) to Cu (proton number 29).

5/7/2013

Physical Properties
Atomic Radius The atomic radius of the transition elements is shown in the table below. *

5/7/2013

10

Physical Properties
Atomic Radius The d-block elements show little variation in their atomic radii as compared to the Period 3 elements. From Sc to Zn, the number of protons in the nucleus and the number of electrons increases. However, each additional electron is added to an inner 3d sub-shell. These additional inner electrons are able to shield the outer electrons from the nucleus and to a large extent cancel out most of the effect of the increase in the number of protons in the nucleus. Hence, the effective nuclear charge increases only slightly resulting in only a small change in the atomic radius. 5/7/2013 11

Physical Properties
Density The table and graph below shows the variation of the density of the transition elements. *

5/7/2013

12

Physical Properties
Density All transition elements have high densities (compared to Al=2.70 gcm-3). This is because of their small atomic size and the close packing of the atoms in the solid lattice. The density increases gradually across the d-block elements because although the atomic size (and hence the atomic volume) does not change much, the relative atomic mass increases gradually.

5/7/2013

13

Physical Properties
Boiling Point and Melting Point The variation of the melting point and boiling point is shown in the table below. *

5/7/2013

14

Physical Properties
Boiling Point and Melting Point All transition elements are typical metals (except Zn) with high melting points (in excess of 1000oC) and high boiling point (in excess of 2000oC). This is due to the presence of strong metallic bonds in the solid lattice. Due to the small difference in energy between the 3d and 4s sub-shell, the transition elements are able to make use of the electrons from these two subshells in the formation of metallic bonds. On the other hand, Ca (a Group 2 metal) is soft with low melting point (850oC) because Ca has only two valence electrons (4s2) available for the formation of the metallic bond.
5/7/2013 15

Physical Properties
Boiling Point and Melting Point Both the melting point and boiling point drop at manganese. This is because in manganese, [Ar]3d54s2, the d-subshell is half full, with five unpaired electrons in each of the d-orbitals. This e.c makes the d-electrons less available to take part in metallic bonding.

5/7/2013

16

Physical Properties
Ionization Energy The table and graph below show the variation of the first, second, third and fourth ionisation energies of the d-block elements. *

5/7/2013

17

Physical Properties
Ionization Energy The first, second, third, and fourth ionisation energy refers to the following processes: M(g) M+(g) + e- first ionisation energy M+(g) M2+(g) + e- second ionisation energy M2+(g) M3+(g) + e- third ionisation energy M3+(g) M4+(g) + e- fourth ionisation energy

5/7/2013

18

Physical Properties
Ionization Energy There is little change in the first and second ionisation energy from Sc to Zn. This is because the electrons are removed from the outer 4s orbitals which is shielded from the nucleus by the increasing screening effect. However, the second ionisation energy of Cr and Cu are higher than expected because the second electron removed from these two elements is from an inner 3d subshell that is closer to the nucleus. Furthermore, the electrons are removed from a stable configuration of 3d5 (for Cr) and 3d10 (for Cu.)
5/7/2013 19

Physical Properties
Ionization Energy *

5/7/2013

20

Physical Properties
Ionization Energy The third ionisation energies of Mn and Zn are higher than expected because the third electron is removed from a stable configuration of 3d5 (for Mn) and 3d10 (for Zn). *

5/7/2013

21

Physical Properties
Ionization Energy On the other hand, the third ionisation energy of iron is lower than expected because the Fe3+ ion formed has a more stable configuration of 3d5. *

The fourth ionisation energy of iron is also higher than expected because the fourth electron is removed from a stable 3d5 configuration. *
5/7/2013 22

Physical Properties
Ionization Energy Generally, the difference between successive ionisation energies of the transition elements is not large because of the close proximity of the 4s and 3d orbitals.

