d-BLOCK ELEMENTS AND THEIR COMPOUNDS

Gntroduction
3 4 5 6 7 8 9 10 11 12
4th Sl Sl
Period Sc Ni
T V Cr Ann Fe Co Ge 2h
3dseries 21 Zz 23 24 25 26 27 28 29 30
5th SI SI SI SI SI SO SI
Period Nb Mo Ta Ru Rh Pd Cd
y
4dseries 3G
2 Ag 48
o Ai 412 43 44 45 416 47
6th fodl Sl Sl
Period La Hf2 Ta3 W Re Os Ir Pt Au
Sd series 577 7 7 74 75 76 77 78 797
Hg
803
7th
period Ac Rf Db Sg 13h Hs Mt Ds Roy Club
Gd Series 89 1047405 107 108 109 H2
406 Ilo Ili

In the elements of d block last electron

enters into n Dd subshell
I 2 l lo
General configuration ns n Dd
iPad 755 xd

Transition Elements

a A transition element is defined as the one

which has incompletely Cn 1 d subshell
filled its
in its ground state in
or
any
one
of
oxidation state
They are called transition elements because
their position in periodic table is in between
reactive S block metals and less reactive p block
metals Their properties are transitional between
S and p block metals

S block configuration n 1 do or n Dd
p block
Transition
metals
configurating 1 d to Cn 1 d

Gr 12 elements 2n Cd
Hg of d block
are not considered as transition elements why
SOI 2h o 2h42
d
Idg ateY en Dd
gy
They have fully filled 1d sub shell in ground
state as well as in their ale known ox States

QQ Cu Au have completely filled D

Ag
d subshell still are included in
they How
transition elements
Ai Ag Au Ground state n 1 do
cut2 d9
Agt3 da's
Aut
General Properties
i Atomic radius

General trend across the period

A First size decreases upto near middle

Reason ghc in 2effective
dominating
B Then size remains almost constant
Reason gnc in nuclear charge is counterbalanced

by inc in e e repulsions

c size increases in last

Reason e e repulsion dominates

General trend in a
group

3d series
Reason in shells
vine inc no of
4d series
eggett almost Reason if poor shielding inc Zeff
Same
5d series Lanthanoid contraction
2 Ionisation Au Ae Ag
Energy so y La learn

Gene itrend across the period t.ee

IE inc from left to right due to Inc Zeff

In 91.2 cacening
Lacy so
General trend in a group
except Gr 3
3d series
Sd series
Icd series
more
Zeff
In 3d Series gn block
d ZeffHish
stablefnfig
Maximum IE Zn Maximum IE Hg
Least IEi so Maximum in each
IE
Maximum IE Cu agt og Period is from Gr 12
Maximum IEz zn Entdg Least IE 1 La
maximum IE Sc setting largest size
Ni Cu Zn rarely exhibit ox State more than
2 in their compounds r d'sp dia
put Inner
Reason very high IES Ni fo
QI
Zn no compound
Ni Cu sase few examples

0
3
Density

0
General trend acrossperiod
the
Density increases from left to right but decreases
in end or near end

Trend down the group as

3d series
4d series Vino
V
Sd Series
Maximum in 3d series cu CooNi
density
Maximum density in d block Ir os

Min density in d block se

4 Typical metallic properties
Nearby all d block metals display typical
metallic properties
Tensile Strength High
Ductility
Malleability
Thermal conductivity
Electrical conductivity
Metallic dust use u

Hardness High
volatility Low

All d block metals except zn.ee HI MI

have typical one or more metallic lattice
structures
BcfCfpHcpPfp
at normal temperatures
5 Melting point
The high melting point of d block metals
are attributed to the involvement of
greater number of electrons from Cn 1 d orbitals
in addition to the ns electrons in
the interatomic metallic bonding
a factors affecting melting point
i No of unpaired electrons
ii 2 effective
iii size
iv Packing

General Trend in a period

middle
First increases
nearly upto d electrons
Reason inc no
of unpaired
dec size

