1.

Vanadium Pentoxide, Va0s

ammonium metavanadate,
Preparation. It can be prepared (i) by heating VOcl
oxychloride,
NH,VO, or (i) by the hydrolysis of vanadium (V)
 Modera Inorganie Chemity

2NH,VO, V,O+2NH,+ H,O

2VOCl+3H,0 V,O,
V,O,+6HCI
 V,O,
(al
is used: t as a catalyst in a numbermanufacture
ofreactions.ofSome
H,SO, by
eactions are oxidation of SO, to SO,used in the
ntact procesa, (6) oxidation of anthrucene to anthraquinone. (e) oxidauon o
pbenanthrene to phenanthraquinone (di oxidation of toluene to benzaldehyde
phe
acid (e) oxidation of ethyl alcohol to acetaldehyde. iül in the preparation
henzoie

af vanadium glass. This glass is prepared by adding0.02% vanadium as V,O, to

ordinary glass, This glass cuts out completely the harmful actinic rays
injure the eye and brings about fadings of organic compounda. Such glass iswhich
used
particularlyn textile store windows.Such glasses proteet the eyes againstday-
light glare n the preparation of ferro-vanadium alloy which in used as a
sCaVenger in the manufacture of uperial sdeole 1See uer of vonadium
Cp dand FBlock Elementa
465
3. Ammonium
Molybdate, (NH J,MoOP
hi
NHOH s compound is
n
aporating the obtained by the
treatment of o0s
solution to
crystallisation.
Prop a white
alcohol. NHMo0, crystalline powder, soluble in water and
r The solution ensily
of
lo
w h i l e tNHMoOs4 is quite stable insoubie
in
ammonium
-molybdie acid, H,Mo0, H.o molyvbdate
ate in dil. HN0,
n dil HNO, slowly deposits yellow
slowly depositN yellow
-molybaie eio, faMo0 The ich, on
two acids
warming
have
at 70'C with H0 forms white
pressure. hen solution of ammonium
a
different X-ray spectra and
moly bdic Bcia 1s oblained. molybdate and HCl is dialysed,
On heating the
obtained (see the
preparation of Mo0. When salt alone or with
HNO3,
coloa
heated with cone. HNO, and (NH oO
a
phosphate
an or is
arsenate
phosphomolybdate,
NH)GAsO. 12Mo0, tNH,PO,
obtained 12Mo0,is
outon, yellow precipitate of ammonium
or
ammonium arsenomolybdate.
Cad PO arsenomolybaae
+6HNO,
12INH,,Moo,+ 21HNO,3CalNO,+
H,P0 2HH,PO,
NH),PO, 12Mo0, 12H,021NH ,NO
monium pho
t e (yellow Pp
molybdat
12/NH ,Mo0,+ 21HNO, H,Aa +

NHhAsO, 12Mo0,+
Ammonium arseno
12H,0 21NH,NO,
molybdate (yellow ppt
Uses () On the basis of the
above
reactions,
laboratory for the detection and estimation NH,Mo0, is used in the
or POand As0ionsWhen As,SS
AsSs 18 boiled with cone. HNO, arsenie acid, H,AuO, is produced which
a yellow precipitate of ammonium arsenomolybdate, (NHJSAsO,
12Mo0, with
H,MoO
As S,+ 1oHNO, 2H,As0,+ 10NO, +2H,0 35s
As Sy+ 10HNO, 2H,AuO, 10NO, 2H,0 5S +

H,AsO, 12/NH), Mo0,+21HN0,

NH,hAsO,.12MoD, +21NH, NO, 12H O
yelluw py
(i)
(NH ) Mo0, is also used as a catalyst for dehydrogenation in petroleum
and coal technology
 Dhscuss1on o f d Block Element
up
1381

Group 4 B):
Tigg Zr 4o» Hf2 and
VB of the
periodie table consists of four Ku104
GrouPm
co (Zr), Hafnium(H) and
which are itanium
elements whi
called tilantlum group Kurchatovium (Ku). These eleme
elements.
er n of Titanium Group
posof Titanium in the Periodic Elements in the Periodic die Table:
p o s is
taition
Table
sion of titanium group elements
Tnestified by the similarity and gradationin inthetheir
able1s Justifh
same group of iodic
the per ssed
elow
properties as
alse
eelectronic conngurauons ol these elements in the
9)2, 8, 10,2 (3d4s ), Zr (Z= ground state given
40)-2,8,
1 8 , 32, 10, 2 (6d-6s) indicate that the 18, 10, 2 (4d.5s"); HI

