- CHAPTER 07
d and f-Block
Elements
[TOPIC 11 d-Blocl< Elements and
their Compounds
1.1 d-Block Element
c\
When dl1Tcrcn1ln1it1~ clcc1ron of an clement enters in d-subshcll, clemen t is said 10 bead-blo3 1
·
clemcn l. The d-block clements lying in the middle of the periodic table belong ing to groups11
in which the d-orbi1nls nre progressively filled in each of the four long periods are known
~.
transllion clemen ts because their properties nre inlcrmedinte betwee n those of s- and p-block
clemen ts.
For an clemcnl to be a Irnnsition clement, it ~hould have incomp letely filled d-orbital in its
ground state or in ils most common oxidation state.
Series of Transition Metals
(Y to CdI
There arc ~1ainly three se.ri~s ~)f the transition metals, i.e. Jct-series (Sc to Zn), 4 d-scries
and 5d-scn cs (La to Hg, om1ttmg Cc to Lu).
General Configuration . \. I
11
Genera l electronic configu ration of transition lllCl"'ls i•·s ( I) d 1.10 1. 2 S . 1.11,, ,--xc~p1io11.~'
, .. u • , 11 - ns . 01nc o1 -- "'
•
due to very littl, , . d'l't· ( 1) d nod m
observe d m ekcln.>m<.: conhgu rntioll, 10 . I C cnctgy l crencc betwee n JI - ·t:
, . . .• 5 al.
orb1lill :mch as C1 • 3d 4,\ , Cu. 3d 4s . Howeve r (Z ) d . . , ·y (HS) nt
· c n , en m1um (Cd), mc1cu
, 2111 1 l,1,1
. . lllcwls dll
represented by a gc:ncrnl formula (11 - l)tf10 ns2 Tl . , .
. Id -orb't1 a1s. · lCse me not regarde d as trnns1t1on
compIcte Iy 1··11
I c<
a
TER 7 : d-ond f·Blocl< Elements
c~AP 159
properties of d-Block Elements (viii) Most of the transiUon mctaJ s are
il Nearly, all the tr~nsition elements exhibit pa ramagnetic cJ uc to the presence of
l · !llctallic properties . They ( except Zn, Cd and unpaired electrons (as paramagnetic
Hg) arc very 1:1uch ~ard and have low character o:: number of unpafrccJ electrons) .
volatility. Their f!leltmg p.nd boiling points are The species having all paired electrons ar c
high due to strong metallic bonding. Greater diamagnetic in nature.
the number of valence electrons, stronger is (ix) The magnetic moment is determined by
the resultant bonding. They have high the formula, µ = ✓n(n + 2) BM where, n is
enthalpy of atomisation. the number of unpaired electrons and BM is
(Ii) From Sc to Cr, atomic radii decreases because Bohr Magneton (unit of magnetic moment).
effective nuclear charge increases. The atomic (x) Most of the transition metals and their
sizes of Fe, Co and Ni are almost same compounds are used as catalyst because
because pairing of electrons in d-orbitals they show variable oxidation states and
causes repulsion and hence, effective nuclear have ability to form complexes, e.g. finely
charge does not increase appreciably. divided iron in Haber's process, V20 5 in
(iii) Density of the transition metals from Sc to Cu contact process, etc.
increases due to high atomic mass and small (xi) Transition elements form coloured ions
atomic volume. due to the presence of unpaired electrons
(iv) Ionisation enthalpy increases with increase in in d-orbitals as they can undergo d-d
nuclear charge along each series. However, transition by absorbing colour from visible
the first ionisation energy of Cr is low region and radiating complementary colour.
because loss of one electron gives stable (xii) Transition elements forrri complexes due to
configuration and the value for Zn is higher smaller size, higher charge on cation s and
because it represents an ionisation from the presence of vacant d-orbitals, e.g.
completely filled 4s level. [Pe(CN) 6 ] 3- , [Cu(NH 3 ) 4 ]2+ etc.
(v) Transition metals show variable oxidation (xiii) Transition elements have lower value of
states due to the participation of (n - J) d as reduction potential and there is irregular
well as ns electrons in bond formation. The variation in reduction potential due to
maximum oxidation states are shown by Mn, irregul?r variation in ionisation energy,
i.e. from +2 to +7 (in first series) . Sc shows hydration energy, etc.
