Chapter:‐8 The d‐and f‐Block Elements

POINTS TO BE REMEMBERED: ‐‐‐
1. The eíements of períodíc tabíe beíongíng to group 3 to 12 are known as d‐Bíock
eíements.
2. The generaí eíectroníc conñguratíon of these eíements ís (n ‐1)d
1‐10
ns
1‐2

3. d‐ Bíock eíements are coííectíveíy known as Transítíon Eíements because
propertíes of these eíements vary ín between s‐Bíock and p‐Bíock eíements.
4. A transítíon eíement shouíd have partíaííy ñííed (n‐1) d orbítaí.
5. Group 12 eíements í.e. Zn, Cd, Hg have compíeteíy ñííed (n‐1) d‐orbítaí ín
atomíc & íoníc state & thus these eíements are consídered as Typícaí Transítíon
Eíements.
6. Aíí these eíements are metaís. They are íess eíectroposítíve than s‐bíock
eíements & more eíectroposítíve than p‐bíock eíements.
7. The atomíc radíí decreases from group 3 to 6 (í.e. Sc to Cr) because of íncrease
ín ehectíve nucíear charge graduaííy.
8. The atomíc radíí of group 7,8 9 &10 eíements (í.e. Fe,Co,Ní) ís aímost same
because paíríng of eíectrons take píace ín (n‐1)d orbítaí causíng repuísíon í.e.
shíeídíng of (n‐1)d orbítaí.
. Group 11 &12 eíements í.e. Cu & Zn have bígger síze due to strong shíeídíng of
compíeteíy ñííed (n‐1)d orbítaí.
1!. The transítíon eíements show varíabíe oxídatíon state due to smaíí energy
díherence between (n‐1)d &ns orbítaí as a resuít both (n‐1)d &ns eíectrons take
part ín bond formatíon.
11. The híghest oxídatíon state of an eíement ís equaí to number of unpaíred
eíectrons present ín (n‐1)d &ns orbítaí.
12. Transítíon eíements have hígh enthaípy of atomízatíon/ subíímatíon Because
of íarge number of unpaíred eíectrons ín theír atoms, they have stronger
ínteratomíc ínteractíon and hence
13
.strong metaíííc bondíng ís present between atoms.
Most of transítíon eíements are paramagnetíc due to presence of unpaíred
eíectrons ín (n‐1)
d orbítaí.
14. Most of transítíon eíements are used as cataíyst. It ís due to (í) partíaííy ñííed
(n‐1) d orbítaí (íí) Varíabíe oxídatíon state (ííí) Abíííty to change oxídatíon state
frequentíy.
15. Most of transítíon eíements form coíoured compounds due to presence of
unpaíred eíectrons ín (n‐1) d orbítaí & thus they can undergo d‐d transítíon.
16. Most of transítíon eíements form compíex compounds due to (í) smaíí síze (íí)
hígh charge (ííí) presence of vacant d‐orbítaí of suítabíe energy.
17. Transítíon eíements have íower vaíue of Reductíon Potentíaí due to hígh
íonízatíon potentíaí, hígh heat of subíímatíon & íow enthaípy of hydratíon.
18. Transítíon eíements form ínterstítíaí compounds because síze of ínterstítíaí
voíds ís símííar to síze of non‐ metaís C, N, O, H.
19. Transítíon eíements form aííoys due to símííar íoníc radíí.
20. The oxídes of transítíon metaís ín íower oxídatíon state are BASIC,
íntermedíate oxídatíon state are AMPHOTERIC, híghest oxídatíon state are
ACIDIC.
"#$T%#$&'(): ‐‐‐
1. The 14 eíements after Lanthanum havíng atomíc number 58 to 71 are
coííectíveíy known as Lanthanoíds.
2. The generaí eíectroníc conñguratíon of these eíements ís |Xe| 4f
1‐14
, 5d
0‐1
,
6s
2
.
3. Most common oxídatíon state of these eíements ís +3, but Ce shows +4, Eu
+2, because they acquíre stabíe conñguratíon.
4. The síze of Lanthanoíds and íts trívaíent íon decreases from La to Lu due to
poor shíeídíng
of 4f eíectrons. It ís known as íanthanoíds contractíon.
#CT'$&'():
1. The 14 eíements after Actíníum havíng atomíc number 90 to 113 are
coííectíveíy known as Actínoíds.
1
2. The generaí eíectroníc conñguratíon of these eíements ís |Rn| 5f
1‐14
, 6d ,
7s
3. The síze of actínoíds and íts trívaíent íon decreases from Ac to Lw due to
poor shíeídíng of 5f eíectrons. It ís known as actínoíds contractíon.
4. The eíements after U (92) are man made known as transuraníc eíements.
*&T#))'+, ('C%-&,#TE:
*reparat.on: It takes píace ín three steps‐
(í) Conversíon of chromíte ore to sodíum chromate.
(íí) Conversíon of sodíum chromate to sodíum díchromate.
(ííí) Conversíon of sodíum díchromate to potassíum
díchromate Foííowíng reactíon take píace:‐‐
4 FeCr2O4+ 4 Na2CO3
+7O2
2 Na2CrO4+ 2Fe2O3
+8 CO2
2Na2CrO4 + 2
H
+
Na2Cr2O7 + 2 Na
+
+ H2O
Na2Cr2O7 + 2
KCí K2Cr2O7 + 2 NaCí
The chromates and díchromates are ínterconvertíbíe ín aqueous soíutíon
dependíng upon Ph of the soíutíon.
A) In Acedíc medíum(PH<7)
2CrO4
2‐
+ 2H
+
Cr2O7
2‐