Then decreases from middle to end

Reason dec no of unpaired d electrons

G trend within a
group
Sd series Icd series 3d series
metal metal metal
Reason Zeff down the
Gnc group

in d block W
Max
melting point
in d block Hg
Min
melting point in 3d series
Max
melting point vegs
mainst
be Y La
Cd
En leg

1915 goo
QQ Melting points of Group iz metals
are lowest in respective series
why 2
ANI no e
from d involves in interatomic
metallic bonding weaker atom atom
interaction Low m lots

The order metallic bond strength t

down the of de
group generally among
3d 3d Cad Ud Dd Dd
opposite toor Inert pairelements
effect f block
because Tin down the
of Zeff group
enception is 3rd group 12thgroup
Sc Y La
En ed
reg
W Tungsten maze nap
min nap
Hg Mercury
AM atomisations 3d series Kasem V
min In
in d block nanltransition
generally
9 1
se
I in atm w
Copp Logy
torn p same as in
2n Cd
rap
ng
leg
6 Enthalpy of atomisation Datt

Curve similar to melting point curve

Here Da Ho A sublimation H

Transition elements exhibit high Datt

due to involvement of more no of electrons
in metallic bonding stronger atomic interactions
 General trend across the period
Sati increases upto near middle and then
decreases

The maxima is at about the middle

of each series indicates that one unpaired
electron per d orbital is particularly
favourable for stronger atom atom interaction

General trend down the group

3d series 4d series 5d series

Greater Date if ed and Sd series metals

than corresponding 3d series metals is
responsible for much more occurrence of
metal metal bonding in the compounds
of
heavy transition metals
chemical
Reactivity
bath affects
ERed EX

why zinc has lowest sate in 3d series

ANS No e from 3d is involved in metallic
bonding weaker interatomic interaction
 7 oxidation States
ooo d block elements exhibit more number of
oxidation States due to involvement of
more no of e s in bondformation ns Ch Dd
3 4 5 6 7 8 9 10 11 12
Sc Ti V Cr Ann Fe Co Ni Cu Zn
I
2 t2 t2 t2 2 f 22 It22 It22 t2
t33 3 1 3 f 33 13 It 33 t 33 FaZe
tf tf tf tf tf tf 4
erased
rare
55 5 5
6 6 6
f 7 Tiny Feq2

Most common OX circledonesare Boled ones are the

in generalthe most common ox
State in 3d series 12 most stable ox States for respective
Statesfor respective elements
elements

variable oxidation series elements

among 3d
is not shown by Sc Zn

T2 oxidation State
among 3d series elements
is not shown by Sc

Cr a co
oxidation
Except highest
state shown by a 3d series element ht2
n total no of unpaired electrons
Maximum number of oxidation States in 3d
series is shown by Mn

Lesser number of oxidation States occur in

Extreme left extreme sight
due to less no of electrons due to less availability
are present Less no of of e s fr bond format
on due to
unpaired e s pairings

The elements which exhibit more no of

oxidation States occur in the middle
portion of series f they have more unpaired Es

Negative or zero oxidation States are also

shown by d block elements in their
compounds but only when there is synergic
bonding backbonding M
Oni
IT
ez coke Fe Cohn

Highest oxidation state in d block is

shown by Os Ru which is equal to 8

Os04
8
Stability of oxidation States

HT
M S Mntag

bait
dhydH

BiH DEHz DiHn point

Mfg g

M S tag Mnfaq t ne

DHT Da H t it t
Dhyd H
E E I
Less positive safe less positive site and
Mose
Dhyd.tl supports for greater
te
stability
of metal in th oxidation state

CAI d't configuration is

generally very
unstable in ions i
ez set ion is not known o
explanation Resonance ga
The energy used in ionisation of all electrons
is compensated re DhydH or more
by more
more ve BeatriceH
After removal of d e'T noble gas configuration
is obtained
131 do d d configurations generally provide
more
stability
e
Tilt stableTist 2h24 stablezn3t
nan2tstable Mn3t
d d d5 dt dw dg
noblegas exactly fully
config half filled filled
C stable icon of Cr in ag solution cyst
are in
as in d all é tag more.SE
D Stable ox States of Co Ni in complexes Cots Nits

