Ee

The most striking feature transition metal chemistry

of
the plethora compounds and the variety
are
of of colors of
the compounds
 Multiple ox states of metals

Ability to form complexes with a wide range of

ligands

D Block Transition Elements Itf 117

A transition element is defined as the one which has incompletely
d orbitals in its ground state
filled 9
or in
any
one
of its ox states

d db ds
2n Cd Hg are not transition elements
All transition elements are d block elements but reverse isn't true
0 2
General electronic config Cn 1 d ns

All these elements are metal

3d series to Ze
yd series to CE
Sd series La to
omitting Leto Lu
Ig
Gd Series Begins with AI but is incomplete

Most stable 0.5 3 2 I 12

 ns
In transition elements valence e are present in outermost as well as
inner d orbitals Ultimate t penultimate
ch Dd
Unexpected e
config
5 due to small energy gap b w
Cr au fat Us 3d
Lg 4S 3d
Cle gg ART 45 3D filled
stability of
half filled config
5 16 17
Un Cr Mn form 4045 Crout and Manoj

Tetrahedral ions

Fe co Mi are all ferromagnetic and all IMCHaold

form
Octahedral
ions in water and finely72 ion
3 O S is Fe less common Co and
very
common
for for
very
rare
for Ni
Ti a hard silvery white metal is the least dense of the
transition metals Its most common core is Rutile Ti Oz

702 lot 2C Is t 26 Ig Tidy g t ICO 1g

A 1,2mg l RA
Kroll's Process
2
T Ti Is 2 Mgk l

Cr is found as chromite Feckoy

Transition metals 8 their compounds also exhibit catalytic property
and paramagnetic behaviour
There greater horizontal similarities in the properties of transition
are

elements in contrast to the main group elements

 g p

led series

Unexpected e config d5dd

Mo U2 5s 4d5
Pd UG 5s 4d

Ag 47 5s Ud

55cLSeries

fun expected e
config
Pt 178 Gs 5d9
Au 79 Gs 5d
PhysicalProperties
 M
beingpoints
o

strong metallic bonds w the

b

atms these elements are

of
responsible for the high 1
top
Tc have
Mn
abnormallytow
m
p

Enthalpy of Atomization

5d The dip in the m.p of

Ud
3d inn II 8 Re can be
5d explained on the basis
their half filled
ad of
3d d orbitals stable
I
e are less delocalized
He
Weaker metallic bond
2g MIC Character
Both ns and Cn Dd e participate in metallic bonding
strength of bond 2 No
of unpaired d
e

Cr Mo W have max no
of unpaired d
e and are

therefore hard metals whereas Zn Cd Hg aren't very hard

metals due to the absence e
of unpaired

3 Variation in atomic ionic radii

I along the period

Sd
Ud but small variation
3d
At the end there is
a small 9 in radii

Irregularities can be explained on the basis

of
Zea
Shielding Effect
 Near the end the 9 repulsions btw added e
of series e e

in the same orbitals are

greater than attractive force of
Zea

For Atomic radii 9 down the group but are almost same
for
series d
qforbitalsbefor e.cl
whichresull sinaregulardecrease.in micradiicalled
Lanthanoid Contraction

Due to Lanthanoid contraction following pairs have almost

identical sizes
Nb Ta Mo W
fgg
p
ne d
r f Man T

Density d in metallic radius coupled with 4 in atomic mais

4 the
density across a period
Zn is an exception due to large atomic volume
 Ie

E
 FROST

Diagram

Ti V Cr Hn fe lo Ni Cee
Ionization orgy

0 O
000 O
 Transition metals are lers EI than Steck
I.E
of EI EI Itg are
very high
because
of their fully filled
n Dd Ons config
2nd I E V L E MI
of
Nic Cee Zn

f Oxidation States
 If

Miss Migs
DHsub É MMG
T.gs
N'teas
 Standard Electrode Potentials
Thermodynamic stability of a compound
septal
e IE t IE
g Nit
Ni 2.5 103 Kolmol
py2t
p 2 66 103 KI mol