oresented by (n-1d.ns showing that thevalence-shell

extra
configurations
electron
Thus
these are d-block goes to (7-1a
bitals. (transition)
elements. All the elements have
ons in the outer most shell. More common oxidation states are +2, *o a
+ 2 oxidation State 1s very unstable and strongly
d reducing that it reduces
so

rater 8nd itself is oxidised to +3 state. +3 oxidation state is

dable and hence the compounds in this comparatively more
state are reducing agents. Since M
3 Oxidation state) have one
unpaired electron |M 10n5
(n-1d1, the compounds
in this Oxidation state are
paramagnetic. Due to d-d transition of
electron, the compounds ot (n-1d
1ons show one band in the visible spectrum
one
and
hence are purple coloured. +4 Oxidation state is most common oxidation state fo
these elements. Compounds of M** ion have the following properties : (i) Since
the amount of energy to remove all the four (n-1\dns electrons to get M* ions
is large, the anhydrous compounds having M*" ion (e.g. TICl,) are covalent. (ü) The
covalent compounds are tetrahedral. (iit) Since the element in +4 oxidation state
has no electron (d configuration), the compounds in this state are diamagnetic
and colourless or white. Lower oxidation states undergo disproportionation into
higher and more lower oxidation states. Zero, -I and-2 oxidation states are
ahown in [Ti(dipy),1°, Li[Ti(dipy)sl. 3.5 THF and LiglTi(dipy)1, 5 TIIF respectively.
H tetrahydrofuran). The covalent radii inerease trom Ti to Zr and then decrease
t lonic radii of M ions increase from T to Hfr , No definite hydroxides,
OH) are known. The hydroxides are really hydrated oxides. These metals, on
ngwith Og above 800°C, give dioxides (MO,) which are stable, non-volatile
nsoluble and become refractory on heating. TiO, is amphoterie (though more
t h a n basic). It dissolves in alkalies to 1orm titanates and in acids to form
compounds. ZrO, and HfO are more basic and lesS acidic. The metals also
peroxides and proxy compounds when reaeted with H,Og Ti and Zr give
iete series of tetrahalides. Hf gives only Hir and Hid MA, tetrahalides
ormed by the interaction of the metal with halogen. 11C4 is formed by
n g TiO with carbon and chlorine. Other tetrahalides of can be prepared

hile Dy the reaction with appropriate HA 1etralluorndes are largely ionie

are predominantly covalent volatile substances
e r tetrahalides
Odes all other tetrahalides are readily nyaroly
sed by H,0. The extent of
1382 Modern Inorganic Chemistry
jec
hydrolysis decreases from Ti to Hf. TiX, compounds are hydrolysed to TiO, while
ZrX, and HIX, give ZrOX, and HrOX Tetrahalides act as electron pair acceptor
(Lewis acid) donated by the donor atoms like F, C, phosphines (R,P), arsines
(RAs), R,O, NHg, pyridine and (CH, N and form complexes or addition
compounds. These elements are very hard metals, good conductors and possess
high melting and boiling points. These are unreactive at ordinary temperature
but combine on heating with O, to give dioxides (MO) and with halogens to give
tetrahalides (MX). Hydrogen, nitrogen, carbon and boron give hydrides (MH17
20, nitrides (MN), carbides (MC) and borides (MB and MB,) respectively. These
are interstitial compounds, very hard and refractory (can withstand high datie
These metals are not attacked by dil. acids or alkalies. This is due 3
temperatures).
to the formation of a protective oxide film. Ti dissolves slowly in hot and conc. aler
acids and explodes in fuming HNO. Zr dissolves in acqua regia and to a smaller ital
extent in hot conc. H,SO. The best solvent for Ti is HF which forms hexafluoro ple
omplex with it. As a result of lanthanide contraction Hf has almost the same
atomic (covalent) ionic radius as Zr. The similarity in size of the atoms and ions
of these two elements is responsible for similarity in their properties. The chemical t
properties of the two elements are so similar that till recently their separation due
from each other was considered difficult. Now these are separated by ionexchange
technique. Ti does not form any normal salt with oxy-acids. However the normal Ithe
salts of Zr ion like Zr(SO,), have been obtained. he
d ca
Group 5 (VB):Vas Nbg and Taza
Group VB of the periodic table consists of three elements which are Vanadium
(V), Niobium (Nb) and Tentalum (Ta). hy
Position of Vanadium Group Elements in the Periodic Table:
Position of Vanadium in the Periodic Table
The inclusion of vanadium group elements in the same group is justified by
the similarity and gradation in their properties. Some of these properties are
discussed below :
The electronic configurations of these elements in the ground state given as
a
V(Z= 23)2, 8, 11, 2 (3d54s ); Nb (Z = 41)2,8, 18, 12, 1 (4d.5s); Ta (Z =73)
2 , 8, 18, 32, 11, 2(5d.6s) show that,
excepting Nb, the valence-shell
configuration of the remaining two elements can be represented as (7-Id".ns. In
case of Nb one electron from 5s orbital gets shifted to 4d orbital and hence the
valence-shell configuration of Nb becomes 4d'5s instead of the expected
configuration namely 4d.5s. The valence-shell configurations also show that the
extra electron goes to (n-1d orbital and hence these are d-block (transition)
elements. It is also evident that these elements have 5 electrons in their valence
shell. They show a variety of oxidation states. The stability of +5 state increases
trom V to Ta. Thus V +5) compounds are reduced all the
way to Ve+2)
compounds
and Nb (+5) and Ta (+5)
V+5) compounds are
compounds remain stable towards reduction.
Consequenty
good oxidising agents while those of Nb (+5) and Ta (*o
being
stable, are not, Lower oxidation states become less stable on moving
dow
from V to Ta. The ionic character
of compounds of each element decreases
WI
 piscussion of d-Block Element

