D & F block elements:

 Defined as elements where the differentiating electron

enters the (n-1)d subshell.
 There are 10 groups (3 to 12).
GVEC of d-block: (n-1)d1-10 ns0-2
 There are 4 series:
4th Period (1st transition series) 3d series (Sc to Zn) GVEC of transition (n-1)d1-10 ns0-2

Bcz , Pd : [Kr]5s0 4d10.

Sc Ti V Cr Mn Fe Co Ni Cu Zn

5th Period (2nd transition series) 4d series (Yt to Cd)

Transition elements:
 Elements that have at least one
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd unpaired electron in their ground
state (or) any of its oxidation
6th Period (3rd transition series) 5d series (La and Hf to Hg) states.
 These elements typically belong
La Hf Ta W Re Os Ir Pt Au Hg to groups 3 to 11.
 (12th group) Zn , Cd , Hg are
non transition elements.
7th Period (4th transition series) 6d series (Ac and Rf to Cn)
Ac Rf Db Sg Bh Hs Mt Ds Rg Cn
Elements with “notable” electronic configurations:
Cr Cu
Nb Mo Tc Ru Rh Pd Ag  La (Z=57) is : [Xe] 5d1 6s2 . It
La Pt Au deviates from the Aufbau
principle (5d orbital in preference
Ac Rg
of 4f orbital which is of lower
energy.)
Serie Eleme
Serie Eleme Outermost E.C.  Similarly: Actinoids
Outermost E.C. s nt
s nt  There are greater similarities in
Pd 4d10 5s0 the properties of the transition
Cr 3d5 4s1 4d elements of a horizontal row in
3d Ag 4d10 5s1
Cu 3d10 4s1 contrast to the non-transition
5d1 6s2 (but all elements.
Nb 4d4 5s1 La  However, some group
5d having 4f14)
Mo 4d5 5s1 5d similarities also exist.
Pt 5d9 6s1  in 1937, technetium (Tc)is the
4d Tc 4d6 5s1 first artificial element hence its
Au 5d10 6s1
Ru 4d7 5s1 name (from technetium =
6d Rg 6d10 7s1 'artificial‘)
Rh 4d8 5s1
6d1 7s2
Ac (but all 6d
having 4f14)
Among the following series of transition metal
ions, the one where all metal ions have 3d2
electronic configuration is
Sc (Z = 21) is a transition element but Zn (Z = 30) is not because

A Ti3+, V2+, Cr3+, Mn4+

both Sc3+ and Zn2+ ions are colourless and form white
A
compounds
B Ti+, V4+, Cr6+, Mn7+

B in case of Sc, 3d orbitals are partially filled but in Zn

Ti4+, V3+, Cr2+, Mn3+ these are filled

C
last electron is assumed to be added to 4s level in case of
C
Ti2+, V3+, Cr4+, Mn5+ Zn
D
both Sc and Zn do not exhibit variable oxidation states
D
With the exceptions of Zn, Cd, Hg and Mn, they have one or more typical metallic
structures at normal temperatures.
 NOTE
 Among all ‘W’ has highest
M’pt( high △aH )

 “Hg” M’pt = -380C (liq at RT)

w  Zn, Cd, Hg. lowest M’pt in
their series (due to “d10 “ not
available for metallic bond ).
Re
 In graph, there is a dip in
Rh
Mo the M’pt of Mn and Tc.

 Due to “Mn” has satble

Ru (3d5 half & 4s2 fully filled) &
it has typical str like Zinc
Tc
Cr  ∴ 3d e- tightly held by the
atomic nucleus. ∴ weaker
metallic bonding than in the
Fe previous element

