D and F Block Part-1
D and F Block Part-1
D - BLOCK ELEMENTS OR TRANSITION ELEMENTS An element which has incompletely filled d-orbital in
its atom or at least one of its ions.
POSITION IN PERIODIC TABLE: Placed in 4 horizontal rows b/w s and p block elements, and are
classified into four series.( Gp 3 to Gp 12)
First transition series (3d series): From Sc(21) to Zn(30) Have incomplete penultimate 3d orbitals
Second transition series(4d series): From Yttrium(39) to Cd (48) Have incomplete penultimate d-orbital
Third transition series(5d series): From La(57) and hafnium(72) to Hg(80) Have incomplete
penultimate 5d orbital
Fourth transition series (6d series): Incomplete penultimate 6d orbital
Ques 2: On what ground can you say that scandium (Z = 21) is a transition element but zinc (Z = 30)
is not?
Solution: Scandium atom in its ground state (3d1) has incompletely filled 3d orbitals, so, it is regarded as a
transition element. On the other hand, zinc atom has completely filled d orbitals (3d10) in its ground state
as well as in its oxidised state, hence it is not regarded as a transition element.
Ques 3: Silver atom has completely filled d orbitals (4d10) in its ground state. How can you say that it
is a transition element?
Solution: For an element to be termed as a transition element, it should have partially filled d orbitals in its
atom or in commonly found oxidation states. Silver can exhibit +2 oxidation state (3d9) in which it has
partially filled d-orbitals. Due to this reason, we can say that silver is a transition element.
Ques 4: Name the transition elements which do not have partially filled d- orbitals in their atoms or in
commonly found oxidation states.
Solution: The last member of each of the transition series i.e. Zinc (Zn), Cadmium (Cd) and Mercury
(Hg) are the transition elements which do not have partially filled d- orbitals in their atom as well as
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simple ions (having oxidation state of +2). Therefore, these elements do not possess characteristic
properties of transition elements and hence, generally not regarded as transition elements.
Solution:
(i) Cr3+ : 1s2 2s2 2p6 3s2 3p6 3d3 Note – Remove electrons from 4s first and then from 3d.
(ii) Ni2+: 1s2 2s2 2p6 3s2 3p6 3d8
(iii) Mn2+: 1s2 2s2 2p6 3s2 3p6 3d5
(iv) Fe3+:1s2 2s2 2p6 3s2 3p6 3d5
(v) Cu+: 1s2 2s2 2p6 3s2 3p6 3d10
(vi) Zn2+ : 1s2 2s2 2p6 3s2 3p6 3d10
1.Typically metallic- high tensile strength, ductility, malleability, high thermal and electrical conductivity and
metallic lustre.
2.All have typical metallic structures at normal temp except Zn, Hg, Cd and Mn
3. Hard and low volatility ( except Zn, Hg and Cd).
4. High densities.
5.Electropositive nature.
6.Form coloured compounds
7.Variable Oxidation States and paramagnetic behaviour.
8.Tendency to form complexes and used as catalysts.
PHYSICAL PROPERTIES
1) ATOMIC RADII and IONIC RADII:
Intermediate as that of s and p block elements (in a period smaller than s block but larger than p block
members)
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• Normally the size of 5d series > 4d series > 3d series but the size of 5d series is comparable to 4d series
because of the intervention of the 4f electrons before the 5d electrons which will cause very less shielding
and increases nuclear attraction and hence reduces the size of 5d series. This filling of 4f before 5d orbital
results in a regular decrease in atomic radii called Lanthanoid contraction which essentially
compensates for the expected increase in atomic size with increasing atomic number.
• Trend-In a transition series the atomic radii decrease initially and then varies irregularly becoming almost
constant.
• In First transition series the atomic radii decrease from Sc to Cr and then is almost constant up to copper
but the last element Zn has larger radii than copper.
• Reason: With increase in atomic no. the e- are added in the penultimate d-orbital that increases the nuclear
charge and thereby decreases the atomic radii. But the increased no. of e- in penultimate shell increases the
shielding effect (inner e- shield outer e- from nuclear attraction) due to which outer e- tend to be away from
nucleus i.e. e- cloud expands resulting in the increase in atomic radii. Thus with increase in nuclear charge,
the nuclear attraction as well as the shielding effect increases. But as the shielding effect counterbalances
the increased attraction there is small decrease in atomic radii.