E In aqueous solution
stability of
x
cut ae2t
dio stable Dg
Reason IEa of Cu is compensated by
faiqige.ae IE of Cat
Ahyd.tl of cut
2
more ve
cut undergoes disproportionation in aq solution
2aytaq cud t cuff v mT

F From group 4 to group 10 higher ox

States of ad and Sd series elements are
more stable than higher ox States of their
corresponding 3d series elements Reason qdisd
opposite of inert pair effect morgeese
more D
i Ano VI W VI Ztable CHI
medium
CHI is oxidiser in form of Crzof in acidic
1 03 in WO42 non oxidiser
G ox State
 7
ii ranof oxidiser
7 strong
non oxidiser
Regi

G Lower oxidation estates are

generally reducing
Tik feat v2t Crat
ex and they form
bonds with heavier halides not with 02 or F
Br I

CHI Higher oxidation States are

generally
to 7
crit rant cost feast and
ex
oxidising
with 02 or f not
they form compounds
with Br I As BE I are strong R A so
will reduce metal ion to lower
state
known x not known
5 5 er 2

V'Fgf V205C VBzf VII CoFz

VBky X VIS X VII Cours COBB Cots
rug is less stable it readily hydrolyses in
moist air as Clg 1 H2O vous 1 ZHU
f1
Gex u Iif X
X A CUFa v
Br I

Getz and Feig are not known

cut2 fet3 oxidiser I strong Zeducer
262 4 I 2cm If to Iz
2
Fest I Fe Iz t Iz
 The fluorine to stabilise
III ability of the
higher oxidation estates is due to
E release high LE in ionic compound formation
ex CoEg

il release high bond enthalpy in covalent

compound formation ex Es EEE
205 Ertz toting
The oxygen to stabilise the
ability of
highest oxidation States is more than that of
due to its 2T bond forming capacity
fluorine
ex
14
Highest manganese fluoride Mnfa
Highest Manganese oxide ran of

7
In simple halides of Mn Mnet is not
known due to steric crowding
O O
Il k
o Mon O
MIB MIE
lol b
k Fe
In 3d Series
Beyond Mn
only
and co form trihalides
ez Feltz COB
X I
6
L Ferrate ion Feaf is known in alkaline medium
but readily decomposes
Nazfe04 Fez031 02 t Na O
 9 Trends in Ennis1M
BHO
M S an cagey

Date

v
Mlg BhydH

o o
Aith t Dina M2t g

DOH DaHot Ai Hit AiHao t DhydH

It 7
more re shoo
more ve DOH supports

more t ve Fox
1
more ve
Eked

The trend towards less

general negative
values from left to across the
right
f period is related to general increase in sum
BiH t Dilla from left to right
 O
O

0 Too
É at at 0.15311 Ect Cu 0.52W
 Eoaetlae is positive due to
i High Datt
Ii Low bhyd.lt than it DiH2

oooo
Unique behaviour of copper accounts for
its to liberate Ha
inability E
gas
from acids
f.at Hatfnt2
a Ae reacts with those acids which
only
are
oxidising in nature like H Nos conc Has04
E
Cut HNOz Cut2 t NOz t

E values for Mn Ni and 2n are more

negative than expected from the trend

i Mn2t d5 resists reduction
2nA dio staffergation
ii Ni2t highest re Ihydte resists seduction

In 3d series most ve DhydH Mat Ni Cu

ooo d block elements of 3d seriot
cu react with acids to liberate tea
but in reaction
gas node
StHops after they start due to formation
of insoluble protective film
Fe Cle Rusto 2h20
IO Trends in Epnt3 path o

cutout HCl no reach

a Aging
pants Cot3 oxidisers
Tspp tve
a
cut dit stronger no reach
42509
mineralFet3 mild oxidiser
acid cus09 5029 420
cut
dit HClTit2 Vt Crt2contax
Reducers
Not 420
y a y MN 032
liberate Hz gas from
dilute acids
Cuero 3 263T
Hz t at Hoyt 420
cut t come
2 Crying 2Htaq
E
Enant31 rant2 is due to very high
positive
IE3 Of Mn