5/7/2013

23

General Properties of the Transition Elements

Transition elements -are hard -have high melting points and boiling points -have high densities -exhibit variable oxidation states in their compounds -form complexes -form coloured compounds -show catalytic properties

5/7/2013

24

General Properties of the Transition Elements

Variable Oxidation States Due to the small difference in energy between the 3d and 4s subshells, atoms of transition elements can make use of the outer 4s electrons as well as some or all of the inner 3d electrons for chemical reactions. Hence, they show variable oxidation states. e.g. the two important oxidation states of iron are +2 and +3. Fe: [Ar]3d64s2; Fe2+:[Ar]3d64s0; Fe3+: [Ar]3d54s0 The oxidation states of the transition elements in their compounds are shown in the table. The more common oxidation states are circled.
5/7/2013 25

General Properties of the Transition Elements

Variable Oxidation States *

5/7/2013

26

General Properties of the Transition Elements

Variable Oxidation States The table below lists the more stable oxides and chlorides of the transition elements. *

5/7/2013

27

General Properties of the Transition Elements

Variable Oxidation States The table below lists the common aqueous cations and oxo-ions of the transition elements. *

5/7/2013

28

General Properties of the Transition Elements

Variable Oxidation States The higher the oxidation states do not exist in the form of free aqueous ions. This is because their high charge density would polarise the water molecules that are coordinated to them resulting in the formation of oxoanions. The common oxidation state for each element include the +2 or the +3 or both. The +3 state is relatively more common at the beginning of the series, while the +2 oxidation state is more common towards the end of the series.
5/7/2013 29

General Properties of the Transition Elements

Variable Oxidation States The maximum oxidation state of the element corresponds to the maximum number of electrons available for bonding. It increases from Ti(+4) to Mn(+7) as electrons from the 4s and 3d subshells are used for reaction. *

5/7/2013

30

General Properties of the Transition Elements

Variable Oxidation States The decrease in the maximum oxidation state from Mn to Cu is due to the decrease in the number of unpaired 3d electrons. e.g. Ni [Ar]3d84s2 has two 4s electron and two unpaired 3d electrons available for bond formation. Hence, the maximum oxidation state for Ni is +4. *

5/7/2013

31

General Properties of the Transition Elements

-Relative Stability of the +2 and +3 Oxidation State -Higher Oxidation States of Transition Elements

5/7/2013

32

General Properties of the Transition Elements

Complex Ions Formation Complex ions are ions that are formed when a central atom or ion is bonded to a group of atoms, molecules or ions (known as ligands) by co-ordinate bonds. Ligands are species that have at least one lone-pair of electrons that are readily donated to a metal atom or ion to form a co-ordinate bond. Ligands are Lewis bases. e.g. The oxygen atom in H2O, nitrogen atom in NH3, carbon atom in CN- and chlorine in Cl- are known as donor atoms.

5/7/2013

33

General Properties of the Transition Elements

Complex Ions Formation All cations have some tendency to form complex ions as they tend to attract the lone pair electrons of surrounding ligands. However, this tendency is exceptionally strong amongst the transition metal cations. This is because of their high charge density and the presence of ample empty orbitals in their valence shells. In the formation of complex ions, the central metal ion accepts the lone pair electrons from the ligands. The central metal ions act as Lewis acids. Examples of complex ions are [FeCl4]2-, [Fe(CN)6]4-, and [CoCl4]2-.
5/7/2013 34

General Properties of the Transition Elements

Complex Ions Formation In the formation of the tetrachloroferate(II) ion, [FeCl4]2-, the Fe2+ ion makes use of the empty 4s and 4p orbitals to form co-ordinate bonds with the Cl- ions. *

5/7/2013

35

General Properties of the Transition Elements

Complex Ions Formation In the formation of the [Fe(CN)6]4- ion, the six electrons in the Fe2+ ion first undergo pairing. The Fe2+ ion then makes use of the empty 4s and empty 4p orbitals and two of the empty 3d orbitals to form co-ordinate bonds with six CN- ions: *

5/7/2013

36

General Properties of the Transition Elements

Complex Ions Formation The formation of the [CoCl4]2-, which is tetrahedral, can be visualised and is represented as follows. *

5/7/2013

37

General Properties of the Transition Elements

Complex Ions Formation Complex formation is a displacement reaction. e.g. the copper(II) ion exists in solution as the [Cu(H2O)6]2+ ion. However, on the addition of excess aqueous ammonia, a dark blue solution containing the [Cu(H2O)2(NH3)4]2+ complex ion is formed. In the reaction, ammonia ligand displaces the water ligand: [Cu(H2O)6]2+ + 4NH3 [Cu(H2O)2(NH3)4]2+ + 4H2O