1383
a
cret ofmdscationic
compounds a r e
size
(Fajans's
are more 1onie rule).
compounds (e.g. VCI) are
than ehus,
those of
since V(+2) > V (+3) > V
co V (+3) and (V *
But, on
heating. covalent. These etals Conseque
oera nts give M,05 type they show theirmetals are are unreactive at ordinary
uni
v.Os 1he basic characte pentoxides.
entoxido
Vanadiumreactivity.
also
On
ne
V,O,
g with O
in addition
v,Os 1s
amphoteric
amphoteric (but more acidi
(but gives V
us than basic. This acidie than e s nereases from VO, to Ta,O5
basic) while
hat the metalne ype variation in the basic
ot
s Nb,0s a are
shows cnaracter of the elements character ot V
ding the group. The 10nic
xides
isce tate of the element character of their increases from
pounds are less
increases. For
example compounds
V
pounds decreases
+2) ae e
as the

y+ 1onic while V (+4) compounds a ionic.

ovalent. Since the compounds with compounds
e
rbitals, ese are coloured, while those
these are d

oletely-filled d-orottats are

(e.g.
lower oxidation states VCI)
with lhigher oxidation have
are
d
ae
incompie
states which
o and TaO, have completely colourless, For example the pentoxides have
NO filled aney
however, red-orange. Its orange d-orbitals and are, therefore,
colour is considered to colourless.
the crystal
due to charge transter. structure of the oxide.
The colour of NbX, is
be aue e

be C. VI, halides yanadium, on

heating with considered to
al VCl while Nb and Ta halogens, gives VFs, V5
Al these halides are covalent and are, give only MX, pentahalides (M
On heating with N2 Ha and carbon, these therefore, volatile and get readily
nd carbides (MC and MCa). elements form nitrides (MN), hydrolysed
are interstitial, refractory and Nitrides are interstitial compounds. MC type hydrides
hard while
MC2 type carbides are ionic and carbides
with water to liberate acetylene. Hydrides are reaCt
af hydrogen absorbed depends non-stoichiometric and the
onthe
and TaHo76 are the examples of non-stoichiometrictemperature and pressure. VHo.71 amount
NDo86
these elements to forms the hydrides. The tendency ot
complexes decreases with the
increase of atomic
Thus vanadium which has the smallest size forms the size.
by while Ta gives the smallest number. Tetraperoxy
largest number of
complexes
=V, Nb and Ta) are known. In compounds of [MO2,type (M
these compounds Nb and Ta are in +5 oxidation
state. KalV(O,)4] is obtained by adding
V,
alcohol to the blue solution obtained
treating V,0, with KOH and H,O,. Ka VO,)4] is isomorphous with by
3
KgINb{O,)al and KaTa(O,)4l can also be prepared by similar methods. KalCr(O,)l.
In
el toIV(O),l vanadium also gives [HV(OrOg)}%l HvO)O)%F and addition
In
peroxy compounds. [V(OxOil
ne

ed

he Group6 (VI B): Crz Mo4e and Wz4

nl
Group VI B of the periodic table consists of three elements which are Chromium
E
Molybdenium (Mo) and Tungsten (W). These are called Chromium group
es
elements.
ds Position of Chromium Group Elements in the Periodie Table
The inclusion of chromium group elements in the same group is justified by
S m i l a r i t y and gradation in their properties. Some ot these properties are
Wn