Mn
 129pm
Cu
Atomic radius
Sc > Ti > V > Cr > Ti > Mn > Fe > Co > Ni > Cu Zn

Zn = Mn
137pm

M+2 Ionic radius V

V > Cr > Ti > Mn > Fe > Co > Ni > Cu Zn

Zn
Cu
NOTE
M, M+2 , M+3 radius always Ni is smaller one.
Remember

 The atomic radii for  The atomic radii of the second and
transition metals are smaller third transition series metals are
than their corresponding s- nearly same due to lanthanoid
block elements. contraction.
 3d < 4d =5d < 6d atomic radius.
 Atomic radius
Sc > Yt > La > Ac
 IE Ionisation Enthalpy
(kJ mol– Sc Ti V Cr Mn Fe Co Ni Cu Zn
)

IE1 631 656 650 653 717 762 758 736 745 906

IE2 1235 1309 1414 1592 1509 1561 1644 1752 1958 1734

IE3 2398 2657 2833 2990 3260 2962 3243 3402 3556 3837

 along each series from left to right due to an increase in Zeff. (exceptions marked in yellow)
 The variation in IE along a series of transition elements is much less in comparison to the
non-transition elements
 Successive IE do not increase as steeply as in the case of non-transition elements.
 The magnitude of the increase in the IE2 and IE3 for the successive elements, is much
higher along a series than IE1.

IE: Sc < V<Cr <Ti < Mn <Ni < Cu <Co < Fe < Zn. (Mnicucofez)

IE2: Sc <Ti < V < Cr < Mn < Fe <Co <Ni < Cu < Zn

IE3: Sc <Ti< V < Cr < Mn < Fe <Co <Ni < Cu < Zn

Density increases in the series Zn is lower than Cr
 Enthalpy of atomisation: △aH:
Q) Why do the transition elements exhibit higher enthalpies of
atomisation?
Because of large number of unpaired electrons in atoms, they
have stronger interatomic interaction and hence stronger bonding
between atoms resulting in higher enthalpies of atomization.
Inspection of Fig. 4 .
 4d & 5d series have greater △aH than 3d series. (larger is the
“d” more effect overlap)
 This is an important factor indicating more frequent metal-metal
bonding in the compounds of heavier transition elements (third
series).
.
 Both vanadium and chromium exhibit metallic bonding, but
vanadium has a more effective overlap of d-orbitals in
its metallic bonds. This results in stronger metallic bonds
in vanadium compared to chromium
 highest in 3d series is Vanadium.

V > Ti > Mn >Zn

1st & 2nd highest 1st & 2nd lowest
 They show variable O’states (groups 4 through 10). due to comparable energies of
“ns (n-1) d “ valency orbitals.
Sc Ti V Cr Mn Fe Co Ni Cu Zn

+1
+2 +2 +2 +2 +2 +2 +2 +2 +2 NOTE
+3 +3 +3 +3 +3 +3 +3 +3  The common
+4 +4 +4 +4 +4 +4 +4 oxidation state are
+5 +5 +5
in red.
+6 +6 +6
+7  Sc3+, Zn2+ and Cd2+
have fixed O.S.
 Middle of the series elements show’s greatest number of oxidation states.
 Os & Ru = +8 O’st
 Ti+4 is more stable than Ti(III) or Ti(II). (in d-block)
 The Max O’st. due to sum of the “s” and “d” electrons upto “Mn” (Ti IV O2 ,
VVO2+ , Cr VI O4- ,Mn VII O4- ) followed by a rather abrupt decrease in stability  Mn =+7 (in 3d )
maximum
of higher oxidation states. that the typical species to follow are FeII, III, CoII,
III,, Ni II, ,, CuI, II, ZnII.
 For d-block elements their oxidation states differ from each other by unity, in contrast with
non transition elements where oxidation states normally differ by a unit of two.
 From group 4 to 10, the higher oxidation states are favoured by the heavier members, which
is opposite to p-block elements (where heavier members tend to occur in lower oxidation states
due to inert pair effect).
Cr+6 Thus, Cr6+ in form of Cr2O72– is a
 Example: In group 6,
Stability strong oxidizing agent whereas
Mo6+
↑’s MoO3 and WO3 are not.
W 6+

 Low oxidation states are found when a complex compound has ligands capable of π-acceptor
character in addition to the σ-bonding.
 For example, in Ni(CO)4 and Fe(CO)5, the oxidation state of nickel and iron is zero.
 Standard Reduction Potentials
 All 3d series elements have negative M2+/M electrode potential except
for Cu.
 Electrode potential value depends upon thermodynamic parameters
 △Htotal (lower the value higher is the stable O’st).