5/7/2013

38

General Properties of the Transition Elements

-Classification of Ligands -Nomenclature of Complex Ions -The Geometry of Complex Ions (Stereochemistry of Complexes) -Stability of Complexes

5/7/2013

39

General Properties of the Transition Elements

Colour of Complexes Most complexes of transition metals are coloured. The colour of a complex depends on the nature of the central metal ion, the oxidation state of the metal ion, and the type of ligand. The colour of some complexes are given in the table below:

5/7/2013

40

General Properties of the Transition Elements

Colour of Complexes *

5/7/2013

41

General Properties of the Transition Elements

Catalytic Properties According to the Arrhenius collision theory, for a reaction to occur, the reaction particles must collide with one another. However, only those collision with energy equal to or greater than the activation energy will result in the formation of products. A catalyst increases the rate of reaction by lowering the activation energy of the reaction so that more collision will have sufficient energy to overcome the lower activation energy.
5/7/2013 42

General Properties of the Transition Elements

Catalytic Properties The energy profile of a catalysed and an uncatalysed reaction is shown below: *

5/7/2013

43

General Properties of the Transition Elements

Catalytic Properties Most transition elements and their compounds are important catalyst especially in commercial purposes. Their catalytic property is due to their ability to exhibit variable oxidation states or have empty orbitals in their valence shells. The table below lists some reactions that are catalysed by transition elements or their compounds. *

5/7/2013

44

General Properties of the Transition Elements

Catalytic Properties

5/7/2013

45

General Properties of the Transition Elements

Homogeneous Catalysis In a homogeneous catalysis, the catalyst and the reactants are in the same physical states. For example: * The suggested mechanism for the oxidation of I- by S2O82- is as follows: *

The suggested mechanism requires a lower activation energy because they involve the collision of oppositely charged particles, whereas, the uncatalysed route involves the collision of negatively charged particles.
5/7/2013 46

General Properties of the Transition Elements

Heterogeneous Catalysis In heterogeneous catalysis, the catalyst is in a different physical state from the reactants. For example: * Consider the reaction between hydrogen and iodine. The nickel atoms at the surface of nickel metal make use of their empty orbitals to form temporary bonds with the H2 and I2 molecules. This is called adsorption. *

5/7/2013

47

General Properties of the Transition Elements

Heterogeneous Catalysis This weakens the covalent bonds in the H2 and I2 molecules, thus lowering the activation energy for the reaction. Furthermore, the H2 and I2 molecules are correctly orientated for new bonds to be formed. After that, the HI molecules leave the surface of the catalyst, and other H2 and I2 molecules can be adsorbed. *

5/7/2013

48

Isomerism in Complexes
The existence of two or more different compounds having the same molecular formula is called isomerism. Three types of isomerism occur in transition element complexes: -Geometrical isomerism -Optical isomerism -Structural isomerism

5/7/2013

49

Isomerism in Complexes
Geometrical Isomerism Geometrical isomerism (or cis-trans isomerism) is shown by: -Square planar complexes with the formula of Ma2b2 -Octahedral complexes with the formula of Ma4b2 and Ma3b3 -Octahedral complexes with the formula of M(x-x)2b2 [a and b are monodentate ligands, x-x are bidentate ligands]

5/7/2013

50

Isomerism in Complexes
Geometrical Isomerism Complexes of Ma2b2 *

5/7/2013

51

Isomerism in Complexes
Geometrical Isomerism Complexes of Ma4b2

5/7/2013

52

Isomerism in Complexes
Geometrical Isomerism Complexes of M(x-x)2b2

5/7/2013

53

Isomerism in Complexes
Geometrical Isomerism Complexes of Ma3b3 *

5/7/2013

54

Isomerism in Complexes
Optical Isomerism Optical isomerism occurs in octahedral complexes which do not have a plane of symmetry. The complex cannot be divided into two equal halves through any plane. Optical isomers occur in pairs. One is the mirror image of the other and they are not superimposable. Optical isomers also called enantiomers. They are optically active. One isomer will rotate plane polarised light in the clockwise direction (the dextro or + isomer), while the other will rotate plane polarised light in the anti-clockwise direction (the laevo or isomer).
5/7/2013 55