+H2O
B) In basíc medíum (PH >7)
C)
2CrO7
2‐
+ 2OH

Cr2O4
2‐

+H2O
*&T#))'+, *E-,#$/$#TE:
*reparat.on: ‐‐
It takes píace ín two steps:‐
(í) Conversíon of pyroíusíte ore ínto potassíum magnate
(íí) Conversíon of potassíum magnate to potassíum
permaganate Foííowíng reactíons take píace:‐
2
MnO2
+ 4 KOH +
O2 2 K2MnO4 + 2H2O
3
MnO4
2‐
+4H
+
2 MnO4

+MnO2
+2H2O
0+E)T'&$ #$)1E-)
2T1& ,#-3
0+E)T'&$)4
O.1‐Expíaín bríeñy how +2 oxídatíon state becomes more and more stabíe ín the
ñrst haíf of the ñrst row transítíon eíements wíth íncreasíng atomíc number.
A.1‐In M
2+
íons, 3d‐orbítaís get occupíed graduaííy as the atomíc number
íncreases. Sínce, the number of empty d‐orbítaís decreases, the stabíííty of catíons
íncreases from Sc
2+
to Mn
2+
.Mn
2+
ís most stabíe as aíí d‐orbítaís are síngíy
occupíed.
2
O.2‐ Expíaín why transítíon eíements have many írreguíarítíes ín theír eíectroníc
conñguratíons? A.2‐In the transítíon eíements, there ís a ííttíe díherence ín the
energy of (n‐1) d‐orbítaís and ns‐ orbítaís. Thus, íncomíng eíectron can occupy
eíther of sheíí. Hence, transítíon eíements exhíbít many írreguíarítíes ín theír
eíectroníc conñguratíons.
O.3‐What are díherent oxídatíon states exhíbíted by Lanthanídes?
A.3‐The common stabíe oxídatíon state of íanthanídes ís +3.However some
members aíso show oxídatíon states of +2 & +4.
O.4‐How ís the varíabíííty ín oxídatíon states of transítíon metaís díherent from that
of the non‐ transítíon metaís? Iííustrate wíth exampíes.
A.4‐The transítíon eíements use íts (n‐1)d, ns and np orbítaí and the successíve
oxídatíon states díher by uníty. For exampíe, Mn shows aíí the oxídatíon states from
+2 to +7. On other hand non transítíon eíements use íts ns, np and nd orbítaís and
the successíve oxídatíon states díher by two uníts e.g. Sn
2+
, Sn
4+
etc.
O.5‐ Why do transítíon eíements show varíabíe oxídatíon states?
A.5‐ The transítíon eíements show varíabíe oxídatíon state due to smaíí energy
díherence between (n‐1) d &ns orbítaí as a resuít both (n‐1)d &ns eíectrons take
part ín bond formatíon.
O.6‐Why are Mn
2+
compounds more stabíe than Fe
2+
compounds towards oxídatíon
to +3 state? A.6‐The eíectroníc conñguratíon of Mn
2+
ís |Ar| 3d
5
, í.e. aíí ñve d‐
orbítaís are síngíy occupíed. Thus thís ís stabíe eíectroníc conñguratíon and further
íoss of eíectron requíres hígh energy .on other hand síde the eíectroníc
conñguratíon of Fe
2+
ís |Ar| 3d
6
, í.e. Loss of one eíectron requíres íow energy.
O.7‐To what extend do the eíectroníc conñguratíon decíde the stabíííty of oxídatíon
state ín the ñrst seríes of the transítíon eíements? Iííustrate your answer wíth an
exampíe.
A.7‐In a transítíon seríes, the oxídatíon state whích íead to exactíy haíf ñííed or
compíeteíy ñííed orbítaís are more stabíe.e.g. the eíectroníc conñguratíon of Fe ís
|Ar| 3d
6
,4s
2
. It shows varíous oxídatíon state but Fe(III) ís more stabíe than Fe(II).
O.8‐What ís meant by dísproportíonatíon? Gíve two exampíes.
A.8‐Those reactíons ín whích same substance undergoes oxídatíon as weíí as
reductíon are caííed
dísproportíonatíon
reactíons.e.g. ¬
Cu
2+
+ Cu 2Cu
+
¬
3 MnO4
2‐
+4
H
+
2 MnO4