Ni compounds are thermodynamically more than Pt

compounds
IE TIE TIE TIE y
Ni 11.3 103 Kalmof
Pt 9 36 103 KI mol
Pt compounds are
relatively more stable than Ni compounds

Katia exists but Kania doesn't

In solutions stability depends on electrodepotentials

i
Qualitatively the stability of transition metal ions in different
ox states can be the basis deception data
of
More ve the SR os
determined Higher stability in
geum
e M na SRP 15
g N't is stable
Y
more
Nat y than Mat
 SRP Oxidising Power

Trends in the MTM standard Electrode potential

Element MMM SRP

Ti 1.63
V l 18
Cr O go i

Hn 1.18
Fe 0.44
Co 0.28

Ni O 25
m

cu t 0.34

Zn 0.76 indicates that Zn is more preferable

DD

DD

values of E for Mn and Zen are more ve than expected

 of fo e p
from the trend due to M Cds and Cd
2
stability of
config
No
regularity due to irregular variation of LIZ
SRP values are lower in magnitude compared to S block
metals Due to
high atomism Energy t.ee
Zn has low Ha and fairly large EHuya 2nA But
it has also low SRP C01,6 due to high IE IEz
Cee has tver least reactive metal
The to transform
Explains its inability hiney
to
cu wit g is not
liberate Hzf ids
FalancedTy its DIIHyd
and hot cone Hasoy
Only oxidising acids HILO react with Cee

where acid gets reduced

e.g Cuco U HNOg l Cee

Mos Iss t 2k101g 12420
conc

Alls t 2112504 l CUSOy t SOz t 21420

12
papist Mn
g

eg
Cr Us 3ds
9 tag es TE tg
arts k
th
 1
L

man

te M2tspp
HI Trendsinnnstlpqztsp.TN

3 More stable testable

Soft is stable due to noble gas config hence low sRP
very
Mn is stable due to discernfig
particularly
 fROSI e

e3
Cr o

ft
I

The comparatively low value for 11 is related to the stability of

11 due to half filled tag in octahedral field

8 tag
Trendscinstabilityofhighero.SI

mmmm

agio ME
s 16

7
 3
M Properties

B.M
 I

Tt d d transition

II Colour in compounds
 T.in
oyotscoottno0sZnfez0y
Zn0tfez0zFezOy
Feo fed t

Mn Oy 2M no Mn Oz

at Pb304 2Pbo t Pboz P Block

Spf These are special type of mixed oxides in which

the oxygen atoms constitute a fee lattice the metal ions

occupy the interstitials

 rest occupy OHV
e
g Enfezoy Emeline
Zn't occupy TIV
IFE
I

Inverse spinel feat occupy

rest occupy THU of

SaltscontainingoxoanionsofMetal

The oxides Cros Molly NO Mn 0 are strongly acidic

There oxides when dissolved in
ag alkali solutions form
discrete oxo metal ions e.g
Croy Cra07 Moog 4042 Mnoy

1 Potassium Dichromate KzCr20y

chomtoremates
Yellow
ifeng.org
orange
Dichromates

crontzreostsco
oxagent yellow
Yellow solution is acidified with Hasty
of Nazcroy filtered
to give a solution from which orange NazCra0 can be

crystallized
2 Nazcroy t 2Mt Nazca0 t 2Nat t 1120
Yellow orange
 nge

Sod dichromate is more soluble than Potdichromate

t t 2 Nacl
NazCraO 211 Kaczo
Orangefstals

Kaczor is preferred over

Nago as a
primary standard
or metric estimation b'coz
Mako is hygroscopic in
nature but
It is not

Orange red crystalline compound

Moderately soluble in cold water but freely soluble in hot water
liberates Oz on strong heating
d
2kg620 2K Croy t Cry03 302
On heating with alkalies its converted to chromate
K 20 t 2KOH 2kg604 t 120
Orange Yellow

