D

f Block Elements
I

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 Leto Lu

Ig omitting

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 d5dd

config

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

beingpoints

strong metallic bonds w the

atms these elements are

of

responsible for the high 1

top
Tc have
Mn
abnormallytow

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

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

Ionidinnergy

Transition metals are lers EI than stoles

I I E
of Ee CI very high because of their fully filled

Leg are

n S2

config

I 2nd I E
of
V LEI MI

Nic Cee Zn

Oxidation states

It

M rant ranta


4 Standard Electrode

Potentials

Thermodynamic stability of a compound x 1

I E
ofmetal

IE t IE2

e.g Nit

Ni 2.5 103 Kymof

2 60 103kHmol
Pt

Pt

NIH compounds are thermodynamically more than Pt

compounds

IE t IE t IE 11Ey

Ni 11.3 103 Kolmol

g 36 103 KIlmol

Pt

Ptt compounds are

relatively more stable than Ni compounds

Kaptus exists but K Nick doesn't

In solutions stability depends on electrodepotentials

DHsub DHHyd
MCD

Mlg s MtCg in Cag

0.25

Io Isr
MID

DH AHeeb I E t DH t

wyd

Qualitatively the stability of transition metal ions in different

ox States can be determined on the basis

of elected data

More ve the SPI Os in

Higher stabif avium

M M SRP 105

e.g Net is more stable

Na N SRP 1.8 than MH


Trends in the MTM standard Electrode potential

Element

MMM SRP

Ti 1.63

V l 18

Cr O go i

Hn l 18

Fe 0.44

Co 0.28

Ni O 25
m

cu t 0.34

Zn 0.76

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


of fo p

from the trend due to

stability of ME d5 and 2 Cd

config

No
regularity due to irregular variation of LIZ

SRP values are lower in magnitude compared to S block

metals Due to
high atavism energy tree

Zn has low Ha and fairly large EHuya kn But

it has also low SRP C01,6 due to high IEy Ez

Cee has tver least reactive metal

14 The to transform

Explains its inability hingy

to liberate
cu wit g is not

Hzf ids

FalancedTy
its DIIHyd

Only oxidising acids HILO and hot cone Hasoy 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 502 t 21420