+MnO2 + 2
H2O
O.9‐ Whích metaí ín the ñrst seríes of transítíon metaís exhíbíts +1 oxídatíon state
most frequentíy and why?
A.9‐ Copper wíth conñguratíon |Ar| 3d
10
4s
1
exhíbíts +1 oxídatíon state. Copper
íoses 4s
1
eíectron easííy and achíeved a stabíe conñguratíon 3d
10
by formíng Cu
+
.
O.10‐ What are ínner transítíon eíements?
A.10‐ The f‐bíock eíements ín whích the íast eíectron accommodated on (n‐2) f‐
subsheíí are caííed ínner transítíon eíements. These íncíude atomíc numbers 58 to
71 and from 90 to 103.
O.11‐ The paramagnetíc character ín 3d‐transítíon seríes eíements íncreases upto
Mn and then decreases. Expíaín why?
A.11‐ In the 3d‐transítíon seríes as we move from Sc (21) to Mn (25) the number of
unpaíred eíectrons íncreases and hence paramagnetíc character íncreases. After
Mn, the paíríng of eíectrons ín the d‐orbítaí starts and the number of unpaíred
eíectrons decreases and hence, paramagnetíc character decreases.
O.12‐ Comment on the statement that eíements of the ñrst transítíon seríes
possess many propertíes díherent from those of heavíer transítíon metaí
A.12‐The foííowíng poínts |ustífy that the gíven statement ís true:‐
(í) Ionízatíon enthaípíes of heavíer transítíon eíements are hígher than the
eíements of 3d seríes. Consequentíy, heavíer transítíon eíements are íess reactíve
íncomparíson to 3d‐eíements.
(íí) Meítíng poínts of heavíer transítíon eíements are hígher than 3d‐eíements.
(ííí) Hígher oxídatíon states of heavíer transítíon eíements are stabíe whereas íower
oxídatíon states are stabíe ín 3d‐eíements.
O.13‐What are transítíon eíements? Whích d‐bíock eíements are not regarded as
transítíon eíements and why?
3
A.13‐ An eíement whích has partíaííy ñííed (n‐1) d orbítaí ís known as transítíon
eíements. Group 12 eíements í.e. Zn, Cd, Hg have compíeteíy ñííed (n‐1) d‐orbítaí
ín atomíc & íoníc state & thus these eíements are not consídered as Transítíon
Eíements.
O.14‐What are ínterstítíaí compounds? Why are such compounds weíí known for
transítíon metaí?
A.14‐ Compounds of transítíon metaí wíth reíatíveíy smaííer non‐metaís are known
as ínterstítíaí compounds. These compounds are weíí known for transítíon metaís
because síze of C, N, O, and B ís símííar to síze of ínterstítíaí voíds of transítíon
metaí
O.15‐For the ñrst row of transítíon metaís the E
0
vaíues are:‐
E
0