Emts Mta is most positive for which 3d

series metal Cobalt

Theoretical value of

i Ernst1 mat should be most positive

for which 3d series metal Zinc
Highest IES in 3dseries
Ii Ernst1 mat should be most negative
So
for which 3d series metal
 Very Important Questions their answers
only for board exams
i which is
stronger reducing agent between
Cft and feet and why
ANSI Cyst is stronger seducer than feat
Gt3 Cost e Fetz fest e

Hao ligandfield H2o ligand field

cyst Deg re CFSE
feast Fdeg CFSE o

tag pyigg
cyst is morestabilised than ret3
ii cat and ran't both have d4 configuration
still cr2t is reducer while Mn3t is oxidiser
why
ANI cr3t stable in innt2 stays n
og Sohn
lower 1Ez of Cr E V high IEz of Ann
Mose ne Dhydte
of Ccr3T

iii Enanstinarft is much positive

more than
ee3t1Feet and Ecy3t1cz2t why
ANI very high IEz

iv COLI is stable in aqueous solution but

in presence of complexing reagents it is
easily oxidised why
ANI cot2 Cost
complex stability complex
more ve
FSE
v How would you account for the increasing
oxidising power or vofcczof c.mn Of
ANS of
Due to increasing stability of lower species to
which they are seduced
fy3tzv3t
pnnt2fg.ge

Q
II Formation of coloured compounds
In aqueous solution Hao act as ligand
and colour arises due to d d transition
Most of the d block compounds aze coloured

Aqueous ion colour

soft colourless
Titt colourless
Ti 3T Purpletriolet
4T Blue
3T Green
2T violet
Cy2t Blue
e Cy3t Green

J
ann2t afnfegysteffffpl.netactually
fest yellow
feat Green
coat Pink
my Nist Green
Cu2t Blue

Zn2t colourless

1
oused
7mn20 7 Green oil
6
MCT due to Croz orange red solid
Eog orange yellow solid
12 Formation of complex compounds
d blockmetals form large no of
complexes due to
i comparatively small size
Ii High ionic charges
iii Availability of vacant d orbitals

General co ordination no of 3d series

metals E
I3 Catalytic property
Transition metals and their compounds
have catalytic activity due to
i Ability to adopt variable ox States
ii complex forming ability with reactants

catalysts at a solid surface involves the

formation of bonds between reactant species
and atoms present surface of catalyst
on

increased concentration of reactants at

Mn Oct Mn042 Croft Cra07 VOI
weakens the
Oo Cla Cho5
bonds in
s
catalyst
reacting
surface
species ie
lowering of activation
energies
 feet3
E fi LI t 52082 Iz t 25042
Mech
catalyst
Fest I feet 1 Iz
feet feet3
52082 2 Sql

ii 2502 02 cffffeyst 2503 conptoadess

Mech
15 14
502 t 05 503 t big
Traqt Oa s
205

catalyst Process

e
 4 Interstitial compound formation
small atoms like H B c N et are

trapped inside the crystal lattice of the

metals
non stoichiometric and neither
They are
covalent nor ionic
typically
3mcentite Tic VHo 56 NizB
P2 catalyst

any normal
They do not correspond to
oxidation state of metals

Properties
i Their melting points are more than
respective metals
Ii Hardness Higher

Iii They conduct Heat and electricity

Iv are
chemically inert
They
15 Alloy formation

Because of similar sizes and other

characteristics d block
metals can be
easily replaced by other d block metals
That is why d block metals have very
high alloy forming tendency
German silver
Hardness High cut Nit 2h
Alloys
High stainless steel
melting point fetertctni
Ti t Cee

BRASS Cut 2h BRONZE Cut Sn

15 Nature of oxides
Higher ox state Acidic
3 5

Lower ox St
3
4 Basic
generally
Intermediate Amphoteric
ox state gen 43
oxide Nature oxide Nature
Sczoz Basic MMO Basic
Tio Basic E Mn 02 Amphoteric