?nly + 3 oxidation state. High oxidation state (xiv)Transition elements form interstitial
is shown by their fluorides and oxides compounds which are non-stoichiomet ric
be~a~se fluorine and oxygen are strong (e.g. Mn 4N, TiH1.7 , TIC, etc) . They also
ox1d1sing agents. form alloy due to similar size.
11,1) Th
e electrode potentials of first row of Alloys are formed by the atoms with
tran · · elements generally show an
. s1t1on metallic radii differ for about 15 per cent
increase with increasing atomic numbers. from each other. Because of similar radii and
Electrode potential M 2+ iM of a metal is other characteristics of transition metals
dependent upon three parameters viz. alloys are readily formed by these metals. '
r:nth
. aIPY of atomisation,
. enthalpy of (xv) Transition m~ta_l o~ides in lowest oxidation
irmi<ati
_•
d
on an enthalpy of hydration. o f M2+ · state are basic, m mtermediate oxidation
1
-1 ) llJ l ' . state are amphoteric and in hi~hest
· is more stable than cu+ due to lower oxidation state a re .:!'~ · •li e,
rtduction
h potential which is due to higher
/it 4t1on energy. cu+ compounds
are
(xv/)Transltio~ metal halide~ 1n lower oxidation
state are 1onlc and In higher oxidation
d~&labLe ln aqueous solution and undergo !State ate covalt:nt. M01Hly fluorldeg are
'Ptoponloha Hon. ionic and chl'1rldes and tit o.n1ldti1 afe!
Jtu+--...+ cu 2+ + Cu covahmt.
0 c\iopterwlse CBSE
160 Solved Papers .
· CHE~\~
f
CHAI
1.2 Potassium Oich Structure of Chrom
Potassium dichrom
r omate Oichromate Ion
ate and
at e 2
compound in which (K 2C rp 7) is an acidic
Cr is presen\ in + 6 The st ru ct ur e o f
state. Potassium di oxidation ch ro m at e io n is te
chromatc is prepar di ch ro m at e io n co trah
sodium chromate, ed from ns is ts o f tw o tetrah l( M n(
which is obtained on e co rn er w it h C ~dral¼l
chromite ore (FeCr by fusion of r - 0 - C r bond an el :nedit
20 4 ) with sodium ca g eraofsh12~:
excess of air, which rb onate in 0 2- 6
on acidification w it Mn
sulphuric acid give h '
orange sodium dich
solution Na Cr O , romate \ Mn
2 2 7 this formed Na C Cr
reacts with KC\ to gi 2 r2O7 th en
ve potassium dich
(K C rp ). lt is or
2 7 ange coloured solid
romate o/\~o stru
.
4 FeCr: P + 8 Na
4 2CO3 + 7 0 2 - 4
0 Perr
Chromate ion
8 Na 2CrO4 + 2 F Them
(Wa1cr soluble)
ep 3 + 8CO2
(Waler insoluble)
(M nO ,
2 Na2CrO4 +2 H+ -
4 Na 2Cr2O1+
2 Na+ +H2O 1.3 Potassium
N a 2Crp7 + 21<.C
l - - ) K.2Cr2O1 +
(Less soluble)
2NaC\
(More soluble)
Permanganate
(i) lts co~our depe Po_ta_ssi um pe rm an
nd s u11on the p H of ga na te (K.MnO 4) 0 -::
s~l~tion. ln ?cidic the aci~ic ~ompound is also an
pH, it is orange in w hi ch M n is pr
dKhromate ions) w (exis
hile in basic pH it ts as oxidation state. P
ot as si um permanga
esent intl
yel_low _(e xists as chromate io . nate is
ns). The is prep~red by fu si on
ox1dat_1on state ol' ch of pyrolusite ore (M n
romium in chromat alkali m et al hydrox n0 1\111t (l
and d1chr-om ate is e ide in th e presence
same. dark purple colou of0 1.lli
2Cro ,t +2H + - - ) red crystalline solid
Cr2O~- +HJO 2MnO2 + 4K O H + . Rea c1
Cr20 72- + 2 0 - 0 2~ 2K 2Mn0 4 +2Hi0
H - - ) 2Cr02- + H- 3 M n o! - + 4H + ~ Import ,
( '" 0 2MnO4 + Mn0 2+2Hf
") lt is used _as 4
primary standard so 2 It is prepared by al In acid
volum lution . kaline oxidative fu
2- etnc analysis in MnO 2 followed by sio nof (i) 10
aci·ctlC
· mediu . m. m el ectrolytic oxidatio
n
... Cr2O1 +14H + + 6e- ~ 2C 3+ m an ga na te ion. o(
(111) lt acts as a r +7H 20 Mn0
ac idi\'ied K stCro r
ng oxid' .·
2
Fu se d wi th KOH,
ox idised with air
or~
(ii) s.
