d-BLOCK ELEMENTS AND THEIR COMPOUNDS

Introduction
3 4 5 6 7 8 9 10 11 12
Hesiod
se Ti v Cr Mn Fe Co Ni Ge Zn
3dseries 21 22 23 24 25 26 27 28 29 30
FIriod
Y 2 Nb Mo To Ru Rh Pd Ag Cd
AdSeries 3g 40 41 42 43 44 45 46 47 48
FIriod Pt
La Hf Ta W Re Os Ir Au
Hg
Sd series 577 72 73 674 75 76 77 78 797 80
FIriod Ac
Rf Db Sg Bh Hs Mt Ds
Rg Club
Gd series 89 1047405 106 107 108 109 110 III 112

elements d block last electron

In the of
enters into n 1 d subshell

General configuration nst n 1 d

Pd 4G 554110

Transition Elements

A transition element is defined as the one

which has incompletely n 1 d subshell
filled
in its ground state or in
any
one
of its
oxidation States
They are elements because
called transition
their position is in between reactive s block metals
and less reactive metals of p block Their properties
are transitional between s and p block metals
in Da s do or do
subshele

Transition Cn Dd s d to d
elements subshele

Gr 12 elements Zn Cd
Hg of d block
are not considered as transition elements why
ground
41g state g Dd zntz
Cdt
1 do
91
They have a config in ground state as well as in
ox state

QQ Cu Ag Au have completely filled 1

d subshell still are included in

they How
transition elements
SI Cu Ag Au Gigante n 1 do
cut d9
Agt d
Aut3 d8
General Properties
i Atomic radius

General trend across the peridot

A First size decreases upto near middle

Reason in
inc Zeffective
B Then size remains almost constant
Reason inc innuclear charge is almost
counterbalanced inc in ee
by
repulsion
c size increases in last
Reason e e repulsion dominates

General trend in a
group

3d series
reason
inc in shells
Kdisiries
no
of
Eet almost Reason
same tf poor shielding zeffine
5d series Canthanoid contraction sizecontracts

A
2 Ionisation Energy

General trend across the period ts

to with many
Generally inc from left right
irregularities
General trend in a group 2

except Gr 3 Sc Y La Yasi's
3d series
series
ad series gg sd

In 3d series In d block
Maximum IE 2n [Link] skiable
fg
Least IE so 978 Maximum in each
IE
Maximum IEa a fathom Period is from Gr 12
Maximum I Eg 2n ester Least IE La largestsize

Ni Cu Zn rarely exhibit ox state more than

2 in their compounds
Reason very high IES
Zn no compound where ox no 2
m rarely few amp
kg mop

O
3
Density
O

glans
General trend across the period
Density first increases upto end or near end
Decreases in last

Trend down the group 7

ad series

Maximum in 3d series Cu co Ni
density
Maximum density in d block Ir Os
Min density in d block se
 4 Typical metallic properties
Nearly all d block metals display typical
metallic properties
Tensile strength High
Ductility
Malleabilility
Thermal conductivity
Electrical conductivity
Metallic lust use
Hardness
High
volatility con

of All d block metals except 2n Cd Hg Mn

have typical one or more metallic lattice
structures at normal temperatures
Typical metallic structures BCC ECP HCP
5 Melting point
other high melting point of d block metals
are attributed to the involvement of
greater number of electrons from n 1 d
in addition to the NS electrons in
the interatomic metallic bonding
factors affecting melting point
i no of unpaired electrons
ii Zeffective
iii size
iv Packing in solid State

General Trend in period

a

First increases
nearly upto middle
Reason as inc no
if unpaired és
dec size Inc Zeff
Then decreases from middle to end
Reason dec no of unpaired e s

General trend within a

group_
sd series 4d series 3d series
metal metal metal
Reason inc zeff down the group

Max
melting point in d block W
in d block Hg
Min
Max
melting point in 3d series Cr
melting point Board mains
 metals
Melting points of Group 12
are lowest in respective series
why
ANI No electron from d involves in inter
atomic metallic bonding from group 12
elements weaker atom to atom interaction
lower m lot I
Zn ed Hg volatile metals
6 Enthalpy of atomisation Hati

curve similar to melting point curve

Here Dali Enthalpy of sublimation

Transition elements exhibit high batt

due to involvement of more no of electrons in
metallic bonding stronger atom atom interaction
 General trend across the periods
First increase nearly upto middle then dec
v Ti Ni Co 2n Dali in 3d series