vaíues V Cr Mn Fe Co Ní Cu
M
2+
/M

1.18 ‐0.91 ‐1.18 ‐0.44 ‐0.28 ‐0.25 +0.34
Expíaín
the
írreguíaríty ín
the
above
vaíues.
A.15‐The E
0
( M
2+
/M) vaíues are not reguíar whích can be expíaíned from the
írreguíar varíatíon of
2T%-EE ,#-3 0+E)T'&$)4
íonízatíon energy and subíímatíon energy of Mn due to haíf‐ñííed
orbítaís.
O.1‐ Decíde gívíng reason whích one of the foííowíng paírs exhíbíts the property
índícated:
(í)Sc
3+
or Cr
3+
exhíbíts
paramagnetísm
(íí)V or Mn exhíbíts more number of oxídatíon
states
(ííí)V
4+
or V
5+
exhíbíts coíour
A.1‐ (í) Sc=|Ar|
3d
1
4s
2
; Sc
3+
=|Ar| ; ít has no unpaíred eíectron so díamagnetíc
Cr=|Ar|
3d
5
4s
1
;
Cr
3+
=|Ar|3d
3
; ít has three unpaíred eíectrons
paramagnetíc
(íí) V=|Ar|
3d
3
4s
¬ 2
Mn=|Ar| 3d
5
4s
2
Thus
¬
V exhíbít oxídatíon states of +2, +3, +4, +5
Whereas Mn exhíbít oxídatíon states of
+2 to +7.
(ííí) V
4+
=|Ar|
3d
1
Coíoured V
5+
=|Ar| Coíouríess
O.2‐(a) Descríbe the generaí trends ín the foííowíng propertíes of the ñrst seríes of
the transítíon eíements:‐
(í) Stabíííty of +2‐oxídatíon state
(íí) Formatíon of oxometaí íons
(b) Wríte steps ínvoíved ín the preparatíon of KMnO4 from K2MnO4
A.2‐ (a) í‐The eíements of ñrst transítíon seríes show decreasíng tendency to form
dívaíent catíon as we move íeft to ríght ín the seríes. Thís trend ís due to generaí
íncrease ín the ñrst and second íonízatíon energy. The greater stabíííty of Mn
2+
ís
due to haíf ñííed d
5
conñguratíon and that of zínc ís due to d
10
conñguratíon.
(íí) Aíí metaí except Sc from oxíde of type MO whích are basíc. The híghest
oxídatíon number ín aíí oxíde, coíncíde wíth the group number and ís attaín ín Sc2O3
to Mn2O7. Formatíon of oxoaníons ís due to hígh eíectro negatívíty and smaíí síze of
oxygen atom.
2‐(b) It takes píace ín two steps:‐
(ííí) Conversíon of pyroíusíte ore ínto potassíum mangnate.
(ív) Conversíon of potassíum mangnate to potassíum
permanganate. Foííowíng reactíons take píace:‐
2
MnO2
+ 4 KOH +
O2 2 K2MnO4 + 2H2O
3
MnO4 2‐
+4H
+
2 MnO4

+MnO2
+2H2O
O.3‐(a) Wríte the steps ínvoíve ín the preparatíon of K2Cr2O7 from chromíte ore.
(b) What ís the ehect of pH on díchromate íon soíutíon?
A.3‐(a):‐ It takes píace ín three steps‐
(ív) Conversíon of chromíte ore to sodíum chromate.
(v)Conversíon of sodíum chromate to sodíum díchromate.
(ví) Conversíon of sodíum díchromate to potassíum
díchromate Foííowíng reactíons take píace:‐‐
4 FeCr2O4+ 4 Na2CO3
+7O2
2 Na2CrO4+ 2Fe2O3
+8 CO2
2Na2CrO4 + 2 H
+
Na2Cr2O7 + 2 Na
+
+ H2O
Na2Cr2O7 + 2
KCí K2Cr2O7 + 2 NaCí
4
(b) Díchromate íon ís orange ín acídíc soíutíon
(pH<7)
¬
and turns yeííow ín basíc soíutíon. It
ís due
to ínterconversíon of díchromate íon to chromate íon. Foííowíng reactíons take
píace:‐
2 Cr04
2‐
(yeííow) +2 H
+
¬
Cr2O7
2‐