E° (Mn2+|Mn) , E° (Ni2+|Ni) E° (Zn2+|Zn), SRP = –Ve than expected.

Lower the SRP , greater
(d5 orbital, more -Ve (ΔhydH) d10 orbital ) the stability of O’state

NOTE

 Mn+3 , Co+3 are good oxidising agents.

 Positive value for Cu - inability to liberate H2 from acids E°
(Cu2+|Cu) = +Ve is not balanced by its hydration enthalpy.
 IMP NOTE: Although Cr³+ and Co2+ ions have same number of
unpaired electrons but the magnetic moment of Cr³+ is 3.87 B.M.
M3+/M2+ . and that of Co2+ is 4.87 B.M. Why?
 low valve for Sc due to stable E.C 1. Cr3+ ion The electronic configuration in a crystal field is
symmetrical (𝒕𝟑𝟐𝒈 ). Due to this, there is no orbital contribution
 high value for Zn3+/Zn2+ (fully filled)
to the magnetic moment for Cr³+. The magnetic moment
 Comparatively high valve Mn3+/Mn2+ . (half
primarily arises from the spin contribution.
filled )
 Comparatively Low valve Fe3+/Fe2+ . (half filled 2. Co2+ ion : The electronic configuration in a crystal field (𝒕𝟓𝟐𝒈 𝒆𝟐𝒈 )
) is not symmetrical. This asymmetry leads to an appreciable
 The comparatively low value for V is related to orbital contribution to the magnetic moment for Co2+ , in addition
the stability of V2+ (half-filled t2g level, Unit 9). to the spin contribution.
 Trends in stability of higher oxidation state :
 High O’st TiX4 (tetra halides), VF5 and CrF6. MnF7 not exist but MnO3F is known, and
beyond Mn no metal has a tri halide except FeX3 and CoF3.
 Ability F2 to stabilize high O’st. due to
CoF3, (High L.E) , VF5 and CrF5 higher B.E.
 Although VV is represented only by VF5, the other halides, however, undergo hydrolysis to
give oxo halides, VOX3.
 Another feature of fluorides is their instability in the low oxidation states e.g., VX2 (X = CI, Br
or I).
 the same applies to CuX. On the other hand, all Cu(II) halides are known except the iodide.
 In this case, Cu+2 oxidizes I- to I2
 2 Cu+2 + 4I- ⟶ Cu2I2 + I2

 However, many copper (I) compounds are

unstable in aqueous solution and undergo
disproportionation.
 2Cu+ ⟶ Cu+2 + Cu
 The stability of Cu+2(aq) rather than Cu+ (aq)
is due to the much more negative △hydH:
 Cu2+(aq) than Cu+, which more than
compensates for the second ionization
enthalpy of Cu.
oxygen stabilize higher oxidation states
 The ability of oxygen to stabilize these high oxidation states exceeds that of fluorine.
 Thus the highest Mn fluoride is MnF4 whereas oxide is Mn2 O7 .
 The ability of oxygen to form multiple bonds to metals explains its superiority.
 The highest oxidation number in the oxides coincides with the group number and is attained
in Sc2 O3 to Mn2 O7.
 Beyond Group 7, no higher oxides of Fe above Fe2 O3, are known, although ferrates
 (VI)(FeO4) 2-, are formed in alkaline media but they readily decompose to Fe2 O3, and O2.
Besides the oxides, oxo cations stabilise VV as 𝑉𝑂2+ , VIV as 𝑉𝑂2+ and TiIV as Ti𝑂2+

Remember EX.1 MnO . Mn2O3 . MnO2 . MnO3, Mn2O7 . .