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 c 4d series c sd series
inc Zeffectie

Greater Date if ad and 5d series metals

than corresponding 3d series metals is
responsible for much more occurrence of
metal metal bonding in the compounds
of
heavy transition metals I SEIKI the
chemical reactivity
Dat affects
Éoxidation Éreduction

why zinc has lowest sate in 3d series

e from 3d is involved in metallic bonding
ANI No
weaker atom atom interaction
 Oxidation states
71
d block elements exhibit more number of
oxidation states due to involvement of
more no of electrons in bond formation ns and 1 d

Sc Ti v Cr Mn Fe Co Ni Ce Zn
I
2 2 2 2 42 2 2 2 42
33 3 3 3 3 33 33 3
t t t t t t t t t t t 4
55 5 5
6 6 6
7
Most common ox circledonesare Boled ones are the
in generalthe most common ox
no in 3d series the [Link] nsetgtmesenfosr respective
elements

variable oxidation series elements

among 3d
is not shown by se Zn

series elements
2 oxidation state
among 3d
is not shown by Sc

Except or co on oxidationhighest
state shown by a 3d series element 2 2
n total no of unpaired electrons
Maximum number of oxidation states in 3d
series is shown by Mn ie 7

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 bonds of unpaired electrons for
bond formation

The elements which exhibit more no of

oxidation states occur in the middle
portion of series more unpaired és in middle

Negative or zero oxidation States are also

shown by d block elements in their
compounds but only when there is synergic
bonding in compound
ez Cr CO 6 NICCOLI FecCola Co COL

Highest oxidation state in d block is

shown by Os Ru which is equal to 8
8804 Rudy
EY Stability of oxidation States

T
in s pantag

Date
DhydH

inn
m g DithetDiaz pantig

M s tag Mag t ne

DHT Date BiH T

Dhyd H

Less positive date less positive bite and

Mose he
[Link] supports for greater stability
of metal in th oxidation state

EIF d
configuration is
generally very
unstable in ions
ez set ion is not known
explanation
al IE do t e
poet Matt
compensated byhigher LE or

higher hydration energy

 B do d5 d configurations generally provide
those stability
e
Titty Tist man't must zn2t zn3t
d d as dt d dg
noblegas
Taffyed filled
C stabletion of Cr in ag solution 3

D Stable ox States of co Ni in complexes Cots Nit

ÉÉI an aqueous solution of stability

Mdlof Al tdg
Reason IE of Cu i.e IE of cut is compensated by
more ve Dhydfl of cult
cut undergoes disproportionation in ag solution
2 Cutrona cuts t Cag
EFFIE From group 4 to group 10 higher ox
States of Id and sd series elements are
more stable than higher ox States of their
corresponding 3d series elements
opposite of inert pair effect
ez i Mo VI W VI Table Cr VI
arts oxidiser e ref oxidiser cross oxidism
note Wto non oxidised Moog wot wog
non oxidised
 ii innof oxidiser
ReOI non oxidiser

G Lower oxidation States are

generally reducing
ex Ti't Felt it Cr't and they form
bonds with heavier halides not with 02 or F
BT I AST AI I HIT
H
Higher oxidation States are generally
307
ex Cret Mnt cost Fest and
Txidising
they form compounds with 02 or F not
with Br I Ect Etc of a

known x not known

ÉFgH VE 056 IBIG Feat EEC
IBB X FIS X BBGCTIA
Ian Cota x
Tt vie is less stable it readily hydrolyses in
moist air e Vast H2o vocytated
aix u a E
ditz
X I B2 I GE
É F CuI2 and Fetz are not known
cut Fet3 oxidiser I strong reducer
262 41 2 MII t Iz
2Fe3t 6 I 2Fe Is t Ia
 The to stabilise
III ability of fluorine the
higher oxidation states is due to
I high LE released on formation of ionic bond
ex CoE
ii high bond formation energy released on covalent
bond formation ex Cre VE

