Transition Elements

• General characteristics
Learning Outcomes
• Describe electronic structures of elements and ions of d-block elements
MCQs = 3
Course Outline

• Partially filled ‘d’ or ‘f’-sub-shells

• d = Main transition elements
• f = Outer transition elements
Transition series
• st
1 series = Sc to Zn (3d-series)
• 2nd series = Y to Cd (4d-series)
• 3rd series = La and Hf to Hg (5d-seires)
• 4th series = Ac and Rf to Cn (Coppernicium) (6d-series)

➢ Non-Typical Transition  IB ( Sc, Y, La  Tri-positive, d0) IIIB (Zn, Cd, Hg  d10,not involve
in bonding)
➢ Coinage metals  Au, Ag, Cu

3d – series elements
Electronic 3d 4s
Elements
Configuration
Sc (21) [Ar] 3d14s2
Ti (22) [Ar] 3d24s2
V (23) [Ar] 3d34s2
Cr (24) [Ar] 3d54s1
Mn (25) [Ar] 3d54s2
Fe (26) [Ar] 3d64s2
Co (27) [Ar] 3d74s2
Ni (28) [Ar] 3d84s2
Cu (29) [Ar] 3d104s1
Zn (30) [Ar] 3d104s2

Max unpaired es for Cr = 6

No of unpaired electrons Ni+2, Cr+2?
(n-1) d10 ns2 is the general electronic configuration of
a) Fe, Co, Ni b) Cu, Ag, Au c) Zn, Cd, Hg d) Se, Y, La
2
Have 3d electronic configuration
(A) Ti+4, V+4 Cr+6 Mn+7 (B) Ti+2, V+3 Cr+4 Mn+5 (C) Ti+3, V+2 Cr+3 Mn+4 (D) Ti+4, V+3 Cr+2 Mn+3
Which one of the following pairs of ions have the same electronic configuration
a) Cr+3, Fe+3 b) Mn+2, Fe+3 c) Co+3, Fe+3 d) Sc+3, Cr+3

Which pair of transition elements shows abnormal electronic configuration? (2012)

Sc and Zn C) Zn and Cu
Cu and Sc D) Cu and Cr
Electronic configuration of chromium (proton number 24) is: (2020)
a. [Ar] 3d4 4s2 b. [Ar} 3d5 4s2
5 1
c. [Ar] 3d 4s d. [Ar] 3d6 4s2
Which of the following is the electronic configuration of Cr? (2019)

A) [Ar] 3d5 4s2 B) [Ar] 3d6 4s0

4 2
C) [Ar] 3d 4s D) [Ar] 3d5 4s1
The anomalous electronic configuration shown by chromium and copper among 3-d series of
elements is due to: (2016)
A) Colour of ions of these metals
B) Variable oxidation states of metals
C) Stability associated with this configuration
D) Complex formation tendency of metals
Which element of 3d series of periodic table shows the electronic configuration of 3d8, 4s2? (2016)
E) Copper C) Zinc
F) Cobalt D) Nickel

Atomic Size
• Atomic radii = Decreases(attraction) then constant then increase (repulsion)
• Density = High

Magnetic properties
• Paramagnetic = Weakly attracted by applied magnetic field
• Diamagnetic substances = Weekly repelled by applied magnetic field
• Ferromagnetic = Strong paramagnetism
• Fe+3 Mn+2 = Max
• Unpaired es  Paramagnetism
• do, d10 = Diamagnetism
• Sc+3, Ti+4 = do
• Zn, Cd, Hg, Cu+1, Ag+, Zn+2, Cd+2, Hg+2 = Diamagnetism
Same paramagnetic behavior
(A) Ti+3, Cu+2 (B) Ti+3, Ni+2 (C) Ti+4, Cu+2 (D) Mn+2, Cu+2

In 3rd series of transition elements, paramagnetic behavior is maximum for Mn +2 and: (2020)
a. Cr3+ b. Ti3+ c. V3+ d. Zn+2