(orange) + H2O
Cr2O7
2‐
(orange) +2
OH

2Cr04
2‐
(yeííow)
+ H2O.
O.4‐ (a) What ís íanthaníde contractíon? What ehect does ít have on the chemístry
of the eíements, whích foííow íanthanoíds?
(b) The chemístry of actínoíd eíements ís not so much smooth as that of
íanthanoíds. |ustífy these statements by gívíng some exampíes from the oxídatíon
state of these eíements.
A.4‐ (a)The síze of Lanthanoíds and íts trívaíent íon decreases from La to Lu. It ís
known as íanthanoíds contractíon.
Cause: ‐ It ís due to poor shíeídíng of 4f eíectrons.
Consequences of íanthaníde contractíon: ‐ (í) Basíc strength of hydroxíde decreases
from La(OH)3 TO Lu(OH)3. (íí) Because of símííar chemícaí propertíes íanthanídes
are dímcuít to separate.
(b) Lanthanoíds show íímíted number of oxídatíon states í.e. +2, +3, +4 (out of
whích +3 ís most common) . Thís ís because of a íarge energy gap between 4f, 5d
and 6s subsheíí. The domínant oxídatíon state of actínídes ís aíso +3 but they show
a number of other oxídatíon state aíso e.g. +4, +5, and +7. Thís ís due to smaíí
energy díherence between 5f, 6dand 7s orbítaís.
O.5‐ Gíve exampíes and suggest reasons for the foííowíng features of the transítíon
metaí chemístry:
(í) The íowest oxíde of transítíon metaí ís basíc, the híghest ís amphoteríc/acídíc.
(íí) A transítíon metaí exhíbíts híghest oxídatíon state ín oxídes and ñuorídes.
(ííí) Of the d
4
specíes, Cr
2+
ís strongíy reducíng whííe manganese(III)ís strongíy
oxídízíng. A.5‐(í) The oxíde of transítíon metaís ín íower oxídatíon states are
generaííy basíc whííe those ín the hígher oxídatíon states are acídíc. Acídíc
character íncreases wíth íncrease ín oxídatíon state ís due to decrease ín síze of
metaí íon and íncrease ín charge densíty.e.g. MnO (basíc), Mn3O4 (amphoteríc),
Mn2O7 (acídíc).
(íí) A transítíon metaí exhíbíts hígher oxídatíon states ín oxídes and ñuorídes
because oxygen and ñuoríne are the most eíectronegatíve eíements and thus
easííy can unpaír eíectrons of metaí atom.
(ííí) Because oxídízíng and reducíng property depends on E
0
vaíue. Sínce E
0
vaíue
of Cr
3+
/Cr
2+
ís negatíve whííe that of Mn
3+/
Mn
2+
ís posítíve, as a resuít Cr(II) act as
reducíng agent and Mn(III) ís
strong oxídízíng.
O.6‐For M
2+
/M and M
3+
/M
2+
systems ,the E
o
vaíues for some metaís are as
foííows:
Cr
2+
/Cr ‐0.9V Cr
3+
/Cr
2+
‐0.4V
Mn
2+
/Mn ‐1.2V Mn
3+
/Mn
2+
+
1.5V
Fe
2+
/Fe ‐0.4V Fe
3+
/Fe
2+
+0.8
V
Use thís data to comment upon :‐
(í)the stabíííty of Fe
3+
ín acíd soíutíon as compared to Cr
3+
or Mn
3+
and
(íí)the ease wíth whích íron can be oxídízed as compared to a símííar process for
eíther chromíum or manganese metaí.
A.6‐ (í)E
o
for Cr
3+
/Cr
2+
ís ‐0.4V í.e. negatíve, thís means Cr
3+
íons ín the soíutíon
cannot be reduced to Cr
2+
easííy í.e. Cr
3+
ís stabíe. As Mn
3+
/Mn
2+
ís +1.5V í.e
posítíve means Mn
3+
can easííy reduced to Mn
2+
íons ín comparíson to Fe
3+
íons.
Thus reíatíveíy stabíííty of these íons ís:‐
Mn
3+
< Fe
3+
< Cr
3+
