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
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 state
91 d d
Zn Cd Hg are not transition elements
All transition elements are d block elements but reverse isn't true
10
General electronic config n 1 d ns
All there elements are metal
3d series Sc to Zn
yd series Y to Cd
Sd series La to Hg e to Lu
omitting
Gd series Begins with Ac but is incomplete
[Link] tz
In transition elements valence outermost well as
e are present in as
inner d orbitals ultimate t penultimate
Cn Dd
Unexpected e config
5 due to small energy gap b w
Cr 24 Ar Us 3d
US 3d
stability of filled
to
9 129 car ys z
half filled config
aiiii
mannn
[Link] ii
Fe Co Mi are all ferromagnetic and all 1191120767
form
ions in water and tally ion
3 O S is Fe less common Co and
very
common
for for
very
rare
for Ni
Ti ahard silvery white metal is the least dense of the
transition metals Its most common ore is Rutile Tio
Ti 021st 2C 15 24 1g Tilly g 21019
D 1,2ing ie rA
Kroll's Process
Ti is 21Égazle
Cr is found as chromite FelizOy
Transition metals 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
Unexpected e config d5 d
Mo 42 5s 415
Pd 46 5504110
Ag 47 5s 4110
Unexpected e config
Pt 78 651509
Au 79 6s 5110
Physical Properties
Melting boiling points
strong metallic bonds w the
b
atoms these elements are
of
responsible for the high mp
b
p
Tc have
Mn
abnormally low
map
Enthalpy of Atomization
59 The dip in the map of
Ud
39 Mn Tc Re can be
sd explained on the basis
their half filled
yd of
3d d orbitals stable
e are less delocalized
Weaker metallic bond
2 Metallic character
Both ns and n 1 d é participate in metallic
bonding
d é
strength of bond α No
of unpaired
Cr Mo W have max no unpaired d e and are
of
therefore hard metals whereas Zn Cd Hg aren't very hard
metals due to the absence é
of unpaired
3 Variation in atomic ionic radii
along the period
5d
ad Tsmavariaion
3d
At the end there is
a small in radii
Irregularities can be explained on the basis
of
Zett
Shielding Effect
Near the end series the é e repulsions b w added é
of
in the same orbitals are
greater than attractive force of
Zett
r
Atomic radii down the group but are almost same for
Ud 5d series due to Uf orbitals before 5d
filling of
which results in a
regular decrease in atomic radii called
Lanthanoid Contraction
Due to Lanthanoid contraction following pairs have almost
identical sizes
Ir Hf Nb Ta Mo W
160pm 159 pm
4 Density in metallic radius coupled with in atomic mais
the density across a period
In is an exception due to large atomic volume
Ti V Cr Mn Fe Co Mi la
IEainnergy
Oxidation States
Miss Migs
DHsub É MMG
[Link]
n'teas
Standard Electrode Potentials
Thermodynamic stability of a compound α
effetal
e IE IE
g Nist
Ni 2 5 103 Kolmot
ml pz2t
Pt 2.60 103 kJ
ᵗ
N compounds are thermodynamically more stable than Pt
compounds
IE IE IE IEy
Ni 11.3 103 Kolmol
Pt 9.36 103 KJ mol
i Pt compounds are
relatively more stable than Ni compounds
K2PÉcl exists but K Nill doesn't
In solutions stability depends on electrodepotentials
MCs b Mig s Mt g 4 Mt ag
DH ΔHsub ΔHHyd I E
Qualitatively the stability of transition metal ions in different