. \~sm
2 2O1 OX \( 1s g agent. Thus,
~ul\~llUr, Fe (l l) salt es sulphid
im.hne and nitrite . s to Fe . ~s to Mn04
l·
tO . (lll ), io ' l) \ (iii) sc
2 s nitr ates dides to Mangana11~
Crp 7- + 3H 2S+8H+ .
. 2- 3+ M n o 2- Elcc1roly1ic oxida
1ion in a
C rp -, + 1 41-1➔ +6Fe ~ 2 C r + 3 S + 7 H O
4 , \kal~
Mani:ana1e io n I (iv) 5S
2+ ~
2C r1 + 2
c . () .> -- Pern1JnsJol MnO~c11\
. 1., 7 +- 11\H +6Fe3 + + 7H 0 ln \ b I (v ) SS
" +G I . a oratory it ca n be
~ 2Cr3 + 2 manganese (l l) io pr ep ared by oxida\ · n l\
n sa lt by peroxodisu \O,
C 1· <) 2 lpnatt· '\
• l ·1 +O, I \ ' +3 (j + 7H O .i 'l l 2M 2 +
n + s S20~- + 8
~
"1
,1 J. ·- , 2 Cr~' 2 r .J 2 H 20 2Mno~- ·'
1- -i-1~~\
+ 10S0~ , ln 1, "' ut
I<M n o 4 t Iec
..
om \ ~~ -~
on l1Ci'\ t' po se s to oivcs K ,M 0 ;11\l
• m g an d evolve o -
n ~ I '
li) . . ~,
s o ,. .:: n
R . d-ond f-Block Elements
c~AprE 7 .
161 7
0 ~. 513 K ➔ K2MnO4+MnO 2 +O 2 (ii) 8MnO;j + 3Sp~- + HP--➔
2I(J\1Il 4 2- I
0- +e- ~ MnO4 8MnO 2 +6SO~- +2OH- I
4
. agen t m
Mn as an ox1·ct·1smg . a ll t h e t hr ee
\I I
(iii) 2MnO4 +3Mn2+ +2HP--➔ 5MnO 2 +4H+
l(MJJ04 a~ts acidic, alkaline and neutral.
·,,rT1S 1.e.
nedJLJ.J••
_ 4 »++ 3 e- --➔ MnO 2 + 2H 2O
MJl04 + 2
- +B H+ +5 e---➔ Mn + + 4Hp
1Af104 PREVIOUS YEARS'
structure of Manganate and EXAMINATION QUESTIONS
permanganate Ion TOPIC 1
anate (MnO /- ) and permanganate
Themang 0 1 Mark Questions
(Mn0 -) ions are tetrahedral.
4
1. Write the formula of an oxo-anion of
o- manganese (Mn) in which it shows the
1
oxidation state equal to its group number.
Delhi 2017
~ Mn
o~II "--o- 2
2. Zn2+ salts are white while Cu + salts are
coloured. Why? All India 2015
o
Tetrahedral Tetrahedral 3. Why do transition elements show variable
manganate ion permanganate ion
(Paramagnetic) (Diamagnetic) oxidation states? Delhi 2014C
4. Transition metals are much harder than
Reactions of KMn0 4 the alkali metals. Why? All India 2D14C
Important oxidising reactions of KMnO 4 are: 5. Which of following cations are coloured in
aqueous solutions and why?
