Potassium permanganate KMnO4
• Potassium permanganate forms dark purple crystals which.
• The salt is not very soluble in water but when heated it decomposes at 513 K.
• 2KMnO4 → K2MnO4 + MnO2 + O2
Preparation of KMnO4 :-
• KMnO4 is a dark purple solid consisting of two ions:- K + and MnO 4-
(permanganate ion)
• It is a strong oxidizing agent and also posses' medication properties → to
clean wounds and dermatitis.
KMnO4
• Fusion of powdered pyrolusite Ore (MnO2) with an alkali metal hydroxide like
KOH in presence of oxidizing agent like KNO3 leads to formation of dark green
potassium manganate (KMnO4)
• K2MnO4 disproportionate in a neutral or acidic medium to form potassium
permanganate.
2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O
3MnO 2- + 4H+ → 2MnO - + MnO + 2H O
4 4 2 2
• Potassium permanganate is commercially prepared by an alkaline oxidative
fusion of pyrolusite are (MnO2) and again by the electrolytic oxidation of
manganate (4) ion.
2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O
MnO 2- + (electrolytic oxidation) → MnO - + e-
4 4
KMnO4
Physical Properties :
• It is purple coloured crystalline compound.
• Sparingly soluble in water at room temperature.
Chemical Properties
• Effect of heating
• Effect of pH
KMnO4
• KMnO4 shows strong oxidising nature.
• It shows different oxidising nature in different medium
• Acidic medium:
• Neutral or faintly alkaline medium:
• Strongly alkaline medium:
Inner Transition Elements
.
Inner Transition Elements
The f block consist of 2 series
i. Lanthanoids – 14 elements following Lanthanum
ii. Actinoids - 14 elements following Actinium
The elements in which the last electron enters the outermost f orbital is called
as f block elements
• In Lanthanoids the last electron enters into 4f orbital
• In Actinoids the last electron enter into 5f orbital
• The Lanthanoids are also called as 4f series and Actinoids are also called as 5f
series.
Lanthanoids in PT
Lanthanoids
Lanthanoids configuration
.
Lanthanoids
• Starts from cerium(Ce) and ends at Luthenium(Lu) but Lanthanum is not
included under Lanthanoids as it does not have an e- in 4f orbital.
The general formula of Lanthanoids are
[Xe]4f1-14 5d0-1 6s2
• Atoms of these elements have electronic configuration with 6s2 common but
with variable occupancy of 4f level
• The electronic configurations of all the tripositive ions (the most stable
oxidation state of all the lanthanoids) are of the form 4fn (n = 1 to 14 with
increasing atomic number).
Atomic size and Ionic size
As we move from Lanthanum to Lutetium the atomic and Ionic radius decreases
due to Lanthanoid contraction.
The gradual decrease in the atomic and ionic radii of lanthanoid elements with
increase in atomic number is called as lanthanoid contraction
• Reasons:
• Lanthanoid contraction is due to Poor shielding effect of 4f electrons
• Addition of e- to the same shell increases effective nuclear charge therefore
the size of Lanthanoids steadily decreases with increase in the atomic number
Lanthanoids
Trend in ionic radii of lanthanoids
Consequences :
• Their separation is difficult as they have small difference in size.
• Resemblance of second and third transition series.
e.g- 4d and 5d transition series have almost same atomic radii. (Zr
and Hf have similar properties due to similar size)
• Basic character- Basic strength of hydroxide decreases from left to
right. ( La(OH)3 is more basic than Lu(OH)3
Lanthanoids
Oxidation state
• +2,+3,+4 are the possible oxidation state of lanthanoids
• +3 is the most common oxidation state
• Eu2+ and Yb2+ show +2 oxidation state and are good reducing agent
(attain f7 and f14)
• Ce, Pm,Nd,Dy show +4 oxidation state only in the MO2 and are good oxidizing
agent.
• (attain f0 and f7)
General characteristics of Lanthanoids
• Silvery white soft metals
• Tarnish rapidly in air
• Hardness increases with increase in atomic number
• Have high boiling point and melting point
• Good conductor of heat and electricity
• Many trivalent Lathanoids are coloured both in the solid
state and in aqueous
Solution.
• Exeption :
• La3+, Lu3+ ions will not show any colour
• EC of La3+ = 4f0
• EC of Lu3+ = 4f14
Lanthanoids:Magnetic property
• Lanthanoid ions other than the f0 type (La3+ and Ce4+) and the f14 type
(Yb2+and Lu3+) are all paramagnetic.
Chemical reactions of Lanthanoids
• Metals when heated with carbon
forms carbides,
Ln3C, Ln2C3 and LnC2
• They liberate hydrogen on
reaction with dilute acids
• Burn in halogens to form halides.
• Burns in oxygen to form oxides LnO2
• Reacts with water to form hydroxides
Ln(OH)3
Lanthanoids
Colour
Many trivalent ions are coloured due to f-f transition .
La3+ and Lu3+ -colourless
Lanthanoids: uses
• Production of alloy steels for plates and pipes.
mischmetall
• A well-known alloy is mishmetal which consists of a
lanthanoid metal (~95%) and iron (~ 5%) and traces of S, C,
Ca and Al.
• Mischmetall is used in Mg-based alloy to produce bullets, shell
and lighter flint
• Mixed oxides of lanthanoids are used as catalysts in
petroleum cracking.
• Some Ln oxides are used as phosphors in television
screens and similar fluorescing surfaces.
Actinoids
Actinoids
Actinoids
• The actinoids include the fourteen elements from Th (at.no.90) to Lr(at.no.103)
• The actinoids are radioactive elements.
• The earlier members have relatively long half lives, latter ones have half life
values ranging from a day to 3 minutes for lawrencium (Z =103).
General Electronic configuration of Actinoids
[Rn] 5f0-14 6d0-1 7s2
• Atoms of these elements have electronic configuration of 7s2 common with
variable occupancy of the 5f and 6d subshells.
• The fourteen electrons are formally added to 5f, though not in thorium (Z = 90)
but from Pa onwards the 5f orbitals are complete at element 103
Actinoids:Ionic Sizes
• There is a gradual decrease in the size of atoms or M3+ ions across the series.
This may be referred to as the actinoid contraction
• Actinoid contraction refers to the gradual decrease in the ionic radii with
increase in atomic number of actinoids.
• Actinoid contraction is due to Poor shielding effect of 5f electrons
Oxidation States
• Actinoids exhibits range of oxidation states, due to
comparable energies of 5f, 6d and 7s levels
• General oxidation state of actinoids are +3. The elements, in
the first half of the series frequently exhibit higher oxidation
states.
Actinoids
• For example, the maximum oxidation state increases from +4 in Th to +5, +6
and +7 respectively in Pa, U and Np but decreases in succeeding elements
Actinoids
Actinoids
General comparison of Lanthanoids and actinoids
Difference between lanthanoids and
Actinoids
i. 4f orbital is progressively i. 5f orbital is progressively
filled. filled
ii. Common O.S is +3 along with ii. . Common O.S is +3 but
+2 and +4. exhibit +4 to +7 also.
iii. Except Pm all are non iii. All are radioactive
radioactive iv. Strong tendency of complex
iv. Less tendency of complex formation
formation v. More reactive than
v. Less reactive than Actinoids Lanthanoids