+2 +3 +4 +6 +7
(i) The oxides in lower oxidation states
Basic Amphoteric Aicidc
are basic in nature.
(ii) The oxides in intermediate
oxidation states are Amphoteric.
EX.2. CrO . Cr2O3 . CrO2 . CrO3,
(iii) The oxides of higher oxidation
states are acidic in nature. +2 +3 +4 +6
(iV) Acidic nature & EN 𝜶 O’St of metal Basic Amphoteric Aicidc
Properties 2. Colour Prop’s. 4. Catalyst.
 Due to unpaired ele.  Ability to form multiple oxidation state.
 d0 & d10(Colour less)  they can change oxidation states

5.Interstitial compounds.
1. Magnetic Prop’s. 3. Formation of co-  small atoms like H, C or N are 6. Alloys formations.
 due to Unpaired ele. ordination compound. trapped inside the crystal lattices of  Homogeneous solid
 small size of cation. metals. solutions.
 𝜇= 𝑛(𝑛 + 2ሻ𝐵𝑀  High ionic charge.  They are usually non stoichiometric  Formed by metallic
 Presence of d- and are neither typically ionic nor radii that are within
orbitals covalent. about 15 percent of
 TiC, Mn4 N, Fe3 H, VH0.56 each other.
Characteristics Interstitial compounds.
 They have high melting points, higher than those of pure metals.
 They are very hard, some borides approach diamond in hardness.
 They retain metallic conductivity.
 They are chemically inert.
 Colour of transition elements due to

D-d transitions. Polarisation

Presence of at
least NaCl, NaBr, NaI ionic and colourless, AgCl also expected to be
one singe electron colurless. but due to polarizability AgCl , AgBr , AgI white ,
in d- Orbital. pale yellow , yellow (Iodide gets more distortion) more
polarizability more intense colour Ag2CO3 Ag3PO4( yellow) Ag2O
Potassium , Ag2 S (black).Charge transfer more intense colour than d-d
manganate.
MnO4-2(d1) Charge transfer

 KMnO4 (purple),K2 Cr2 O7(Orange), LMCT. MMCT.

MLCT.
CrO42-(yellow ) due to LMCT , Potassium permanganate [Fe4[Fe(CN)6 ]3
Presence of CO, CN- ,
which is having do configuration potassium dichromate Prussiun blue
Py , bipy , Phen , NO,
 K2MnO4 (Manganate , green ) , THESE LIGANDS.
due to d-d transition which is [Fe(CO)3 (bipy) ]
having d1 configuration [Fe4[Fe(CN)6 ]3
•Reactivity:
•All most all dissolve in mineral acids, but noble metals are
unaffected by simple acids.
•except copper, are generally reactive and oxidized by 1M
H+,
• but some times rate with oxidizing agents can be slow
(e.g., Ti and V are passive in dilute non-oxidizing acids).

•The inspection of E° values shows a decreasing tendency to

form divalent ions along the series, primarily due to an
increase in the sum of the first and second ionization
enthalpies (IE1 + IE2)

•Oxidizing and Reducing Agents:

•Mn³+ and Co³+ ions are strong oxidizing agents in aqueous
solutions due to their high positive E values for the M3+/M2+
couple.
•V2+ and Cr2+ ions are strong reducing agents and readily
liberate H₂ from dilute acids, as exemplified by the reaction:
2 Cr2+ aq) +2H+ (aq) → 2 Cr3+ aq) + H2 (g).
 Some Important Compounds of
Oxides and Oxo anions of Metals
Transition Elements

 All the metals except scandium form “MO” oxides which are ionic.
 The highest oxidation number in the oxides, coincides with the group number and is attained in Sc 2 O3 to
Mn2 O7. Beyond group 7, no higher oxides of iron above Fe2O3 are known.
 Besides the oxides, the oxo cations stabilize VV as 𝑉𝑂2+ , VIV as VO2+ and TiIV as TIO2+.
 Oxidation number increases, ionic character decreases. In the case of Mn, Mn2 O7, is a covalent green oil.
Even CrO3 and 𝑉2 𝑂5 have low melting points. In these higher oxides, the acidic character is predominant.
 Thus, Mn2 O7, gives HMnO4 and CrO3 gives H2 CrO4 and H2 Cr2 O7