ox states can be determined on the basis
of electrode potential data
More re the SRP Higher stability 0 [Link] medium
ᵗ
e M M SRP 1.5
g ᵗ N us m
N N SRP 1.8 than M
SRP α Power
Oxidising
ᵗ
Trends in the M M Standard Electrode potential
51
Ee 11
V 1.18
Cr 0.90
Mn 1.18
Fe 0.44
Co 0.28
Ni 0.25
Cu 0.34
Zn 0.76 indicates that In is more preferable
Values of E for Mn and Zn are more ve than expected
ᵗ ᵗ
the trend due to stability Mn ds and 2n d
from of
config
No
regularity due to irregular variation of I.E IE
SRP values are lower in magnitude compared to s block
metals Due to high atomization
energy
I E
Cu has tve SRP The to transform
high energy
ᵗ
Explaints its Cu Cu g is not
inability balanced its ΔHHyd
to liberate He from by
ᵗ ᵗ
Trends in M M SRP
TMrestable TMrestable
Sc is stable due to noble gas config hence low SRP
very
ᵗ
Mn is stable due to ds config
particularly
FROST
o
d d
transition
Mixed oxides
CoMoOy COO MOO
Infe 04 ZnO Fe203
Fezly FeO Fe2O3
MnzOy 2M no Mn 02
Pb3Oy 2PbO PbO2 P Block
Spinel These are special type of mixed oxides in which
the oxygen atoms constitute a FCC lattice the metal ions
occupy the interstitials
e
g ZnFe20y normalspinel rest occupy OHV
2n ᵗ occupy THV
FeFé20y Inverse spinel re on
occupy
rest occupy THV
Salts containing oxoanions Metals
of
The oxides Cros Moog NO Mn20 are strongly acidic
There oxides when dissolved in
ag alkali solutions form
discrete oxo metal ions e
g
Croy Cr20 MoOy WOy Mnoy
1 Potassium Dichromate K2Cr20
Chromite Ore chromates Dichromates
4feÉ NaW 0 snaÉ O 2420 802
oxagent Yellow
Yellow solution acidified with
of Na CrOy
is filtered H2S0y
to give a solution from which orange NazCr20 can be
crystallized
2NazCrOy 2H NazCr 0 2Nat 120
Yellow orange
Sod dichromate is more soluble than Potdichromate
NazCr20 2kV K2Cr20 2 Nacl
Orangerystals
is
K2Cr20 preferred over Nazer207 as a
primary standard
in volumetric estimation b'coz NazCr 0 is hygroscopic in
nature but K2Cr20 is not
Orange red crystalline compound
Moderately soluble in cold water but freely soluble in hot water
liberates 02 on strong heating
2kg120 2K Croy 203 3 02
On heating with alkalies its converted to chromate
K2Cr20 2KOH 2K Croy 120
Orange Yellow
CrOy and Cr20 exist in equilibrium and are interconvertible
by altering the pH of the solution
2Cr20y 2H 2H roi Cryo H2O
Acidified K2Cr20 solution reacts with 1202 to give a deep blue
solution due to the formation
of Cros
0 72 M 7
1
Mar
0150
o
04 O
chromate dichromate
Its oxidising action can be represented as follows
Cro 14H 6é 2Crt 7H20 E 1.334
stable
It oxidises
I 12 503 so
Sn shut As033 As0y
3H25 6H 35 be_ HX X2 X U Br I
Fest rest
for detection of Ce ions
Chromyl Chloride Test
When K2Cr20 is heated with conc Hasoy in the presence of
a soluble chloride salt the orange red vapour chromyl of
chloride Croall is formed
[Link] tEt1e
filtered
as
FEEL
Diff
lJΔ
N2 Cr20 H2O
Orange red
vapours
Manganate permanganate
KMnOy is prepared from Mn02 in the presence of alkali
when dark green K MnOy is formed which further
disproportionates to form KMnOy
2 Mino UKOH 02
2K2ÑnOy 2H20
3 MnOy 4H 2mn05 Mn02 2H20
Commercially its prepared by the alkaline oxidative fusion
of MnO2 followed by the electrolytic oxidation of MnOy