Tiz03 Basic Mn 03 Acidic

rTi0z Amphoteric Mnzorf Acidic
VO Basic Feo Basic
203 Basic Fez03 Basic
Vz04 Amphoteric Coo Basic
05 Amphoteric Nio Basic
mainly
acidic
Cro Basic AGO Basic
e C 2O3 Amphoteric CMO Basic
to
03 Acidic ZnO Amphoteric

QQ compare basic of following

z t2 strength
t2 z
oxides Cro VO Feo Tio
ANS Tio VO Cro Feo
Tic Cr Fe EN

QQ which metal of 3d series does not

form monoxide
ANSI Sc set2 not known
 Some important compounds of d block

Potassium Dichromate K 207

Preparation
is prepared chromite
from ore
q2czo7
FearsOf Cfto 5 203
other names Fern chrome chrome iron

Imp points to be used in preparation

Cy3t t Oxidisert alkali Croft
compound chromate

compound solubility zoo

glioomL
N92504 19.4
K2504 I't t
Naz 07 73
Kz 07 13
x
6 to
28042 t 2 Ht Crzoft t H2O
Cz 072 t 2 OH 20042 t H2O
 Step L
3 2 6 2
2 3 0
fusion
Feczoat Nazcoz t 02 Fezozt Nazcrogt CGT
S s s
S exc

2 3 13 2 to 2
o fusion
Feczoat NaOH t 02 Fezozt NazCroattLOT
S s s
S exc

Residue 2 Feroz f Naschy

add
TH20
then
f filter
Residue filtrate
Fez03 Nazlroy ag

Steph

Nazcroft 142504 Nazczof Naas04 t H2O

aq
fooling
Na25044 NazGzO7
Corgi

step 33

Nasckoft KU k
ag ag
207 It Nacfog
OH kzco not usedin step I as kzsot.kzcz.cz sssaoTfbility sdisfhefjcaLtation
 Properties
i red
orange orange solution
solid
crystalline

ii solubility
in cold water moderate
in hot water readily soluble
2420
iii Heating effect
1G 2 t6 13
g
Kzcz Of S Kzcroft Ck03 029
range Lyellow Green

Iv Reaction with alkali

6 6
K 207 t KOH K2 Croft H2O

v Reaction with cold conc Hasek

K 207 t 42504 Hzcroat K 504
40 2031
H2O
kzcrz07 ttb.SI Crozt K2504 t H2O
Vi Reaction with hot conc Hz sq
K 8207 H2S04 t CK 50433t kaSog t 02T H2O
D
yo 3 Crzozt Oz
amber
µzso Crais0413t H2O

Vii Reaction with 4202

A Low tents presence of ether or
amyl alcohol
or pyridine
k 207 t H2504 11202 Crost K2soy 1 H2o
Blue

Eo
Cr05 I cry031 02 f faitragomFeae

CBI High temp

Green
k 207 t H2504 11202 12250ft Cris041st
Oz 1 H2O
onlytfrance
Alkaline medium 30 4202 solution
4O
Z i
6 M t5 l z
K 2074714202 4K OH 2kg Krofft 9h20
Brown
14Peroxide O
16 peroxide o
1 3 Cr 0214
ale peroxideligand
Viii Oxidising actions of acidified k 207 i
die tysq
CROFT Ht orange

I Iz
feetz green
fet3
Sd
H2S
4
502 5042
2

4
252032 504
2
5032 504
NOI Nog
I o
x U Br I HX Xz
Sn2t
3
snit
2 4
204 CO2
H5OH CHINH
13 15
As033 As043

V
Cr3t
Green

t
oooo
k 207 is used as
primary standard
in volumetric analysis
is
k2Cz07 preferred over Nazczoz as
standard in volumetric analysis
primary
as Naa Cz 07 is hygroscopic
chromyl chloride test v.am
ions
Test for a

6 I 6 6 I 6
KzCrz07tNaUtH2S047Cr02U2TtKHSO4ttk0Es3Es
nc.s fed
fonrawnmgey

chloride

Crozclat NaOH Nazor 04 t H2O

Cli yellow Solh

Croft t pb2t Pbcroyd

YeIYn turmeric
some 92 may also be liberated
6
ag
t Cz072
ag
Htag Clint crest Hao