In acid
Basic less basic amphoteric 𝑉𝑂4+
𝑉2 𝑂3 → 𝑉2 𝑂4 → 𝑉2 𝑂5
Dissolution In acid In Base
𝑉𝑂43−
𝑉𝑂2+
Potassium dichromate, K₂Cr2 O7
It is prepared from “chromite ore FeO. Cr₂O₃ (FeCr₂O4)”
1.4FeCr2O4 +16NaOH + 702 → 8Na2 CrO4 + 2Fe2 O3 + 8H2 O. NOTE

2.. 2Na2 CrO4 + H2 SO4 → 2Na2 Cr2 O7 + Na2 SO4 + H2 O  The chromates and dichromate's are
(yellow)Sodium chromate (Orange)Sodium inter convertible in aqueous
solution depending upon pH of the
dichromate
solution.
On cooling, sodium sulphate (less soluble )crystallizes out as  The oxidation state of chromium in
Na₂SO₄.10H2O and is removed. The resulting solution contains chromate and dichromate is the
sodium dichromate. same.
 E’wt = M’wt /6
3. Sodium dichromate is more soluble than potassium dichromate.
Therefore, potassium dichromate is prepared by mixing a hot
𝑷𝑯=𝟒
concentrated solution of sodium dichromate and potassium chloride 𝑪𝒓𝑶𝟐−
𝟒 𝑪𝒓𝟐 𝑶𝟐−
𝟕 (CAD)
in equimolar proportions: Yellow Orange
2Na2 Cr2 O7 + 2KCl ⟶ 2K2 Cr2 O7 + 2NaCl
Sodium dichromate Potassium dichromate
 𝑪𝒓𝑶𝟐− + 𝟐−
𝟒 + + 2H ⟶ 𝑪𝒓𝟐 𝑶𝟕 + H2O
Sodium chloride, being the least soluble, precipitates out from the  𝑪𝒓𝟐 𝑶𝟐− − 𝟐−
𝟕 +2OH ⟶2𝑪𝒓𝑶𝟒 + H2O
hot solution and is removed by filtration. Orange crystals of
potassium dichromate separate out from mother liquor on cooling.
Structure & reactions NOTE
 When ammonium dichromate, (NH4 )2 Cr2
O7, is heated slightly, it undergoes a
decomposition reaction.
 This reaction produces a green solid,
chromium(III) oxide (Cr 2O3), nitrogen gas
(N₂), and water (H₂O). Its releases large
amount of heat (seems like volcano’s)

 Na2 Cr2 O7 is deliquescent enough and

changes its concentration and can not be
taken as primary standard solution whereas
K2 Cr2 O7 has no water of crystallization and
not deliquescent
properties

KCl+ CrCl3 + Cl2 +H2O

4K2CrO4+ 2Cr2O3+ 3O2 Action

of HCl

4H+ + H2O2
K2Cr2O7
H2O + CrO5
Blue colour

Gradually
decompose to
Action 2Cr2 (SO4)3 + 8H2O + 3O2
(Cold ) H2SO4 ⸫ acts as a oxidising agent
Cr+3 + O2
CrO3 + 2KHSO4 + H2O
Red crystalls anhydride form
CAD (At P =4 both equilibrium)
H
KMnO4(Potassium Permanganate ): (Preparartion )

Pyrolusite (MnO2) is fused with caustic potash (KOH) or

(K2CO3 ) in the presence of air (or) an oxidizing agent (like
potassium nitrate or potassium chlorate).