(íí) The oxídatíon potentíaís for the gíven paírs wííí be +0.9V, +1.2V and 0.4V. Thus,
the order of theír gettíng oxídízed wííí be ín the order Mn>Cr>Fe.
O.7‐Account for the foííowíng statements:
(í)Cobaít (II) ís stabíe ín aqueous soíutíon but ín the presence of strong íígands and
aír, ít can be oxídízed to Co (III).
(íí)The d
1
conñguratíon ís very unstabíe ín íons.
(ííí)One among the íanthanídes, Ce (III) can be easííy oxídízed to Ce (IV).
A.7‐ (í) Strong íígands force cobaít (II) to íose one more eíectron from 3d‐subsheíí
and thereby índuced d
2
sp
3
hybrísatíon.
5
(íí) The íon wíth d
1
conñguratíon try to íose the oníy eíectron ín order to acquíre
ínert gas conñguratíon.
(ííí) The conñguratíon of Ce ís |Xe| 4f
1
, 5d
1
,6s
2
. There ís no much díherence
between the energy of 4f, 5d and 6s orbítaís and thus, Ce can utíííze eíectrons
present ín these orbítaís and hence oxídatíon state of +4.
O.8‐ Compare the chemístry of actínídes wíth that of the íanthanoíds wíth specíaí
reference to:
(í) eíectroníc conñguratíon (ííí) oxídatíon state
(íí) atomíc and íoníc sízes and (ív) chemícaí reactívíty
A.
8
Compar.son of "anthano.ds and #ct.n.des
*ropert.es "anthano.ds #ct.n.des
Eíectroníc |Xe| 4f
1‐14
, 5d
0‐1
,6s
2
|Rn| 5f
1‐14
, 6d
0‐1
,7s
2.
conñguratío
n
Atomíc/íoní
Síze decreases from La to
Lu,
Síze decreases from Ac to Lw,
and
c sízes
and síze ís more than
actínídes.
síze ís smaííer than íanthanoíds
due
to poorer shíeídíng of 5f
eíectrons
Oxídatíon
Common oxídatíon ís +3
where Common oxídatíon ís +3 where
states
other oxídatíon states are
+2,
other oxídatíon states are +2,
+4,+5
+4.It ís due to a íarge
energy gap
and+7 due to due to smaíí
energy
between 4f, 5d and 6s
subsheíí
díherence between 5f, 6d and
7s
orbítaís
Chemícaí The earííer member quíte The actínídes híghíy reactíve
reactívíty reactíve but wíth íncreasíng ,especíaííy ín ñneíy dívíded.
atomíc number they behave
ííke
aíumínum.
Compíex
Less tendency to form
compíex
More tendency to form compíex
due
formatíon due to íess charge densíty. to hígh charge densíty.
O.9‐(a) What ís actínídes contractíon? What ehect does ít have on the chemístry of
the eíements, whích foííow actínídes?
(b) Name an ímportant aííoy, whích contaíns some of the íanthaníde metaís.
Mentíon íts uses. A.9‐ (a) The síze of actínoíd and íts trívaíent íon decreases from
Ac to Lw. It ís known as í actínídes contractíon.
Cause: ‐ It ís due to poor shíeídíng of 5f eíectrons.
Consequences of actínídes contractíon: ‐ (í) Basíc strength of hydroxíde decreases
from Ac(OH)3 To Lw(OH)3. (íí) Because of símííar chemícaí propertíes í actínídes are
dímcuít to separate.
(b) An ímportant aííoy contaíníng íanthanoíd metaís ís míschmetaí, whích contaíns
95% íanthaníde metaí and 5% Fe aíong wíth traces of S, C, Ca and Aí. It ís used ín
Mg‐based aííoy to produce buííets, sheíís and ííghter ñínt.
O.10‐ Compíete foííowíng reactíons:‐
(í)
MnO
4
‐ + 2+ ¬
‐‐‐‐‐‐‐‐‐‐‐‐+‐‐‐‐‐‐‐‐‐‐‐‐‐‐+‐‐‐‐‐‐‐‐‐‐‐‐‐‐ + H + Fe ¬
(íí)
MnO4