In acidic solutions
(i) 101- +2 MnO 4 +16 H + --➔ SCa+' y a+' Ti4+, Mn2+
2Mn 2+ + 8 H 2O + 512 (At. no. Sc= 21, V = 23, Ti= 22, Mn= 25)
Deihl 2013
(ii) 5Fe2+ +MnO 4 +8H+--➔ 6. Sc(21), is a transition element but Ca(20)
Mn 2 + + 4H 20 + 5Fe3+ is not. Why? All India 2D12C
(iii) scp;- +2MnO 4 +16H+ --➔ 7. Explain the following observation:
2Mn2+ +8H 2O +l0CO2 Most of the transition metal ions exhibit
characteristic colours in aqueous
(iv) ssi- +2MnO 4 +16H+ --➔ solutions. Delhi 2012
2Mn2+ +8H 2O +5S a. How would you account for the following?
(v) sso~- +2Mno-4 +6H+--➔ Many of the transition elements are
2- known to form interstitial compounds.
2Mn2+ + 3H 2O + 5SO4
Delhi 2012
(Vi) 5No; + 2Mno:; + 6H+ --➔ 9. How would you account for the following?
2Mn2+ + 5NO 3 + 3H2O The E~ 2+ M for copper is positive
1
In neut al .
(0.34 V). Copper is the only metal in the
. r or faintly alkaline solutions
(i) 2M - first series of transition ele ments showing
no4+H 2o + 1- ~
this beh aviour. HOTS; All India 2012
2MnO 2 +2OH- +10 3
[TOPIC 21 f-Block Elements
(Lonthonoids and Actinoids)
s in which differentiating electron enters · whereas trivalent ions of other lanthanoids
Flcn1c Ill ·
.' I trbshcll are called /-block
Ul · S · •
elements. There are are paramagnetic.
·crr·••s which conslllutef-block.
[\\'OS '- • . •
These are 7. Lanthanoids are highly electropositive and
lanlllilnoids and actmo1ds. reactive metals .
8. They easily form alloys with other metals
2.1 Lanthanoids mainly iron. e.g. Mischmetal, an alloy of
lanthanoids metal ( ~95%) with iron
I. The 14 clements after lanthanum are called ( ~ 45%) and traces of S, C, Ca and AJ, used
Janthanoids in which 4 /-orbitals are to make lighter flints, bullets, shells etc.
progressively filled. General configuration of
lanthano1'ds 1s
. 4/1-1-15 do-16 s2. 2.2 Actinoids
2. Most common oxidation state of lanthanoid I. The 14 elements after actinium are called
is+ 3. However, Cc shows + 4, Eu and Yb actinoids in which 5/-orbitals are
show+ 2 oxidation state because they progressively filled. General configuration of
acquire stable configuration. HeI)cc, Ce4+ act . 'd s 1s
actmo1 . 5/1-146 dO ·l 7 s2.
as an oxidising agent, Eu 2 + , Yb 2 + act as 2. In general, actinoids show+ 3 oxidation
strong reducing agents. state. These resemble the lanthanoids in
3. There is steady decrease in the atomic and having more co~pounds in+ 3 s tate than in
ionic radii of lanthanoids with increase in the+ 4 state. However,+ 3 and+ 4 ions tend
atomic number due to lanthanoid to hydrolyse.
contraction. It is a unique feature in the 3. There is a greater range of oxidation states
chemistry of' the lanthanoids. It is due to in actinoids . It is due to the fact that 5f, 6 d
poor shielding effect of /-electrons. and 7s levels arc of comparable energies.
4. The radii of members of 5d-series are similar 4. The steady decrease in atomic and ionic size
to those of corresponding members of the along actinoid series is called actinoid
4d-series clue to lanthanoid contraction, e.g. contraction and it is due to poor shielding
Zr and Hf have almost same radii and due to effect of 5/ -electrons which results in
identical radii, they have similar physical increase in effective nuclear charge.
and chemical properties. Also the basic 5. They show less tendency to form complexes
character of decreases from La(OHh to but greater than lanthanolds.
Lu (OHh due to Janthanoid contraction.
6. They tarnish rapidly in air forming coating
5. Most of the Janthanoids are coloured and
of oxide and thus, are not attacked by
paramagnetic in nature due to the presence alkalies .
of unpaired electrons.
6· Lanthanuids show 7. They are strongly paramagnetic, have lo~
magnetic propcnies . ionisation energies.
3
La i , Lu 3+ arc diamagnetic in nature