• Zn has larger atomic radii than Cu-Due to greater screening effect in Zn (3d104s2) than Cu(3d104s1)
2) IONISATION ENTHALPY:
• Higher than s-block elements but lower than p-block elements.
• I.E of elements of 3d series increase irregularly with increase in atomic no.
Reason:
1) With increase in atomic number the nuclear charge increases, but due to greater shielding effect
caused by inner d e- & little variation in their atomic sizes result in marginal & irregular increase
in first I.E of transition elements.
2) The removal of one electron alters the relative energies of 4s and 3d orbitals. There is thus, a
reorganisation energy accompanying ionisation with the transference of s electrons into d orbitals and from
some gains in exchange energy as the number of d- electrons increases.
3) Elements have high IE because of half and full filled d-orbitals.
Irst I.E of Zn(fully filled 4s) > Cu (half filled 4s) and IInd I.E of Cr> Mn (half filled)
IE1 < IE2 < IE3 for the same element . Magnitude of IE2 and IE3 is much higher.
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Example 1: The first ionisation enthalpy value of zinc shows a higher increase while the second
ionisation enthalpy value drops off in the otherwise increasing regular trend in 3d series.
Explain.
Solution: Zinc has fully filled configuration; (Ar) 3d10 4s2. The first ionisation enthalpy represents the
removal of 4s electron while second ionisation enthalpy consists of the removal of an electron which allows
the production of the stable d 10 configuration. So the second ionisation enthalpy value drop off.
Example 2: Why the second and third ionization enthalpies of manganese and iron show anomalous dip
in the values across the period?
Solution: Manganese and iron attain stable half filled configuration (3d5) in +2 and +3 oxidation states
respectively. So they show anomalous dip in the values across the period.
3) METALLIC CHARACTER: They are metals and show all properties of metals.
Reasons :
• They have low I.E, due to which they lose e- to form cations and therefore show all metallic properties.
• They have incompletely filled d-orbital, so sideways overlapping result in the formation of strong
interatomic metallic bond that increase the strength of metallic bonding in them. Greater the number of
unpaired e- greater is the extent of metallic bonding due to d-d overlapping.
• Cr, Mo, W have high M.P and B.P and are hard whereas Zn. Cd, Hg are soft metals volatile with low
M.P and B.P
• Cr, Mo, W have max. no. of unpaired e- and so strong intermetallic bonding whereas Zn, Cd, Hg have
fully filled d-orbital and so weak intermetallic bonding.
• High M.P & B.P- They have incompletely filled d-orbital, so sideways overlapping result in the
formation of strong interatomic metallic bond that increase the strength of metallic bonding in them.
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• Mn and Tc show a dip in the curve unexpectedly due to Half filled extra stability of Mn and Tc
due to which they do not interact with Surrounding atoms & so metallic bond is weak & M.P is Low.
Electrons are too tightly held and do not delocalize.
• Zn, Cd, Hg are soft and volatile metals. They have low m.p as they do not have unpaired electron for
metallic bonding.
• Cr(3d54s1) is hard and Hg(5d106s1) is liquid at room temperature( melts at -38oC )
6) FORMATION OF COMPLEXES :
Transition metals forms the large number of complexes because -
(i) Smalller sizes of metal ions.
(ii) High ionic charges
(iii) Availability of d-orbitals for bond formation.
Examples are: [FeF6]3-, [Fe (CN)6]3-, [Cu (NH3)4]2+, [PtCl4]2-, [Fe(CN)6]3- etc. In [FeF6]3 Fe3+- central metal ion
and F-- ligand that surround octahedrally around metal ion.
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8) MAGNETIC PROPERTIES:
) ) a) Diamagnetic- repelled by magnetic field- no unpaired e-
b) Paramagnetic- attracted by magnetic field- unpaired e-.
* Greater the no of unpaired e-, greater is the paramagnetic behaviour
Magnetic moment (µ) = √ n(n+2) ,( n= number of unpaired electrons ) (spin only formula)
Example 1: Calculate the magnetic moment of a divalent ion in aqueous solution if its atomic
number is 25.