ET stabilise
The
ability of oxygen to the

highest oxidation States is more than that of

due to its at
forming capacity
fluorine
Fiighest manganese fluoride Intf
Highest manganese oxide inn 07

In simple halides of inn Mnf is not

known due to steric repulsions
MnFg MnFo MnFy unknown

D In 3d series
Beyond Mn
only Fe
and co form trihalides
ex Fexz COB
x I
 The fluorine to stabilise
III ability of the
higher oxidation states is due to
I high LE released on formation of ionic bond
ex CoE
ii high bond formation energy released on covalent
bond formation ex Cre VE

ET stabilise
The
ability of oxygen to the

highest oxidation States is more than that of

due to its at
forming capacity
fluorine
Fiighest manganese fluoride Intf
Highest manganese oxide inn 07

In simple halides of inn Mnf is not

known due to steric repulsions
MnFg MnFo MnFy unknown

D In 3d series
Beyond Mn
only Fe
and co form trihalides
ex Fexz COB
x I
 Trends
Eft in
sÉÉÉI potential
M s
BHT
nation

Datt

v Dhyd H
Mlg

Ain t Ditta
ME g

DHE 141 City Dhydt

more re
Itsy moretendency to
get oxidised
t
more Eve Éox
de
m ve Éred

The trend towards less

general negative
É values from left to across the
right
f Period is related to general increase in
Ain t Ditez
O
 Equation is positive due to
i High Date
Ii Lower DhydH of cuts than init AH

unique behaviour of copper accounts for

its to liberate Hz
inability gas
from acids

a a reacts
wimIÉÉÉÉÉ went
only
are
oxidising in nature like HNoscone Has04

Éredvalues for Mn Ni and 2n are more

negative than expected from the trend

i Pant d5 stable configuration resist reduction
ants an
ii High re [Link] for with resist reduction

d block elements of 3d series except

cu react with acids to liberate Hz
but in most the cases reaction
gas of
stopps after they start due to formation
of insoluble protective film
110 Trends in Énnt3 antz

Mnt Cot3 stronger oxidisers

Fet3 mild oxidiser

to Iihf Reducers

liberate Hz gas from

dilute acids
267g 2Htag Hat t 2Cr3t
ExThe
Émnt3 rants is posited very high
IES of Mn
Ént3 rats is most positive for which 3d
series metal cobalt

Theoretical value of

i Enn I n't should be most positive

for which 3d series metal Zn
ie removalfrom
alofer IES
Ii En't Ina't should be most negative
for which 3d series metal So
testy mffortant Questions their answers

i which is stronger reducing between

agent
Gat and Felt and why
Ang Crt is stronger reducer than Fett
272 237 Fetz Fetz
peg cFse o
[Link]
ii Cr't and Mn't both have d4 configuration
still cat is reducer while Mn't is oxidiser
why
at
tant
Iggy
erst
antes
Mn

IE of inn IE Her
or is morestable in 3 in ag
son Mn is more stable 2 in ag
som
iii Émn3t rant is much more positive than
ÉFe3t Felt and Eat cat why
AI very high IE of Mn

Iv Co I is aqueous solution but

stable in
in presence of complexing reagents it is
easily oxidised why
ANI Cot3 stable due to ve cese
highly
complex
air
Cot ag cot complex
presence of
strongligands
like NH3EN
NOT
C How would you account for the increasing
oxidising power ingots cÉof inn of
ANI due to stability of ox state to which
they are reduced I
mnsIagfgt
II Formation of coloured compounds
In aqueous solution Hao act as ligand
and colour arises due to d d transition

Aqueous ion colour

set colourless d
Tift colourless do
Ti 3T Purple violet
Vtt Blue
v37 green
Vat violet
cat Blue
Cat green
Mn2t almost colourless
Fest yellow
Felt green
coat pink
Nist green
at Blue

2Mt colourless Ilo

Mn 207 green oil

colour due to
203 orange red solid
LANCT
205 orangeyellow solid
12 Formation of complex compounds
d block metals form large no of
complexes due to
i comparatively smaller size
high chargedensity
ii high ionic charges
iii availability of vacant orbitals