Croy and Cray exist in equilibrium and are interconvertible

by altering the pH of the solution

24,04 T 2Mt I 2h GOT F Cra07 T H2O

Acidified Kalra0 solution reacts with 1202 to give a deep blue

solution due to the formation
of Cros
 72

o
a

50 o
i
É
dichromate
Chc
Its oxidising action can be represented as follows
Igof t 14Ht t be 26
3
7120 EE 1.33 V
stable
SRP Power
Oxidising
It oxidises
I Iz 503 soy
Sn't shut As033 Asoy
6Ht 31 be HE X Cl Br 1
3125 E
felt pest

detection of a ions
f Chloridetest for
When Kaczo is heated with conc tyson in the presence of
a soluble chloride Itt
chloride Crall is formed
the
craft vapour of chromyl
adf.at tgE
sEÉ F

FILE J Pb nope Yo A
Is It Crab t 110

FEI EI
orgy
E

dL

it
9

ist

10

I Hu
E I
Il

r
2

n 4

tht I
V I
3
2
3
2 3 16

Cuco CucoH z

I
I

I
E
a

Hg12 K2lHg2y
ScarletRed Soluble

leg 129
 M
anganaterpermanganate
KMnoy is prepared from Mno in the presence of alkali
when dark green Kanno is formed which further
disproportionate to form Kinnoy

2mn02 t UKOH t 02 2K2MnOy 2420

3mn04 t Utt 2mn Oy t Mno t 2120

Commercially its prepared by the alkaline oxidative fusion

Mno followed by the electrolytic oxidation annoy
of of

iing air or KNO

IIinioifinio
Ed in alkaline Purple
soln

É Mfsatt aided by 5208 to Mnoy

Indah is
ie 2mn t 552082 8140 2mn05 t 10504 t IGHT

mi nd
o o
041 o

Tetrahedral Tetrahedral
Manganateion
Paramagnetic 191911
39
Properties
Its a
purple coloured crystalline compound

Not very soluble in water

6.4g 100g at 293K

It decomposes at 513 K
d
2K MnOy KyMnOy Mno t 02
LMC T
Its intense colour is due to the metal CT
ligand
It has weak temp dependent paramagnetism
 Reactions Ox Power a sRP_
Oxidising of Krang
7 6
Mn y t e Annoyed E to 56 V
Finoj t Uti 35 Fatso t 2420 E 11.69 V

n0i t 814 5e Mn utyoeo ti.TV

µ Kanai at 1H't 1M should oxidise H2O but in practice
the rain is extremely slow unless either in ions are present
or the temp is raised

7 12 17 y
µ OH
Manoj Mn oxidises annoy Mno oxidises
I O l 5
I Iz I 105
pet fest 032 5042
thiosuephate
Sof coz
521Has s Mn MnOz
5032 1502 5042

NOI NO
HCHO H OH
X X2
Ct Bi E
19202 Oz

KMnoy is not used in titrations involving Hulu b'coz

Ct is oxidised to Cf
 Used as an oxidant
Used in bleaching wool cotton silk other fibres
of
decolonisation of oils
AlkKMnoy is called Bayer's Reagent
Used in qualitative analysis for detecting x so a SOG
ele
Not a
primary standard is always standardised with

astandardsolutionofoxalicacidI
019 Khanoy acts as an oxidant in neutral alkaline as well as

acidic medium The final products obtained from it in 3

conditions are respectively
a Mn0yd Mnt and Mnt
b Mn02 Mn02 I Hn't Ans b
c MnOz Mn02
1
Mn3T
d Mno Mno Mnt

20

21
silverritscompountaqua Regia
not dissolved

air
No exact
Metallic silver Has
Agas BlackPpt
112504
Ag Soy t 502

HMOs
AgNO NO
Hot conc

HI No Rx

UAg 8 KN t 2120 02 4K Ag CNI UKOH

Silver Nitrate Ag NO Lunar Caustic

D
3 Ag UHNO die 3Agno t NO t 2120

On heating above its m it t 02

d
p forms Agno
2Agno 2 AgNO 02
Irs
heated
2
Agt 211102 02
6 Agno 372 3120 5A t GIO toting

i
whihitturnsblakespeciallyinpresence of light The
 ely
anctissues
Itsthereforestoredincoloredbotes