Isomerism in Complexes
Optical Isomerism Complexes with the formula of M(x-x)3
*

5/7/2013

56

Isomerism in Complexes
Optical Isomerism Complexes with the formula of M(x-x)2b2
*

5/7/2013

57

Isomerism in Complexes
Optical Isomerism EDTA complexes-[Ni(EDTA)]4*

5/7/2013

58

Isomerism in Complexes
Structural Isomerism Structural isomerism occurs in complexes having the same molecular formula but are different with respect to the type of ligands that are bonded to the central ion. An interesting example is a compound of Cr having the molecular formula of CrCl3.6H2O. There are three compounds having the molecular formula of CrCl3.6H2O. One is dark green, the other two are light green and purple respectively.

5/7/2013

59

Isomerism in Complexes
Structural Isomerism They can be differentiated by the number of moles of silver chloride precipitated when excess aqueous silver nitrate is added separately to one mole of each of the compounds. The result of the experiment is shown in the table below. *

5/7/2013

60

Isomerism in Complexes
Structural Isomerism Since chlorine atoms that are covalently bonded to the central Cr3+ ion will not be precipitated, the isomers are different in terms of the number of chlorine atoms bonded to the chromium(III) ion. The structural formulae of the three isomers are given in the table. *

5/7/2013

61

Isomerism in Complexes
Structural Isomerism

5/7/2013

62

The Uses of Cr, Co, Mn and Ti

The Uses of Titanium Ti has the same mechanical strength of steel but with two added advantages: It is lighter and it does not corrode. Ti is used in the making of aircraft body, space capsules and nuclear reactors. Titanium(IV) oxide is used as white pigments in paints. It has the following advantages compared to other white pigments such as lead white PbCO3, Pb(OH)2, BaSO4 and CaSO4. It is non-toxic, it does not darken when exposed to air containing hydrogen sulphide. Titanium(IV) oxide is also used as fillers for plastics and rubber.
5/7/2013 63

The Uses of Cr, Co, Mn and Ti

The Uses of Chromium Cr is used to harden steel and to increase its resistance to corrosion. Stainless steel is an alloy of steel consisting of 18% Cr, 1% Ni, and 0.4% C. Alloy of Cr with Vanadium and tungsten is used in high speed cutting tools.

5/7/2013

64

The Uses of Cr, Co, Mn and Ti

Uses of Cobalt and Manganese The major use of Co and manganese is in alloy making. Alloy of Co and samarium (Sm) is used to make permanent magnets. Alloy of manganese and steel is used to make high speed cutting tools and railway points.

5/7/2013

65

Summary
The d block elements have incomplete inner sub-shells. Transition elements are elements that can form at least one stable ion with an incomplete d-subshells. Going across the first transition series: -the atomic radius does not change much -there is little changes in the first and second ionisation energies -there is a gradual increase in the density of the elements.

5/7/2013

66

Summary
All transition elements have the following characteristic properties: -exhibit variable oxidation states -formation of complexes -formation of coloured compounds -catalytic properties Going across the series of +2 oxidation state becomes more stable than the +3 oxidation state. Generally, lower oxidation states are reducing agents, while the higher oxidation states are oxidising agents.

5/7/2013

67

Summary
Complex ions: -The bonds between the ligand and the central ion/atom are co-ordinate bonds. -The general shape of the complex ion depends on its co-ordination number. Co-ordination number: 2; General shape: Linear Co-ordination number: 4; General shape: Tetrahedron or square planar Co-ordination number: 6; Octahedron -They exhibit structural, geometrical (cis, trans, fac and mer) and optical isomerism
5/7/2013 68

Summary
Complex ions: -Splitting of the 3d orbitals by ligands is responsible for the colour of complex ions. In homogeneous catalysis, the catalyst and the reactants are in the same physical state. In heterogeneous catalysis, the catalyst and the reactants are in different physical state.

5/7/2013

69