ith Sclssed below

 1384 Modern Inorganie Chemisty
The electronic configurations of these elements in the ground stata

Cr (Z = 24)2, 8, 13, 1 (3d42 Mo 2 = 42) 2, 8, 18, 13, 1 h a

w Z=74)2, 8, 1, 2, 12, 2 (6d6y show that, excepting W, the valen5
configuration of the remaining two elements can be represented as (n1 she
case of these two elements one electron from ns -1)dn
orbital gets shifted to
orbital and hence the observed configuration becomes (n-1) dns' inet -1
expected configuration, (n-1) d'ns, The observed valence-shell confio the
W is the same as the expected configuration. The valence-shell confi on o
all the three elements shows that the extra electron goes to (n-1) d orhOn of
hence these are d-block (transition) elements. Itis also evident that these ele a
have six electrons in their valence- shell. These elements show variable oxid
states. This is because of the fact that the energy of (n-1)d orbitals is almo
same as that of ns orbitals and hence the electrons from both the orbitals eoe
used for bonding. Most stable oxidation state for Cr is +3 while that for Mbe
W is +5. This shows that with increase of atomic number the higher oxidat
state becomes more stable while the lower one becomes less stable. The stabil OXidation
of the hexavalent compounds increases with the atomie number. Chromic acia
acid is
one of the well known powerful oxidising agentS; 1t
gives Out oxygen and reverts
to salt which it
a chromic in is positively trivalent. Molybdic
acid is only
oxidising substance but tungstic and uranic acid are stable acids, devoid of oxidisine
aweak
character. In metal carbonyls like Cr{CO)g,
have
Mo(COg, and WCO) these metals
oxidation state. The most stable chromium salts have the
zero
valency 2
(chromous) and 3 (chromic). These are hard silvery metals. These are
harder than
glass and are refractory. onisation energy values of these elements gradually
increases from Cr to W. The density of these elements increases
Cr to W. All the three metals have high melting and gradually from
bonding points and these
values increase with the increase in atomic number. All the
almost the same
three elements have
electronegativity.
The size of M atoms and M° ions
increase
from Cr to W. The size of Mo and W are almost the same because of
contraction. All the three metals form excellent alloys. For lanthanide
example is used in
Cr
making stainless steel, Mo and W, when alloyed with steel, give very hard
All the three metals combine with S and alloys
Na and form sulphides and nitrides
respectively. All the three metals combine with O, and form trioxides of RO,
in which R(R Cr, Mo or W) is in +6 oxidation state. All the three metals
=
type
Oxy-acids of H,RO, type. The strength of these acids decreases from form
strong acid) to HWO, (very weak acid). Their H,CrO, (very
oxidising properties decrease irom
H,CrO, to H,WO,. All the three metals form oxychlorides of RO,Cl, type. These
are obtained
by dissolving R0, oxides in conc. HCI in presence of
direct addition of Cl2 to H,SO, Or D
RO3 oxide.
Position of Cr in the
A look at the
Perioc c able
position of Cr in th periodic table shows that (1) Cr
Mo and W in the
same
sub-group (2) Mn
lies (3)
and Fe lie to its right hand
wi S
15
acting bridge element between the elements of
as a siae
Thus the
position of Cr in the periodic table is sub-groups V1A
An s
of Cr with
the above said justified by discussing the
simi
elements. These similarities are discussed as
tolo
 Gceoup 4 (CVB)
VB the pesLiOdic tale censists e 4 elrmoris uhith
GTeup
CHe Titaniun&Ti), Z YOEhiun tzr) , Hafhun CHf) ahat Kgchatevium
callecd titonium qeup lemenks
These elements Bte geneyaliy
ku)
Titaniun Gtoup

ElecErenic cortigurattern
The elettpnic corntiguations e dhese olements un the gveur
State quen a5

TICz-22) 3d, 4s Hf Cz 72)- 5d bs

zB (z-40)- 4d2 5s
Indicate t a t dhe vatunte shell cenfiguratien can be
epTesented by (h-)d? ns
Ocidaien gtctes
ALL the elements hane 2 etectens tn the eute mest
Siell MeTe cemmen cidation states asa +2, 13 Qnd t4
2 cdatsn State s very wnstable and so Strengly
ucucng agend that t reduces uwater and ttset kidioed to
+3 State
f3 ORidat eon Stote is mnpaatlvely move table and

Sune
herce te cernpeunds in this state evedueing agent.
M13 ions in dus Cxidatian ate hawe cne upauircd electrsh hende

ae paiamagreEC anat they ce purpte coloused.

thy
+4 0XLdatieh state s mest Cenmeh OxLdatieN tate for
thase elcmont M ipn hove he folowing preperties
ane tha amount energy ao Temove all te
4 electors tget n4 lons in donge, They a tovalent
The Covaltnt cempounds ast tewahedral