12

papist pan

tog eg

th

HI TrendsinM3tlM

sR

3 More stable able

Soft is stable due to noble gas config hence IRP

very

Mn is stable due to discernfig

particularly


fR y

e3

Cr o

ft

The comparatively lowvdue for V is related to the stability of

due to half filled tag in octahedral field

tag

Trendscinstabilityofhighero.SI

mmmm

M Properties

BM
mmmm

e m

I
Mn 4503d

Colour in compounds

i i


Effong E
I
I

err

2 I 4
5

Mixedoxide t

ComoOy Coo Moors

ZnfezOy ZnO t fc2org

Fezoy Feo t rezong

Mnzoy LM no Mn Oz

x Pb304 2Pbo t Pboz P Block

Spied These are special type mixedexides in which

of

the oxygen atoms constitute a FINE 8 the medians

occupy the internals



g Znfezoy normalspinel

e rest occupy II

zn4 occupy V

12 3

re

RIX inverse spinel occupy
rest occupy

II

HEfsaltscontainingoxoanionsofmetal t

The oxides Cros Moog Hog

14h20 are strongly aeolic

ag alk ali solutions form

There oxides when dissolved in

discrete

ometal im
ox e.g

Crout Cr Of Moo f hiOy Mn0y

PotassiumDichromate Kacrally

Chromite Ore chromates Dichromates

BasicsEn

4Fear

y
8
NazWg 1702 8 Nazcroy 2k20g 8Coz

Yellow

Yellow solution

is filtered a acidified with

of Nazcroy HzSOy
to give

solution from which orange Nazcrao

a can be

crystallized

2
Nazcroy

2 Ht Nazczo t 2Nat t 110

Yellow orange

nge

Sod dichromate is more soluble than Petdichromate

t 2K 2 NaCl

NazcraO KILO

Orange Crystals

Kaczor is preferred Nadrgoy

over as a
primary standard

in volumetric estimion b'coz Nazczo is hygroscopic in

nature but K 20 is not

Orange red

crystalline compound

Moderately soluble in cold water but freely soluble in hot water

liberates 02 on strong heating

2kg420 2K Croy t CraOg t

3Oz

On healing with alkalies its converted to chromate

KIKO t 2KOH 2K Croy H2O

Orange Yellow

It Crop and CLOT

exist in egdlibn.am and are inlerconvertible

by altering the of the solution

t 2Ht CryOf

2Cz0y2 f 2 HCroy F t H2O

deep blue

Acidified K 20 solution reacts with H2O to give a

solution due to the formation

of CIOs


o 72 72

I 0
if 0

co o Cr Ko

o o
OT Esto
0 Em

chromate

dichromate

Its oxidising action can be represented as follows

6

Cr
MII t GE EE

2sfag 7420 et

It oxidises

I Iz so said

Snu shut As033 Asap

3Has 6Ht t IS t Ge HE CX U Br 1

felt pe3

tt

ChlorideTes TwhenKgCra0

is heated with conc tyson in the presence

of

soluble ch de sett the red vapour

a
orange of chromyl

chloride Cry is formed

ouiffrecr.ae Ifs NaTroytrz7

1
filtered

TOEI

444
1k

IET

I PLEIN

Nat ago Hao

1T

c
I

y ppt

ydI

oYp

dL

it

ist

10

E I

Hu

Il

n 4

tht I

V I

2
3

2 16

Cuco

CucoH z

I
E

Hg12

K2lHg2y

ScarletRed Soluble

leg 129

anganateapermanganate

KMnoy prepared from Mn02 in the presence of alkali

is

when dark green K2Mn0y is formed which further

disproportionate to form KMnoy

2 Mno t UKOH t 02 2K2Mn0y t 2h20

3 annoys t 4Ht

2 Annoy Mno t 2420

Commercially its prepared

by the alkaline oxidative fusion

of Mn02 followed by the electrolytic oxidation of Mnof

fused with KOH Electrolytic

Mino Mn0yd

2 Oxidised with oxidation annoy

air or KNO GET in alkaline Purple

Soen

In the Lab Mn salt is oxidised

by 52082 to Mn05

ie 2 Mn t 55082 t 8420 2 Kanai 105042 t 16Ht

O O
I

11

Mn Mn
O

04 1 O ok 11
0

Tetrahedral Tetrahedral
Manganate ion

permanganate ion

Paramagnetic Diamagnetic

ag ag

Properties

Its a
purple coloured crystalline compound

Not very soluble in water

GUg1100g at 293K

It decomposes at 513 K

2 KianOy K2MnOy Mn02 t Oz

Its intense colour is due to the ligand metal CT

It has weak temp dependent paramagnetism

tt Oxidising Reactions

of Kiang

Mnoy t e Annoyed E to 56 V

Minori t 414 35 Mno t 2420 Eo 11.69 V

n0I t 814 5e Mn UHao E 1.52 V

Mnai 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

µ OH
Manoj

Mn oxidises annoy Mno oxidises

I Iz I 105

pet fest 032 5042

thiosuephate

Sof coz

521Has s Mn MnOz

5032 1502 5042

NO

NOI

HCHO H OH

X
Ct Bi E
X2

19202 Oz

Hulu

KMnoy is not used in titrations involving b'coz

Ct is oxidised to Cf

Used as an oxidant

Used in bleaching wool cotton silk other fibres

of

decolonisation of oils

Alk KMnoy is called Bayer's Reagent

Used in qualitative analysis for detecting X so a Soi

ele

Not a primary standard is always standardised with

a standard solution

of oxalic acid
019 Khanoy acts

as an oxidant in neutral alkaline as well as

acidic medium The products obtained from it in 3

final

conditions are respectively

Annoys Mnt and Mnt

Mn02 Mn02 D Mri Ans b

c MnOz MnOgi Mn3T

Mno Mno Mnt

20

21