𝐻𝑒𝑎𝑡
2MnO2 + 4KOH + O2 2K2MnO4 + 2H2O
green potassium manganate
2MnO2 +2K₂CO₃+0₂ → 2K2 MnO4 +2CO2
MnO2 + 2KOH + KNO3 → K2 MnO2 + KNO3 + H2O
•Oxidation of K2MnO4to 2KMnO4:
•This solution is then oxidized to 2KMnO4 by treating it
with chlorine, ozone, or carbon dioxide.
• dark purple crystals of 2KMnO4 separate out.

2K2MnO4 + Cl2 ⟶ 2KCl + 2H2O + 2KMnO4

2K2MnO4 + 2H2O + O3 ⟶ 2KOH + O2 + 2KMnO4

3K2MnO4 + 2CO2 ⟶ 2K2CO3 + 2MnO2 + 2KMnO4
Purple colour
 e- 𝑴𝒏𝑶𝟐− 0
𝟒 , E =0.56

4H+ +3e- 𝑴𝒏𝑶2, E0 = 1.69V

𝑴𝒏𝑶−
𝟒

8H+ +5e-
𝑴𝒏2+ , E0 =1.52V

 In these rxn’s we observe that [H+]

influencing the reaction.
 The reduction potential values can explain
the occurrence of many reactions, but the
kinetics of the reaction is also an important
factor because the kinetics of the reaction is
affected by H+ ion concentration.
 At [H+] = 1 M, permanganate ion should
oxidise water (E" for H₂O = ON -1.23 V) but
in practice the reaction is extremely slow
unless either Mn2+ ions are present or the
temperature is increased.
 properties
Remember
KMnO4, titrations performed only in
K2MnO4+ H2O + 3O2
the presence of dil. H₂SO₄.
∴ oxygen produced from the reaction of
K2MnO4+ MnO2+ 3O2 Action
KMnO4, with dil. H₂SO₄ is used only for
of KOH
oxidising the reducing agent. KMnO4,
does not produce any oxygen of its own
to act as an oxidising agent. However, it
Action
H2O + KHSO4 +Mn2O7 of (Cold)H2SO4
KMnO4 may be noted that (HCl) or (HNO3)
cannot be used in place of dil. H₂SO₄. In
case HCl is used, the oxygen produced
On Heating
by the reaction of KMnO4, and dil. HCl
will be partially used up to oxidise HCl
to chlorine. In case HNO3, is used, itself
O2 + MnO2
acts as oxidising agent and will partly
K2SO4+ 2MnSO4+ 3H2O +5[O] oxidize the reducing agent. Hence
KMnO4, titrations are carried out only in
the presence of dil. H₂SO4
 f- Block . (inner transition elements )
28 elements

(n-2)f 0 - 14 (n-1)d 0 – 1ns2

Lanthanide Actinide.
 4f- series. Belongs to 6th period  5f- series. Belongs to 7th period
 It consist 14 elements.  It consist 14 elements.
 Only Pm is radio active .  All of them are radio active.
 Common O’state =+3  Common O’state =+3
4f 1 - 14 5d 0 – 1 6s2 5f 0 - 14 6d 0 – 1 7s2

 Lanthanum resembles closely with other lanthanides and

therefore, it is usually included in discussion of
lanthanides.
 Similarly, actinium is included in the discussion of actinides
besides other fourteen elements.
Actinoids
 The actinoids are radioactive elements and the earlier elements have long half-lives, the latter ones
values ranging from a day to 3 minutes for lawrencium (Z =103).
 like those in the lanthanoids are related to the stabilities of the f 0 , f 7 and f 14 occupancies of the 5f
orbitals.
 There is a gradual decrease in the size of atoms or M+3 ions across the series. This may be referred to
as the actinoid contraction (like lanthanoid contraction). The contraction is, however, greater from
element to element in this series resulting from poor shielding by 5f electrons.
 There is a greater range of oxidation states, which is in part attributed to the fact that the 5f, 6d and 7s
levels are of comparable energies
 The actinoids show in general +3 oxidation state. 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
 The actinoids resemble the lanthanoids in having more compounds in +3 state than in the +4 state.
However, +3 and +4 ions tend to hydrolyze.