General co ordination no of 3d series

metals 6

13 Catalytic property
Transition metals and their compounds
have catalytic activity due to
i ability to show 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 on
surface of catalyst
increased concentration reactants at
of
weakens the bonds in
catalyst surface
i activation
reacting species e
lowering of
 ex is 21 5208
Effy 12 2505
Mech
pets I Fet t 12
Fett 52082 s Tet 5042

Ii 205 contact
2502 02 2503 process
catalyst
tech
502 8205 124047503
trio to V55

Catalyst Process
14 Interstitial compound formation
Small atoms like H C B N etc are

trapped inside the crystal lattice of the

metals
non stoichiometric and neither
They are
ionic covalent
typically nor

EI FezC N Ho 56
Cementite Étcatalyst

any normal
They do not correspond to
oxidation state of metals
pitoperties
i Their melting points are higher 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 Nitzn
Alloys
high stainless steel
melting point Fet CtertNi

BRASS Cut Zn BRONZE Cut Sn

15 Nature of oxides
Higher ox stay acidic
5
7
Lower ox
stt
3
Basic
generally
d block Intermediate amphoteric
ox state gen 4
oxide Nature oxide Nature
50203 Basic Basic
Tito Basic Man02 amphoteric
Tinto Basic Mtn03 acidic
Tito Amphoteric major acidic
y Bad Feo Bad
203 Basic Fetoz Basic
204 amphoteric Coto Basic
v30 amphoteric Nito Basic
mainlyacidic
CEO Basic G20 Basic
CEO amphoteric Ato Basic
CEOs Acidic Into Amphoteric
compare basic strength of following
oxides GO V0 Feo Tio

ANI Tio V0 Cro Feo

C TIC VC Crc Fe EN
QQ which metal of 3d series does not
form monoxide
ANI Sc set not known
some important compounds of d block

Potassium Dichromate K 207

Preparation
K 207 is prepared chromite
from ore
Feck 04 Fe Otero
other names Ferro chrome chrome iron

Imp points to be used in preparation

É
Cy3t
compound
t oxidisert alkali crop
chromate

compound solubility
gloom
N92504 19.4
K2504 It Is
N 928207

K2C207 D
202042 2Mt 2072 120
62072 2 OH 26042 Hao
step L Alkaline oxidative fusion

Feczoat Nazcoz 02fusiMFegotNazcroat coat

S S exc S

Feczoat NaOH 02 fusiMFegoztNazcrothof

S
S S exc

Residue 7 Feast Nazca

Id
Itter
Residue filtrate
1203 Nazcroplsoln

step

Nazcroft 42504 7 H2O

ag 0422071
fooling
Nassoat Naz 7

step 3

Nastro t ka Kaczoyt NaCl

ang
 Properties
i red
orange orange solution
solid
crystalline

ii solubility
in cold water moderate
in hot water
readily
iii Heating effect
K2 207 S kzÉOgtCÉoztoz

Iv Reaction with alkali

KzC2O7 KOH karat H2O

V Reaction with cold conc 42504

1 26207 42504 003 1 2804 420
2 207 a 42 07 0,2603
Vi Reaction with hot conc 42504
K2G20 at 42504 Kas at Ost Hao t Cra 5043

83
2 07 a 4220757 2 gÉmg3

con42504
22 5043 a

Vii Reaction with 4202

ÉÉIIow temp presence of ether or
amyl alcohol

K2Cr207t Has It 4202 93 t 12504 420

1
see ad ILme C2Has
03 02
1 of
ÉÉÉ I 129 205 12504 420 0215043
green
CBI High temp
K2Cr207t Has It 4202 Kasa tcz soul qt tho
No detection of Cros