Chlorides which do not respond to

chromyl chloride test
Hgas Hg292 CH3U

dont
exist
CrozBtz Crt oxidises
CrozIz BFI Steffey
Potassium Permanganate Khang
Preparation
janya oxidisertalkgli 3mn92
Kiang is prepared from pyrolusite
ore Mn 02
Step t
fusion
Mnoz
S
t KOH t 02 Kannnoat HIT
S exc
fusion
Mnozt
S
KzC0zt
S
Oz KzMn0 tC0zT
exc

KOH 1 KNO
fusion
Mnozt
S s
K2Mn0 tkNOzt HOT
S
KN 3 kN02102

yayo ggg qyggqusiqg.mg pyo

Kaos 6kW too
Green mass
kzMn0 green
extracted with
water

Given solution
step G2 7
Kanan04 92 Kannoat KU
K2 Mn 041 03 KMn0 t 02
E t 7 14
Khan Mn K
 I

MnofG20
is stable
7 only
structure in strongly alkaline
medium
It
oI
a
undergoes disproportionation in neutral
or acidic medium 13.0 I16
6 14
3mn92 t 4 Ht 2tinnoft inn 02 21420
bridge
or 0 1
commercial method
oxygen
alkaline oxidative
Mn 02 fusion
Mn042
2 Cr O bond
typesofof Mn 042
Electrolysis lengths medium
in alkaline

GE nanoft
Anode cathode
M nO Yo
2
B 0 I 1 66
e P 25
1I
2420
o
Hat 20h

LD
b with bridgeoxygen y
Lab process oxidiser
µ Mrftsalt acidic medium knot
d att d's L MCT H
Oxidisers Pb02 Pbzoz Pb304 Bi05

52082mm't
905
y
rnn2t
t
t
52082 1 H2O
Bi 05 t Ht
o
all ch o
bond lengths
inning
are
Sof
same
Bit 3
1 Ht
annoy 420
ran't t pbozt Ht Ming t Pb2ttHzo
Properties of KMn0
i Appearance
Dark violet 1 Purple Pink Purple
solid solution
crystalline

ii
solubility
In cold water moderate
In hot water
readily soluble
Iii Heating effect
7 2 g tG 4 O
Kann s K2Mn 04T Ran021 02

Iv Reaction with alkali

7 z G
Kmnopt KOH OI t Kanhnoat H2o

V Reaction with conc 142504

Khan 0ft 142504 HMnoat KHS04

InjHfs Mh207 MnoztOz
explosive
vi oxidising actions of Krang
Acidic medium pan2t
Mf 5
17 alkaline
MMOI strong
medium 7mn42 hf L
Mroz hf 3
weakly alkaline
medium

MNOI.tt
I Iz
felt Fest
5 s sod
Hz
4 6
502 5042
2 6
52032 s 5042
EE 4
5032
6
5042
3 15
NOI N 5
I o
x U BFI HX Xz
Sn2t
3
snit
14
2
Of CO2
H5OH CHzcooH
MEET 13
As033 A sq3
5

Fana
colourless
 oxidising actions of Krang in neutral or

faintly alkaline medium

17
H2O t2MnOI t I I 05 t2Mn0zt2OH
date

H2O t2Mn0I t Br 15505 tanning 2 OH

t t2 4 6
H2O 18mn05 1352032 8Mm02 65042 1 28H

7 4
2h04 4Ht
2h20 t2MnOIt3Mn2t 02 2h0 annoz t
catalyst

in
Kinney is not used as primary standard
volumetric titrations why
ANS
I Kiang is photosensitive
Kanno H2o light Mn021 02 t KOH

Teng slow

o
 ann Ann
iFnO pinkllourtole
0
8
I acidic
mo
LMCT o
o
tetrahedral
oxide
Iqn

pathogen Green
Lina F
nnn o Tetrahedral
d td transition l
O

6
Crop yellow 0
11
LMCTI o Tetrahedral
qro o

CrzO72 orange
0 Combination
tract
o cr g 0
of Two
1 1 Tetrahedron
o o
Max Total 6 Cr O bonds are of
equal length
Mn 7 Lancet
O 0
Green
0 1M ran
11 0
If O