+ C2O4
2‐
+
H
+
¬
‐‐‐‐‐‐‐‐‐‐‐‐+‐‐‐‐‐‐‐‐‐‐‐‐‐‐
+‐‐‐‐‐‐‐‐‐‐‐‐‐‐
(ííí) MnO4

+ O H


+ I

¬
‐‐‐‐‐‐‐‐‐‐‐‐+‐‐‐‐‐‐‐‐‐‐‐‐‐‐
+‐‐‐‐‐‐‐‐‐‐‐‐‐‐
4H2
O
A.10‐(í) MnO4

+ 8H
+
+ 5
Fe
2+
¬ Mn
2+
‐ + 5 Fe
3+
+
(íí)
2
MnO4

+ 5 C2O4
2‐
+ 16
H
+
¬ 2 Mn
2+
‐ +
10
CO2 + 8H2O
(ííí) 2
MnO4

+ H2O
+ I

2MnO2 + 2OH

+ IO3

25'6E ,#-3
0+E)T'&$)4
O.1‐Expíaín gívíng reasons:
(í) Transítíon metaís and many of theír compounds show paramagnetíc
behavíour.
6
(íí) The enthaípíes of atomísatíon of the transítíon metaís are hígh.
(ííí) The transítíon metaís generaííy form coíoured compounds.
(ív) Transítíon metaís and theír many compounds act as good cataíyst.
(v)Transítíon metaís have a strong tendency to form compíexes.
A.1‐ (í)Transítíon metaís and many of theír compounds show paramagnetíc
behavíour due to presence of unpaíred eíectrons ín (n‐1) d orbítaí.
(íí) The enthaípíes of atomísatíon of the transítíon metaís are hígh Because of íarge
number of unpaíred eíectrons ín theír atoms, they have stronger ínteratomíc
ínteractíon and hence strong metaíííc bondíng ís present between atoms.
(ííí) The transítíon metaís generaííy form coíoured compounds due to presence of
unpaíred eíectrons ín (n‐1) d orbítaí & thus they can undergo d‐d transítíon.
(ív)Transítíon metaís and theír many compounds act as good cataíyst It ís due to (í)
partíaííy ñííed (n‐1) d orbítaí (íí) Varíabíe oxídatíon state (ííí) Abíííty to change
oxídatíon state frequentíy.
(v)Transítíon metaís have a strong tendency to form compíexes Most of transítíon
eíements form compíex compounds due to (í) smaíí síze (íí) hígh charge (ííí)
presence of vacant d‐orbítaí of suítabíe energy.
O.2‐ Gíve reasons for the foííowíng:‐
(í) Fe has hígher meítíng poínt than Cu.
(íí) |Tí (H2O)6|
3+
ís coíoured whííe |Sc(H20)6| ís coíouríess.
(ííí)The 4d and 5d seríes of transítíon metaís have more frequent metaí‐
metaí bondíng ín theír compound than do the 3d metaís.
(ív)Transítíon metaís some tímeexhíbít very íow oxídatíonstate such
as +1and 0. (v)Hg ís not consídered a transítíon metaí.
A.2‐(í) Thís ís because Fe (3d
6
, 4s
1
) has four unpaíred eíectrons ín 3d‐subsheíí.
Whííe Cu (3d
10
, 4s
1
) oníy one unpaíred eíectron ín 4s sheíí. Hence metaíííc bondíng
ís stronger ín Fe than those ín Cu.
(íí) The oxídatíon state of Tí ín |Tí (H2O)6|
3+
ís +3 and íts conñguratíon ís |Ar| 3d
1
í.e
one unpaíred eíectron and hence ít ís coíoured. Whereas the oxídatíon state of Sc ín
|Sc (H2O)6|
3+
ís +3 and íts conñguratíon ís |Ar| 3d
0
í.e no unpaíred eíectron and
hence ít ís coíouríess.
(ííí)In the same group of d‐bíock eíements, the 4d and 5d transítíon eíements are
íarger síze than that of 3d eíements. Hence, the vaíence eíectrons are íess tíghtíy
heíd and form metaí‐metaí bond more frequentíy.
(ív)+1 oxídatíon state ís shown by eíements ííke Cu because after íoss of one
eíectron, ít acquíre stabíe conñguratíon. Zero oxídatíon state ís shown ín metaí
carbonyí, because [ ‐eíectrons donated by CO are accepted ínto the empty orbítaí.
(v)The characterístíc propertíes of transítíon metaí are due to partíaííy ñííed d‐