Paramagnetic behavior of atoms, ions or molecules is due to: (2010)

A) Paired electrons C) Protons
B) Unpaired electrons D) Neutrons

The paramagnetic character of substances is due to the presence of: (2011)

A) Bond pairs of electrons
B) Lone pairs of electron
C) Unpaired electrons in the atom or molecule
D) Paired electrons in the valence shell of atoms
Binding energy
• Binding energy  Unpaired es  No of bonds  Mechanical strength  Toughness  Melting point
 Hardness
• In 3d series V has max binding energy other wise VIB has max value
• Variation is due to change in metallic structure

M.pt and B.pt: Same as Binding energy

Highest binding energy for
(A) Cr (B) Co (C) V (D) Zn

Variable Oxidation state

• Due to core es
• Mn = Max = +7
• +3 common at starting and +2 at the last
• First and last member no variable oxidation state
• Oxidation No  Covalent character
• Lower = Basic, Ionic, Reducing agent, Mostly colored
• Higher = Acidic, Covalent, Oxidizing agent, Mostly colorless
V +5 ⎯⎯⎯⎯⎯
Reducing agent
→ VO +2 ⎯⎯⎯⎯⎯
Reducing agent
→ V +3 ⎯⎯⎯⎯⎯
Reducing agent
→ V +2 In the above reaction vanadium act as
(a) oxidizing agent (b) Reducing agent (c) Both (d) None
A+1 + Agent ⎯⎯ → A-1 Strong agent is
(a) V+5 (b) V+4 (c) V+3 (d) V+2
Not arrange in correct sequence
(a) d5, d3, d1, d4 = Increasing magnetic moment
(b) MO, M2O3, MO2, M2O5 = Decreasing basic strength
(c) Sc, V, Cr, Mn = Increasing oxidation number
(d) Co3+, Fe3+, Cr3+, Sc3+ = Increasing stability
Correct order of to be reduced
(a) CrCO3 > Cr2(SO4)3 > K2CrO4 (b) K2CrO4 > Cr2(SO4)3 > CrCO3
(c) Cr2(SO4)3> K2CrO4 > CrCO3 (d) Cr2(SO4)3 > CrCO3 > K2CrO4
Which one can form more acidic oxide?
a) Sc b) Mn c) V d) Ti
The compound of manganese with zero reducing power is:
A) 𝐾𝑀𝑛𝑂4 B) 𝑀𝑛𝑂2 C) 𝑀𝑛𝐶𝑙2 D) 𝑀𝑛2(𝑆𝑂4)3
Which of the following is an ionic oxide?
(a) Mn2O7 (b) ZnO (c) CO (d) H2O2

The transition element which does not show variable valences: (2020)
a. Cu b. Sc c. Zn d. Cr
Copper is a typical transition metal. Its atomic number is 29. In which oxidation state does it have
partially filled orbital in d-subshell? (2019)
2+
A) Cu C) Cu
–
B) Cu D) Cu+
Oxidation state of ‘Mn’ in KMnO4, K2MnO4, MnO2 and MnSO4 is in the order (2012)
A) +7, +6, +2, +4 C) +7, +6, +4, +2
B) +6, +7, +2, +4 D) +4, +6, +7, +2
Which one pair has the same oxidation state of ‘Fe’? (2013)
FeSO4 and FeCl3 C) FeCl2 and FeCl3
FeSO4 and FeCl2 D) Fe2 (SO4)3 and FeSO4

Identify the element that has maximum oxidation states: (Reconduct 2017)
A) Zinc C) Vanadium
B) Chromium D) Manganese
 Monodentate Ligands
Neutral -ive +ive

H2O = Aqua Cl- = Chloro H3O+ = Hydronium

NH3 = Ammine CH3COO- = Acetato N2H5+ = Hydrazonium
-
CO = Carbonyl CN = Cyano
-1
NO = Nitrosyl NO2 = Nitro
CS = Thiocarbonyl NO3-1 = Nitrato
-2
NS = Thionitrosyl S = Sulphido
C5H5N = Pyridine NH2-1 = amino
OH-1 = Hydroxo
-2
O2 = per oxo
O-2 = oxo
HS-1 = Mercapto
SCN- =Thiocynato
CO3-2 = Carbonato
C2O4-2 = Oxalato
SO4-2 = Sulphato
en
EDTA