Solid Agno absorbs MH gas with the formation

of an

addition compound AgNO 3MHz

When NH OH is to Agno solution a brown
added ppt
of Aga0 appears which dissolves in excess of Agno

2 Agno t 2N Hyon 920 L t 2 NH NO t Hao

I NH OH
2 Ag Nts NO 3420

Amm AgNO CHECK Ag C d 2nA no

Toller's Reagent white Ppt

canvasing
22

He
 H

a Copper sulphate Cusoy 5h20 Blue vitriol

Cleo HzS0y CUSOy t H2O

Cu OH z 1 42504 CuSou t 21420
 Cusoy t 2 NaOH CeeCote z 1 Blue t NazSOy

2 Cusoy t Noyce t Hao CulOHL t Na soy coat

CusOy 51420 eaten Cusoy 4110 Cusoy H2O

USO
750 C
Cleo SO 102 I
9
acidic oxide

23 HW

au
s

Efg
25

26
I

27

EEIESIE.ro
 Green crystalline compound
EHloresces on exposure to air

Wtnh FesOy is colourless resOy 71420

FecOg t HasOy Fesoy t CO2 1 H2O

Fesoy7h20 resoy H2O

2 FesOy

FeOz 5029 15039 DJ

acidic oxide e

FesOy 6 KCN Ky Fe CN t K soy

It acts as a red agent
Auch t 3 resoy Au feelsoy t Raz
GHgU t Gresty 3kg242 t 2k260g t 2Feds

annoy 8Ht t 5 re 5 rest Ran t 4420

3
Cry f t 14Ht t Gre 6fest 26 t 7420

for
making blue black ink
As mordant in dyeing
An insecticide in agriculture
resOy Nhu soy 6420 resOy t 4202
Mohr's Salt Fenton's reagent
 Mohr's salt
green crystals
light

g
e

I
at Zinc Sulphate 2ns 04.71920 White Vitriol
Its a colourless crystalline solid soluble in water

Slowly effloresces in air

Zn t 142504 2nsOy Hz
ZnO t 192504 2nsOy H2O
ZnO t 11504 2nsOy t 110 t coz

2nsOy7110 3 2nsOy 2nsOy ZnO 15039

6110

eye lotion
for making lithophone Bas 2nsOy
Mordant in dyeing
I Consider the
following reactions JEE Main 2020 TAN

Mall t KzCz0y 42504 A t side products

conc

A t NaOH B t side products

B T Hasoy t 4202 C t side products
dilute
The sum
of the total no
of atoms in one molecule each of A B C is
He f Block Elements Inner Transition

m Lanthanoids 14 elements btw Lanthanum Hafnium

ie Ce 58 to La 71
General Electronic config 4ft 5do 652
5d Uf energy levels are close by Its not always
very
with certainty whether the e has entered
posssdiblog
toy
deucidge

All lanthanoids are silvery white soft metals hardness T

with 9 atomic no
Samarium Sm is as hard as steel
Lanthanoids have typical metallic structure
Good conductors
of heat electricity
a Atomic ionic sizes

the
steadily from
Ce to Lu

Lanthanoid
Contraction

I
almost identical size
Zr 160pm
of
Hf 159 pm

Lanthanoids are electrotre metals that commonly occur in their

Ln other stable
are
only when
compounds as o s an empty
ha lled is produced
or
tubshell
a Oxidation States

Ce Celt Eoceuticest 174 V

f fo
Pr Nd Tb a
Dy also exhibit 4 state but only in oxides

Eu East East
Uf 652 Uf 4ft

Yb yb2 ybst
Uf 652 Gf yfl3

Tb Tb TBH
S
41965 Uf Uf
at