Transition elements [d[d- block elements]

Position in the periodic table

20_431

Sc Y La

Ti Zr Hf

V Nb Ta

Cr Mo W

Mn Tc Re

Fe Ru Os

Co Rh Ir

Ni Pd Pt

Cu Ag Au

Zn Cd Hg

Ac Unq Unp Unh Uns Uno Une Uun Uuu

Ce Th

Pr Pa

Nd U

Pm Sm Np

Eu

Gd

Tb

Dy Cf

Ho

Er

Tm

Yb No

Lu Lr

Pu Am Cm Bk

Es Fm Md

Where are the transition metals?

The transition metals are the block of elements located between group 2 and group 13 of the periodic table. group 2 group 13

Sc Ti V Cr Mn Fe Co Ni Cu Zn Y Zr Nb Mo Tc Ru Rh Pd Ag Cd La Hf Ta W Re Os Ir Pt Au Hg Ac Rf Db Sg Bh Hs Mt Ds Rg ?

Here, the word transition is used to mean in-between.

Why transition metals are called typical metals?

The transition metals are known as typical metals because of their physical properties. They are:  lustrous (bright and shiny).  hard and strong.  high density.  malleable (can be bent and pressed into different shapes) and ductile (can be drawn into wires).  good conductors of heat and electricity.  high melting and boiling points (except mercury, which is liquid at room temperature).

All 'd' block elements are classified into four transition series namely: 3d series in the 4th period 10 elements 4d series in the 5th period- 10 elements 5d series in the 6th period- 10 elements 6d series in the 7th period having incomplete elements.

GENERAL PROPERTIES OF TRANSITION ELEMENTS

All the elements belonging to I B, II B, III B, IV B, V B, VI B, VII B, VIII B (i.e.3 TO 12) are called transition elements. They resemble each other in several physical and chemical properties. They are all metals. They are called transition elements because they are placed between the most reactive metals on the left and nonnon-metals on the right. Their compounds are colored. They exhibit variable valency. They form co-ordination compounds. coTend to be hard and durable. Have high tensile strength. Have good mechanical properties.

Electronic Configuration

General outer electronic configuration is (n - 1) d1-10 ns1-2.  Each additional electron enters the (n-1) sub-shell. (n- sub 'd' block elements are those in which the added electron goes into one of the 'd' orbitals.  These elements have valence electrons in both their outermost and penultimate shells (second outermost)

Energy

4p 3d

4s 3p 3s 2p 2s

1s

Sc -1s2 2s2 2p6 3s2 3p6 3d1 4s2

Electronic Arrangement
El
Sc Ti V Cr Mn Fe Co Ni Cu Zn

Z
21 22 23 24 25 26 27 28 29 30 [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar]

3d

4s

Chromium and Copper

Cr and Cu dont fit the pattern of building up the 3d sub-shell, why? sub-

CHROMIUM

Energy

4p

4s 3p 3s 2p 2s

3d

1s

Cr-1s2 2s2 2p6 3s2 3p6 3d5 4s1

Energy

4p

4s 3p 3s 2p 2s

3d

1s

Cu-1s2 2s2 2p6 3s2 3p6 3d10 4s1

GENERAL CHARACTERISTICS OF TRANSITION ELEMENTS

The members belonging to a given transition series do not differ so much from one another as those of representative elements of the same period. It is due to as there is no change in the number of ns electrons and only change occurs in the (n(n- 1)d electrons from member to member in a period.

Sc3+ and Zn2+ are not the typical TM ions Not all d block elements have incomplete d sub-shells. sub e.g. Zn has e.c. of [Ar]3d104s2, the Zn2+ ion ([Ar] 3d10) is not a typical TM ion  Similarly Sc forms Sc3+ which has the stable e.c of Ar. Sc3+ has no 3d electrons

What is a transition metal?

For this reason, a transition metal is defined as being an element which forms at least one ion with a partially filled sub-shell of d electrons. sub In period 4 only Ti-Cu are TMs! Ti Note that when d block elements form ions the s electrons are lost first

1. Metallic character
Most of the transition elements of the first row form metallic bonds due to the presence of incomplete outermost energy level. So, all the transition elements exhibit metallic characters. The strength of the metallic bond depends upon the number of unpaired d-electrons. As the number dincreases the strength also increases. Due to the absence of unpaired electrons 'Zn' is not a hard metal.