orbítaís.Hg has compíeteíy ñííed d‐orbítaí, as a resuít ít doesn´t show propertíes of
transítíon metaís and hence ís not consídered as transítíon metaí.
O.3‐(a) wríte eíectroníc conñguratíon of eíement havíng atomíc number 101.
(b)Whích eíement show maxímum oxídatíon state ín 3d transítíon seríes?
(c)What ís míschmetaí?
(d) Expíaín why Cu
+
íon ís not stabíe ín aqueous soíutíon?
(e)Name the transítíon metaí whích ís weíí known to exhíbít +4
oxídatíon state? A.3‐(a) |Rn| 5f
13
,6d
0
, 7s
2
.
(b) Mn, Whích shows +7 oxídatíon state ín KMnO4.
(c) It ís an ímportant aííoy, whích contaíns 95% íanthaníde metaí and 5% Fe
aíong wíth traces of S, C, Ca and Aí. It ís used ín Mg‐based aííoy to produce buííets,
sheíís and ííghter ñínt.
(d) Water ís a good compíexíng agent and thus Cu forms compíex by íosíng one
more eíectron from 3d orbítaí.
(e)Ceríum (Z=58)
O.4‐(a) Wríte the preparatíon of potassíum díchromate from íron chromíte. What
happens when potassíum díchromate reacts wíth (í) Hydrogensuíphíde (íí) FeSO4?
(b) Why do Zr and Hf exhíbít aímost símííar propertíes?
(c)Why ís La(OH)3 stronger base than Lu(OH)3.
7
A.4‐ (a) Preparatíon:‐ It takes píace ín three steps‐
(í) Conversíon of chromíte ore to sodíum chromate.
(íí) Conversíon of sodíum chromate to sodíum díchromate.
(ííí) Conversíon of sodíum díchromate to potassíum
díchromate Foííowíng reactíon takes píace:‐‐
4 FeCr2O4+ 4 Na2CO3
+7O2
2 Na2CrO4+ 2Fe2 O 3
+8 CO2
2Na2CrO4 + 2 H
+
Na2Cr2O7 + 2 Na
+
+ H2O
Na2Cr2O7 + 2
KCí K2Cr2O7 + 2 NaCí
Reactíons: ‐ (í) Cr2O7
2‐
+ 8 H
+
+ 3 H2S ¬ 2Cr
3+
+ 7
H20 + 3S (íí) Cr2O7
2‐
+ 14 H
+
+ 6 Fe
2+
¬
2Cr
3+
+ 7 H20 + 6 Fe
3+
.
(b) Because both have símííar íoníc síze
(c)Due to íanthanoíd contractíon síze of La
3+
ís smaííer than Lu
3+
as a resuít Lu‐O
bond wííí stronger than La‐O bond.
O.5‐ Gíve reasons for the foííowíng:‐
(í) Transítíon metaís have hígh enthaípy of hydratíon.
(íí) Zn, Cd and Hg are not regarded as transítíon metaí.
(ííí) d bíock eíements exhíbít a íarge number of oxídatíon state than f bíock
eíements.
(ív)The second and thírd members ín each group of transítíon eíement have
símííar atomíc radíí.
(v) K2 |PtCí6| ís weíí known compound whereas the correspondíng Ní compound
ís not known. A.5‐(í) Transítíon metaí íons are smaííer and have hígher charge,
therefore have hígh enthaípy of hydratíon.
(íí) Group 12 eíements í.e. Zn, Cd, Hg have compíeteíy ñííed (n‐1) d‐orbítaí ín
atomíc & íoníc state
&thus these eíements are not consídered as transítíon eíements.
(ííí)The díherence ín the energy of (n‐1) d orbítaí and ns orbítaí ís very smaíí and
thus both sub‐ sheíís are used for bond formatíon. Whereas ín f bíock eíements (n‐
2)f orbítaís ííe underneath and hence are not avaííabíe for bond formatíon.
(ív) The second and thírd members ín each group of transítíon eíement have símííar
atomíc radíí due to íanthanoíd contractíon. It aríses due to poor shíeídíng of d and f
eíectron.
(v)The oxídatíon state of Pt ín ís +4 whích ís stabíe for Pt. The +4 oxídatíon state
for Ní ís very dímcuít to achíeve because the sum of ñrst four íonízatíon energíes
ís very hígh. Hence ,the correspondíng Ní(II) compound ís known.
8