[Co(NH3)3(NO2)3], [Co(NH3)4Cl2]Cl , Na3[Co(NO2)6], [Cr(NH3)6] (NO3)3 , K3[Fe(CN)6], [Co(en)2 Cl2], [Co

Cl CN NO2(NH3)3], [CrSO4(NH3)4]NO3, (NH4)3[Co (C2O4)3], [Pt (NH3)4(NO2)Cl] SO4
,[Co(NH3)3(H2O)2Cl]Cl2 , K3[Al(C2O4)3], [Pt(NH3)4(NO2)Cl]SO4, [Co(SCN)(NH3)5]Cl2,
K4[Ni(CN)2(C2O4)2], [Fe(H2O)5(SCN)]SO4

Catalytic properties
• Reason to act as catalyst
• Variable oxidation state
• Forming unstable intermediate compounds (interstitial compounds)
• Ability to donate electrons
• Ability to activate reactants
• Fe/Fe2O3 (Na2O, SiO2, Al2O3, K2O)  Haber Bosch process.
• V2O5 Contact process
• Pt Manufacture of HNO3 (Ostwald process)
• TiCl4 Polymerization of ethene/Plastic formation
• Ni, Pd & Pt Hydrogenation of unsaturated hydrocarbons.
• Cu Oxidation of ethanol
• ZnO/Cr2O3 Formation of ethanol
• MnO2 Decomposition of H2O2

In contact process the catalyst used for conversion of SO2 to SO3 is (2011)
Magnesium oxide C)Aluminium oxide
Silicon dioxide D) Vanadium pentaoxide
In contact process for manufacturing sulphuric acid, sulphur trioxide (SO3) is not absorbed because
(2012)
The reaction does not go to completion C) The reaction is quite slow
The reaction is highly exothermic D) SO3 is insoluble in water

Alloys
• Comparable size
• Substitutional alloys

Alloy Composition
Brass Cu = 60 – 80%
Zn = 20 – 40%
Bronze Cu = 75 – 90 %
Sn = 10 – 25 %
Steel Fe = 90 – 95 %
C = 0.1 – 2 %
Gold Au = 70 – 75 %
(18 carat) Cu = 20 – 25 %
Nichrome Ni = 60 %
Cr = 15%
Fe = 25%

Color of complex

• All light absorb  Black

• All light transmit  White
• Complementary colors
• Energy difference is diff form element to element
• V+3 , Fe+2, Ni+2 , Cr+3, ,  Green (Vo Fekar Ni Carta)
• Ti+4, Zn+2, Sc+3 , Cu+1  Colorless
• Cu+2, Cr+2  Blue (CroCudil is blue)
• Co+2 , Mn+2  Pink
• [Ti(H2O)6] +4
 Colorless
• [Ti(H2O)6] +3
 Absorb yellow emit blue and red color is violet
Which of the following pairs of ions is colorless?
(A) Ti+3, Cu+2 (B) Sc+3, Zn+2 (C) Co+2, Fe+3 (D) Ni+2, V+3
WOF ion exhibits color in aqueous solution
(A) Ti+4 (B) Zn+2 (C) Ni+2 (D) Sc+3
The hydrated cations of first transition series that imparts a blue color:
(a) Cr+2, CO+2, Cu+2 (b) Cu+2, Zn+2, Ti+4 (c) Ti+3, Zn+2, Cu+2 (d) Cr+3, Ti+4, Cu+2
Which of the following ions water is colorless?
a) Fe3+ b) Zn2+ c) Cu2+ d) Co2+
Violet color of [Ti(H 2O)6 ] ion is due to the
A) Central metal ion B) Water molecule C) Complex ion D) Outer anion