iii
[Link] iinoi
Green
iiioPurple
in alkaline
soln
In the Lab Mnᵗ salt is oxidised
by 52082 to Mnoi
ie 2Mn 552082 8H20 2mn05 10504 16Ht
in at it Mnoy
0
08
0
018
Tetrahedral Tetrahedral
Manganate ion Permanganate ion
Paramagnetic Diamagnetic
Properties
Its a
purple coloured crystalline compound
Not very soluble in water
6.4g 100g at 293K
It decomposes at 513K
2KMnOy K2MnOy Mn02 02
LMCT
Its intense colour is due to the metal C T
ligand
It has weak temp dependent paramagnetism
Reactions Ox Power SRP
Oxidising of KMnOy
Minor e Finout E 0.56 v
iñnoi UH 3é Mino E 1.690
2H20
MnOj 8H 5é Mn 4H20 E 1.52W
Mnoi at 1H 1M should oxidise H2O but in practice
ᵗ
the rx is extremely slow unless either m ions are present
or the temp is raised
t
Mno Mn oxidises Mnoy MnO oxidises
I Iz I 105
Fest Fest 52032 5042
thiosulphate
C20y CO2
ᵗ
52 15 S Mn Mn02
5032 502 5042
NO NO
HCHO HCOOH
u Br I
X2
4202 02
KMnOy is not used in titrations involving tell Ct b'coz
I is oxidised to U2
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 it so a soul
ete
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 final products obtained from it in 3
conditions are respectively
a Mn0yd Mnt and Mnt
b Mn02 Mn02 I Mm't Ans b
c MnOz Mn02T Mn3T
d Mno Mno Mnt
silverritscompountaqua Regia
Dry or Moist
air
Metallic Silver Has
112504
HMOs
Hot conc
HI
UAg 8kW 2120 02 4K Ag CNI UKOH
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 t CHECK Ag C d 2nA NO
Toller's Reagent white Ppt
H
a Copper sulphate Cusoy 5h20 Blue vitriol
Cleo HzS0y CUSOy t H2O
Cu OH z 1 42504 CuSou t 21420
Cusoy t 2NaOH CucoHad Blue t
Nasty
2 Cusoy t Nazca t 110 Culon t Nasso t Coat
50
Cusoy 5120
Iggy Cusoy 4110 Cusoy Hao
Cusoy
GO t SO O 750T
9
acidic oxide
Green crystalline compound
Effloresces on exposure to air
Anh Fesoy is colourless
Fesoy 7H20
FeCO 42504 Fesoy CO2 H2O
Fesoy7H20 [Link]
2FeSO Fe203
50 50
Tdcoxide
Feso 6 KCN Ky Fe CN K 504
It acts as a red agent
Aull 3Fes0y Au Fea Sou Fell
6HgU 6resoy 3kg242 2 Fe Sou 2 Fell
Mnoy 8H 5re 5 Fe Mnt 4H20
Cryo 14H 6ft 6fe 2Crt 7H20
for
making blue black ink
As mordant in dyeing
An insecticide in agriculture
Fesoy NHy soy 6H20 resoy 4202
Mohr's salt Fenton's reagent
Mohr's Salt
green crystals
light
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
f Block Elements Inner Transition
Lanthanoids 14 elements btw Lanthanum Hafnium
ie Ce 58 to Lu 71
General Electronic config 4ft 500 6s
Sd Uf energy levels are close by Its not always
very
possible to decide with certainty whether the e has entered
Sd or Uf level
All lanthanoids are silvery white soft metals hardness 4
with 9 atomic no
Samarium Sm is as hard as steel
Lanthanoids have typical metallic structure
Good conductors
of heat electricity
Atomic ionic sizes
I
steadily from
Ce to Lu
Lanthanoid
Contraction
I
almost identical size
Zr 160pm
of
Hf 159 pm
Lanthanoids are electroeve metals that commonly occur in their
In other stable
are
only when
compounds as o s an empty
half or
full f subshell is produced
Oxidation States
Cest cent Ecent est 1 74 V
f fo
Pr Nd Tb
Dy also exhibit 4 state but only in oxides
Eu Eat East
45652 477 456
t
Yb 45 yb
4514652 45 4513
t
Tb Tb Tb
47965 478 up x