Solution: With atomic number 25(3d54s2), the divalent ion in aqueous solution will have d5 configuration
(five unpaired electrons). The magnetic moment, μ is μ=√5(5+2) =5.92 BM
Example 2: Calculate the ‘spin only’ magnetic moment of M2+(aq) ion (Z = 27).
Solution: The electronic configuration of the M2+ ion (Z = 27) would be 3d74s2.Unpaired electrons i.e. it has
three unpaired electrons n = 3, therefore its spin only magnetic moment is μ= √3(3+2)=3.87BM (BM =
Bohr Magneton)
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 utilise 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).
For example, iron(III) catalyses the reaction between iodide and persulphate ions.
2I- + S2O82- Fe3+ I2 + 2SO42-
An explanation to this catalytic activity can be given as :
2Fe3+ + 2I- 2Fe2+ + I2
2+
2Fe + S2O8 2- 2Fe3+ + 2SO42-
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10) ALLOY FORMATION :
Alloys are homogeneous solid solutions in which the atoms of one metal are distributed randomly
among the atoms of the other. These are formed because of their similar radii and having property of
metallic bonds.
➢ The best known are ferrous alloys: chromium, vanadium, tungsten, molybdenum and manganese are
used for the production of a variety of steels and stainless steel.
➢ brass (copper-zinc) and bronze (copper- tin)
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+2 +2 +2 +2 +2 +2 +2 +1 +2
+3 +3 +3 +3 +3 +3 +3 +3 +2
+4 +4 +4 +4 +4 +4 +4
+5 +5 +5
+6 +6 +6
+7
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• Out of d4 species, Cr(II) is strongly reducing but Mn(III) strongly oxidizing
Reason: As Cr(II)[3d44s0] loses an e- easily to form stable 3d3(t2g) configuration but Mn(III)
accepts e- to have 3d5 configuration.
Cr+2 Cr+3 + e- Mn+3 + e- Mn+2
4 3 4
3d 3d 3d 3d5
(stable t2g)
• All Cu halides are known except the iodide- because Cu+2 oxidises I- to I2 Cuperous ion- Cu+ cupric-
Cu2+
2Cu+2 + 4I- Cu2I2 (cuprous iodide) + I2 (Disproportionation Reaction)
• Cu(I) compounds are unstable in aq soln –because Cu in +2 O.S are more stable than +1 O.S due to
the large –ve hydration enthalpy of Cu+2 than Cu+1which is much more compensates for larger energy
required to remove second electron.
• High O.S occurs in oxides because of ability of O to stabilize the O.S due to its small size ,high
electronegativity and ability to form multiple bonds.
Oxocations (VO2+, TiO2+) are stable
Example2: Name a transition element which does not exhibit variable oxidation states.
Solution: Scandium (Z = 21) does not exhibit variable oxidation states.
Example 3: Which transition metal of the 3d series exhibits the largest number of oxidation states and
why?
Solution: Manganese (Z=25) exhibits the largest number of oxidation states because it has maximum
number of electrons ns and (n-1)d electrons available for the bond formation. It exhibits all oxidation
states from +2 to +7.
Example 4: How would you account for the increasing oxidising power in the series
VO2+ <Cr2O72– < MnO4 – ?
Solution: This is due to the increasing stability of the lower species; V5+ <Cr6+ <Mn7+ to which they are
reduced. V5+ to v4+ , Cr+6 to Cr+3 , Mn7+ to Mn2+
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TRENDS IN M2+/M STANDARDS
* Smaller the value of ∆totalH in aqueous soln, greater will be the stability of O.S because E0 value are a
measure of ∆totalH and Lower the reduction potential value, greater is the stability of O.S
* Cu has +ve E0 value- least reactive –it cannot liberate H2 from acid- because high energy is required to
convert Cu to Cu+2 is not balanced by its ∆hydH.
The unique behaviour of Cu, having a positive Eo, accounts for its inability to liberate H2 from acids.
Only oxidising acids (nitric and hot concentrated sulphuric) react with Cu, the acids being reduced. The high
energy to transform Cu(s) to Cu2+ (aq) { Δa H(M) +ΔiH1 +ΔiH2} is not balanced by its hydration
enthalpy{ΔhydHO (M2+)}. Hence The stability of Cu2+ (aq) rather than Cu+ (aq) is due to the much more
negative ΔhydH° of Cu2+ (aq) than Cu+, which more than compensates for the second ionisation enthalpy of
Cu.