Hg exists as a liquid at room temperature Mercury has completely filled d10 electronic configuration. Hence the extent of metallic bond formation is less as the orbitals are completely filled. due to weak interatomic forces of attraction, Hg exists as a liquid at room temperature
(Downward trend in melting points from Zn (420C) (420 through Cd (321 C) to Hg (-39 C) (-

2. Atomic and Ionic radii

Atomic radii: In the transition elements the atomic radii decreases with increase in atomic number. At the end of series it slightly increase due to increase in electron-electron repulsion. electronThe atomic radii of 4-d and 5-d series are very 45close due to lanthanide contraction.

Atomic radii :
20_435

0.2 La 1st series (3 d ) Y Atomic ra dii (n m) Hf Zr 2nd series (4 d) 3rd series (5 d) Ta Nb W Mo Au Ag Ir Rh Mn Fe Co Pt Pd Ni Cu

Sc 0.15 Ti

Re Tc

Os Ru

V Cr

0.1 Atomic number

Ionic radii: In the first row transition elements the ionic radii decreases with increase in atomic number. The value of ionic radii also depends on the oxidation state of metals. As the oxidation state increases the ionic radii decreases (nuclear pull increase)and as the oxidation state decreases the ionic radii increases.

3. Colored ions
In the first row transition elements all the elements except Zn form colored ions. As these elements have incomplete d-orbital, some amount dof energy is required to promote the electrons from lower energy level to higher energy level. This process exhibits radiations from which the compounds absorb a particular color. But some elements other than Zn also appear colorless depending on their oxidation state. For e.g., Sc3+, Ti4+ and Cu+ have completely filled d-orbitals and hence they dappear colorless.

Most of the transition elements form colored compounds both in solid state as well as in aqueous solution. It is already studied that the transition metals have incomplete d-orbital. The electrons are to dbe promoted from a lower energy level to a higher energy level. Some amount of energy is required for this process and the radiations of light are observed in the visible region. The compounds absorb a particular color from the radiation and the remaining ones are emitted. For e.g., Cu2+ are bluish green in color due to absorption of red light wavelength. As Zn has completely filled d-orbitals it cannot absorb dradiation and hence Zn2+ salts are white.

Most transition metals form coloured compounds. For example:  Iron (II) oxide (FeO2) is black.

 Iron (III) oxide (Fe2O3) is red/brown when hydrated this is rust.  Copper (II) sulfate crystals (CuSO4.H2O) is blue these can be turned white by heating the crystals to remove the water.

Copper (I) oxide Cu2O is red/brown.

Copper (II) oxide CuO is black.

Color and Magnetism

Electrons in partially filled d sublevel absorbs visible light , moves to slightly higher energy d orbital.

Magnetic properties are due to unpaired electrons.

4. Complex formation
All the first row transition elements form complexes. These complexes contain negative ions or neutral molecules linked to a metal ion. These are called as ligands. Some examples of the complex compounds formed by first row transition elements are: As the transitions metals are small in size they form large number of complexes. [Fe(CN)6]4[Fe(CN)6]4-, [Cu(NH3)4]2+, [Ni(CN)4]2-, [Ni(CN)4]2[Zn(NH3)4]2+32+2+

5. Variable Oxidation State

The transition elements show variable oxidation states. By the study of electronic configuration of transition metals it is understood that variable oxidation state can be formed as there are both ns and (n-1)d (nelectrons in bonding. bonding. The participation of ns electrons in bonding leads to +2 oxidation state which is a lower oxidation state. The participation of (n-1)d electrons in bonding leads to higher oxidation (nstates like +3, +4, +5, +6 etc. These oxidation states depend upon the nature of combination of transition metals with other elements. The oxidation state increases with atomic number. This increase is related to groups. The most common oxidation state of the elements of first transition series is +2. Ionic bonds are formed in lower oxidation state transition elements whereas covalent bonds are formed in higher oxidation states. Zn is an exception among them as it has fully filled d-orbital, it exhibits only d+2 oxidation state. The oxidation states of first row transition metals are shown below.

Oxidation States of TM s
Sc Ti V
+2 +3 +3 +4 +3 +4 +5 +6 +6 +7 +6

Cr
+2 +3

Mn
+2 +3 +4

Fe
+2 +3

Co
+2 +3

Ni
+2 +3

Cu
+1 +2 +3

Zn
+2

Oxidation States of TM s

Stability of OS s
Change from one OS to another is a redox reaction Relative stability of different OS s can be predicted by looking at Standard Electrode Potentials
 E values

Stability of OS s
General trends
 Higher OS s become less stable relative to lower ones on moving from left to right across the series.  Compounds containing TM s in high OS s tend to be oxidising agents e.g MnO4 Compounds with TM s in low OS s are often reducing agents e.g V2+ & Fe2+

Stability of OS s
General trends (continued)
 Relative stability of +2 state with respect to +3 state increases across the series  For compounds early in the series, +2 state highly reducing
E.g. V2+(aq) & Cr2+(aq) strong reducing agents

 Later in series +2 stable, +3 state highly oxidising

E.g. Co3+ is a strong oxidising agent, Ni3+ & Cu3+ do not exist in aqueous solution.