Alkaline medium 30 4202 solution

Kaeo
Kz
t
ÉCO24
I 2136208 9 H2O

all are peroxide

viii oxidising actions of acidified K 2207

CROFT Ht orange

I Iz
Felt Felt
4252 5
5042
802
2032 042
5032 5842

IOI Teos
x Ce Br I HX X
Sn't snit
2042 Ez
C2H5OH CHzcooH
At's033 1750,3

31green
Katz 07 is used as
many standard
in volumetric analysis
is
K 207 preferred over Nazczoz as

primary standard in volumetric analysis

as Nazca 07 is hygroscopic
 chromyl chloride test
ions
Test for ct

KzÉO7t
S
Nail
S
Has 04 Éoadsttkasotivatesottyo
Conc orange red
chromyl
chloride

[Link] NaOH
ag
Nazcroat Nacl H2o
yellowsom

Croft
som
Pbt Pbcroyd
Turmeric yellow

some Cla may also be liberated

Ce Cyo Ht crett dat H2o

chlorides which do not respond to

chromyl chloride test
Hg dz Hg Cla CHzll covalent

És
If BE not exist kzcggatyzmsog [Link]
softH2O
Crt oxidised
Br I strong reducer
Potassium Permanganate Kannon
Preparation oxidiser alkali tin inn of
Ing
KM not is pyrolusitemanganat
prepared from
ore Mn 02
step t alkaline oxidative Fusion
Mtn02 02 sins Kanntnog 4289
S Kg exc
M 02 t 182503 02 tush Kantnoft cost
exc

M 02 knights KantnotKntosttro
Kg
MtnOz Ms
k 0 Kathroat KI t H2o
S Kg
Green mass

Item
water

Green solution
step 2 oxidation into Kinn 04
Karnataka Kinnoat KI
Kamnoat 03 kin not to 2

I Kamina CO2 [Link]

 Mnof is stable only in strongly alkaline
medium
It
undergoes disproportionation in neutral
or acidic medium
3min02 t 4Mt 2Mt oft Mtnozf 2120

commercial method
alkaline fusion
Mno annoy
Electrolysis offinnof in alkaline medium
Anode cathode
Magi nanojte Hot E Hatton

Lab process
Inapt salt oxidiser
nanog
acidic medium

Oxidisers Pbt oxide Bits compound 5208

Mnt 2 52082 t 420 nanoft 5042 tht
pants Bios t Ht nanoft Bist t Hao
rant t Ht Mnoft Pbt H2o
Pb203 OR Pb304
Properties of KMnop
i Appearance
Dark violet 1 Purple Pink Purple
solid solution
crystalline

ii
solubility
In cold water moderate
In hot water readily
Iii Heating effect
7
Kann s
s
Kathy Mn 02 02

Iv Reaction with alkali

7 2
[Link] OH
D
Katmnoytoat H2O

V Reaction with conc 142504

KMn0 t 142504 Hinnoyt Kasout 420

[Link] ne tnnostoz
vi oxidising actions of Krang
Acidic medium Mnt2 Nf 5
7 alkaline
MnOI strong
medium
inn of Nf 1
nei 3
Mn 02 Nf
weakly alkaline
medium

Mn OI Ht Pink purple

I Is
feltZ Fest
S
H2S
4
502 5042
2
52032 s 5042
14
5032 5042
3
NOI N 05
I
Ce Br I HX Xz
3
sn2t sht4
2
Op CO2
H5OH s CHzCOOH
13
As033 As043

Fana
colourless
 oxidising actions of Krang in neutral or

faintly alkaline medium

I
H2O 2mmOI t I Éo5tatÉnozt20H
iodate

H2O 21mmOf t Br Bros 2mn02 28M

Bromate

H2O 18mn05 1352032 65042 8mn 02 2 OH

7
2h20 t2Mn Of t3rnn2t
2ns 04 Minor 4Mt
02 2h0
catalyst
comproportionation

in
Kinney is not used as primary standard
volumetric titrations why
ANS Kanno is photosensitive
Kanno t H2O t throat 02 t KOH
slow
pen
Mn04
14
Pink 0 o tetrahedral
MCT

Mn042
Green
Id o Tetrahedral
LMCT
did transition

2042
yellow
Lrn CT
off o Tetrahedral

22072
combination
range
Leno Irony
Ef o
oftetrahedron

Cmax Six Cr o lengths are

equal together
Mn207
combination
Green tanto
oath o
1
of two
tetrahedron
LMU