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* Varying trends are observed-Except Cu and Zn all show +3 O.S. [M3+ + e- M2+]
Ti V Cr Mn Fe Co
Eo -0.37 -0.26 -0.41 +1.57 0.77 +1.92
M3+/M2+
• Sc has a low Eo value because Sc+3 has stable noble gas configuration.( 4s0 3d0)
• Zn has highest value as it is difficult to remove e- from 3d10.
• Mn has high value –Mn+2(3d5) is stable…. So Mn+3 is unstable.
• Fe has low value indicating extra stability of Fe+3(3d5) than Fe +2(3d6)
• V has a low value due to stability of V+2. (half-filled t2g level)- 4s0 3d3 ** E0 for Mn3+/Mn2+ is more +ve
than Cr+3/Cr+2 or Fe+3/Fe+2? Much large I.E3 (3d5-3d4) +3 state has little relevance.
Example 1: Why is Cr2+ reducing and Mn3+ oxidising when both have d4 configuration?
Solution Cr2++ is reducing as its configuration changes from d4 to d3, the latter having a half filled t2g level
(details will be discussed in chapter of coordination chemistry). On the other hand, the change from Mn3+ to
Mn2+ results in the half-filled (d5) configuration which has extra stability.
Example 2: The EO (M2+/M) value for copper is positive (+0.34V). What is possible reason for this?
Solution: The EO (M2+/M) value for copper is positive (+0.34V) because the sum of first and second ionisation
enthalpies for copper is very large due to exceptionally high second ionisation enthalpy which is not
compensated by the hydration enthalpy (ΔhydH0) of Cu2+ ion.
Example 3: Cu+ has fully filled d10 configuration, but +2 is the common oxidation state for Cu(aq.).
Explain.
Solution: The hydration energy of Cu2+ is more negative than Cu+ and more than compensates the
second ionization enthalpy of copper. So though Cu+ has fully filled d10 configuration, copper exists as
Cu2+in aqueous solution.
Shows Ni(II) is stable than Pt(II), but Pt(IV) is more stable than Ni(IV)
• Lower the reduction electrode potential value, greater the stability of O.S
Cu 2+ + 2e- Cu (E0red = +0.34V)
Cu + + e- Cu (E0red = +0.52V)
So Cu2+ is more stable than Cu+
• Less reactive due to their high I.E, high heats of sublimation & low heats of hydration. Ex: They may
remain inactive also as most of them form a protective inert & sticky oxide layer with conc. Acid & are not
further attacked by it
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• Weak reducing agents- Due to their moderate electrode potential values
• Out of Cr2+ and Cr+3, Cr3+ is more stable in aqueous solutions
Reason -As it has smaller size & high charge density so is hydrated to a greater extent
Assignment
Q1 Which gives coloured aq soln – Co2+, Sc+3, Cr+3 ? how will they respond to magnetic
field.?
Q2 Out Of Ag+, Co+2,Ti4+, which forms coloured solution?
Q3 Which will show greater O.S- Zr, Ti, V, Ni, Mn?
Q4 K2PtCl6 is known but Ni compounds are not known?
Q5 Eo values for Co+2 & Co+3are -0.28V and 1.8V –Which will be a better reducing agent
in water?
Q6 How would you account for inc. Oxidising power of – VO2+<Cr2O72-
<MnO4-
Q7 Based on data arrange Fe+2, Mn+2, & Cr+2 in inc order of stability of +2 O.S
Q8 Cr+2 is reducing but Mn3+ oxidising although both have d4 configuration. Why?
[ Hint - Cr+2(3d4) → Cr+3(3d3-stable half-filled t2g configuration)
& Mn3+(3d4) + e- → Mn2+ (3d5- stable half-filled configuration)]
Q9 Why isCu2+ is more stable than Cu+?
[Hint- ∆hydH is more -ve which more than compensates for I.E2 of Cu2+]
Q10 Consider the E0 values in 1M acidic solutions Fe2+/Fe = -0.4V, Fe3+/Fe2+ = 0.8V,
Mn2+/Mn = -1.2V, Mn3+/Mn2+ = +1.5V
a) Comment on the relative stability of +2 & +3 O.S of Fe & Mn
b) Which of them may be more easily oxidized to +2 Oxidation states.
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