6. Catalytic property
TM s and their compounds are effective and important catalysts due to,  The availability of 3d and 4s e Ability to change OS

f- block elements

20_431

Sc Y La

Ti Zr Hf

V Nb Ta

Cr Mo W

Mn Tc Re

Fe Ru Os

Co Rh Ir

Ni Pd Pt

Cu Ag Au

Zn Cd Hg

Ac Unq Unp Unh Uns Uno Une Uun Uuu

Ce Th

Pr Pa

Nd U

Pm Sm Np

Eu

Gd

Tb

Dy Cf

Ho

Er

Tm

Yb No

Lu Lr

Pu Am Cm Bk

Es Fm Md

The f - block elements are also called as inner transition elements. As the last electron enters the f-orbital fthese elements are called as f - block elements. These are divided into two series: Lanthanides and actinides. Lanthanides are the elements in which the last electron enters into 4f - orbital. Actinides are the elements in which the last electron enters into 5f-orbital. 5f-

Oxidation states
Lanthanides exhibit different oxidation states like +2, +3 and +4. Among these +3 is the most stable oxidation state. The elements that attain stable electronic configuration by losing 2 or 4 electrons exhibit +2 and +4 oxidation states.

Lanthanide contraction
In lanthanides there is a gradual decrease in atomic size, atomic radii and ionic radii with increase in atomic number. This regular decrease is known as lanthanide contraction. Causes In lanthanides, the nuclear charge increases by one unit at each successive element and this new electron enters the 4f-subshell. Due to the peculiar 4fshapes of f-orbitals, there is imperfect shielding of felectrons from the nuclear attraction. As a result of this the size of lanthanide atoms decreases.

METALLURGY OF IRON Ores of Iron

METALLURGY OF IRON -

BLAST FURNACE

METALLURGY OF IRON :Reactions

Combustion Zone Reaction : Combustion of coke Temperature of the region: 2000C 2000

C + O2

CO2

Fusion Zone Reaction: Reduction of carbon dioxide to carbon monoxide Temperature of the region: 1300 C

CO2 + O2

2CO

Decomposition of Limestone The lime stone (CaCO3) decomposes to give carbon dioxide and quicklime (CaO)

CaCO3

CaO + CO2

The above reaction is endothermic and the temperature in the region falls to about 800-1000C. 800-

Formation of Slag The quicklime reacts with acidic impurities such as silica (SiO2) and forms a slag which melts and collects above the iron at the bottom of the furnace. Slag is an easily fusible mass having a low melting point.

CaO + SiO2

CaSiO3

Reduction Zone Reduction of hematite to molten iron takes place here.

Fe2O3 + 3CO

2Fe + CO2

Temperature of the region: 500-700 C 500In the upper region of the furnace, the CO reduces the hematite to molten iron and oxidizes it self to CO2. The molten iron produced is collected, poured into moulds and solidified to give pig iron. Pig iron contains carbon, sulphur, phosphorus, silicon and manganese as impurities

METALLURGY OF COPPER
CONCENTRATION The finely crushed ore is concentrated by Froth-Floatation process. The Frothfinely crushed ore is suspended in water containing a little amount of pine oil. A blast of air is passed through the suspension. The particles get wetted by the oil and float as a froth which is skimmed. The gangue sinks to the bottom.

ROASTING

The concentrated ore is then roasted in a furnace in the presence of a current of air. Sulphur is oxidized to SO2 and impurities of arsenous and antimony are removed as volatile oxides.
2CuFeS2 + O2 Cu2S + 2FeS + SO2 Cuprous sulphide and ferrous sulphide are further oxidized into their oxides. 2Cu2S + 3O2 2Cu2O + 2SO2 2FeS + 3O2 2FeO + 2SO2 [S + O2 4As + 3O2 4Sb + 3O2 SO2 As2O3 2Sb2O3 ]

SMELTING

The roasted ore is mixed with coke and silica (sand) SiO2 and is introduced in to a blast furnace. The hot air is blasted and FeO is converted in to ferrous silicate (FeSiO3). FeO + SiO2 FeSiO3 Cu2O + FeS Cu2S + FeO FeSiO3 (slag) floats over the molten matte of copper.

BESSEMERIZATION

Copper metal is extracted from molten matte through bessemerization . The matte is introduced in to Bessemer converter which uphold by tuyers. The air is blown through the molten matte. Blast of air converts Cu2S partly into Cu2O which reacts with remaining Cu2S to give molten copper. 2Cu2S + 3O2 2Cu2O + Cu2S 2Cu2O + 2SO2 6Cu + SO2

The copper so obtained is called "Blister copper" because, as it solidifies, SO2 hidden in it escapes out producing blister on its surface.

METALLURGY OF ZINC The important ores of zinc are Zinc blende (Zns), important one Calamine (ZnCO3) Zincite (ZnO)

Concentration :by froth floatation. :by Roasting: (calcination if calamine) 2ZnS + 3O2 2ZnO + 2SO2 Reduction: a) Smelting: ZnO + C 2CO + O2

Zn + CO 2CO2 ( burns with blue flame)

b) Electrolytic : Electrolyte : Zinc sulphate ZnO + H2SO4 ZnSO4 + H2O Cathode : Aluminium sheets Zn++ + 2e Anode : Lead Zn
(99.99 % pure)

METALLURGY OF SILVER : Cyanide process

The important ores of silver are: Argentite or silver glance (Ag2S), Copper silver glance (Ag2S Cu2S) Horn silver ( AgCl) Ruby silver (Ag3SbS3). Silver is extracted from the ore-argentite (Ag2S). oreCyanide treatment: The process of extraction of silver is called as cyanide process as sodium cyanide solution is used. The ore is crushed, concentrated and then treated with sodium cyanide solution. This reaction forms sodium argento cyanide. Ag2S + 2NaCN 2NaCN + Na2S AgCN + 2NaCN Na[Ag(CN)2] x2 Ag2S + 4NaCN 2Na[Ag(CN)2] + Na2S Since the reaction is reversible,Na2S must be removed.

The solution of sodium argento cyanide combines with zinc dust and precipitated silver. Na[Ag(CN)2] AgCN + Zn 2Na[Ag(CN)2] + Zn [NaCN + AgCN]x2 Zn(CN)2 +2Ag 2NaCN +Zn(CN)2 + 2Ag

STUDY OF COMPOUNDS
SILVER NITRATE Preparation: In the preparation of silver nitrate dilute nitric acid is used. Silver combines with HNO3 and forms silver nitrate. 3Ag + 4HNO 3 3AgNO3 + 2H2O + NO

USE OF SILVER NITRATE IN PHOTOGRAPHY

Silver nitrate is a photosensitive crystal commonly used in early photography. Today silver halides are photography. used, but silver nitrate is an intermediate step in halides. manufacturing silver halides. Silver halides (Permalink) The light sensitive ingredient in photographic film and photographic papers that is a combination of silver with bromine, fluorine, chlorine or iodine. iodine. Exposed silver halide particles form metallic silver that turns black when developed.

Potassium permanganate
Structure:

The permanganate ion is tetrahedral.

Extraction from pyrolusite ore[MnO2]

Step 1: Conversion of MnO2 to potassium manganate(K2MnO4)
Pyrolusite fused with caustic potash or potassium carbonate in presence of oxidizing agent like KNO3.

KNO3 MnO2 MnO2

KNO2 + 2KOH + O + K2CO3 + O

+ O K2MnO4 + H2O K2MnO4 + CO2

Step 2: Oxidation of K2MnO4 to KMnO4

The green mass of potassium manganate can be oxidised to potassium permanganate by treating it with water and CO2, Cl2 or Ozone.,

3K2MnO4 + 2CO2 2K2MnO4 + Cl2

2KMnO4 +K2CO3 + MnO2 2KMnO4 + 2KCl

Oxidizing Nature
Oxidizing nature in acidic medium:
2KMnO4 + 3H2SO4 K2SO4 + 2MnSO4 + 3H2O + 5[O]

Eg. It oxidizes potassium iodide to iodine 2KI + H2SO4 + O K2SO4 + H2O + I2 ] x 5

Oxidizing nature in neutral or faintly medium:

2KMnO4 + H2O 2KOH + MnO2 + 3[O] Eg. It oxidizes potassium iodide to iodates KI + 3 O KIO3