Ths Compounds a dliamagneHC and

telourtess white
 Louex oicdattbn States undexge dispropontionatioh Unto
higher and more owex oxidatton tates
zero -2 Oxidatton States su haon in
Ti Caupy)a1,
TL Cdiphy)31. CLiaC Ti Cdipy)) xespectively
Radié
The cevalant vadii increases f7om Ti to Zr and than decrense
HF
The Jenie stadi t
M ions increases frem to HfH
Hydaoouides dioouidts
There No duftnlte hydroaides, MC OH)4 au knoun. The
hyd7oxidcs ce eally hyptrated oictes
Thase metals, eh
heating wtth 02 Qbove 8oo'c
9ves
dLcxides CMO2) uhich ae Stabo, hon volatile ard insoluble
Qnd becomE Tetractory hating
en
TiD2
Qmphetertc. tt dissolves in alkalies te fozm
tltanates and in acids to fom
titanyl cempeunds
7702 ancd Hfo e nore b0stc and less acidic
HRi * giro 7hese metals als0 fOTms pookides
Ohd
pro 3xy tompounds tohen Teacted twlth HaO
other ChaactETistics
Thoce elemertS Qs0 very haa metals,
g8ed cenducps
Ound peses ess hugh melting and beiling poinus
These o tun7eactive to at
7dirnky temperatoe but
Combere heating
on wlth
02 to ue dionides
(MO)
twith hokegens give teLrahnlides CMK4). Hydaegun ,
cebon and beren 9ives
hitrogn
hydndes, nitrites (MN), cachtdes CMmc)
and bondes (MB MB,)
vespetkively
oxaep (VLB)
Goeup Vi8 e pLEdUt tabe censists e 3 clwrds whuh ae
Chcmium CC)
moty bdltnuwn (Mo) and Tungsten (W) These aou called
Ch7orniun g7eup lencnts
chzmiurn Group Flemonés
Eloctrenic Cenfigurakisn
Tha oloctonic cortguaatiens ttese etornonts Lh dhe
Stote s gven 08 gund
CT
Cz=24) 3d 49
Mo CZ-42) -3 4d5 55'

WCz=74)-5d es
Show dat, exeptinig w,t valne-chtlD eEntiguaatioh te
7emaung tiue eamords can be
vpresenteds os (n-1) d" na
Oxidotisn state
1 ts also evident thot hesa
tay valerna-shet oarnen hae 6eDectrons n
Thise elerpriSh0w vasiable oridatton &tates
Ths ls becoua te fact that t t
Cahito k ourost the 6une Qs eragy Da
that hs 0hitas
MB&t Stablo teiceHDn tate
for C Ls t3 whilo tht fo
MO ad W t5
>
Ths Shous tat with uncease atomLt mumbo the
ocidotiph state beOTRS n 0 abke tuhilo, tfn lo uez Bhe
hugher
Stako bebmes ess
The &tabllity he hioconalerd Ctnpounds tn creases
thi atomic humben with
ther ChoHQct ONLSALS
Thes as had s l y hetdis
These Q hascic tan giass and ase eNacADV
Ternistlon enizgy values e thes elemunt 93adualily thcrtaszs
frsm Cr W
he ciensity thse elmorts h eas4s 9radually frem
C to W
and beilbng peots
A l l ths tree mctals have high relting
nume
and these elluus incr eoses with te increost in azsmit
Au ts hree camonts hane almost une tlecerpnegativit

The size y Matoms ana MeT tensinomse 7em

C7 D W
AD te ahree me4uls fom aloys
All the thrce netals form oaychiordks
S9eUP 5CVB)
Gosup 68 y the peugdic dable Cosks etoce ctunents which o
vahadium CV), Nieburn (NB) a d tehtaluun CTa)

Vanaduum 70p Olements

Qdecnonic configuuoHen
The electrehic onftginatlon these clurnents un tha one gaocus
Gtate is given qus

VCz-23)-3 4s
Nb C2-4D- 4d1
5s
Ta C2
=Ta)-sd3 6s
Sheu that,
ezpepting Nb, dhe
valerre-shell aonfiguaatich te
0nainihg a etectnen etements con be suproseracd as n-)d ne.

Oxidatien state
t is evident that these olcrroits have 50lectrona in
theis valerte shele

They &hew a
vasuety e} ocidatioh statea
The GLablity y t5 tate intrca8es 79m V t To. t
Couipeurrds eo teduced all th ua to vCt2) compourds
and NbC+5) and ta. C 45) Compsuurds axe xemaih Stohle dbuas
reducttiorh
sequhtiy vCts) compou.nds ou good vridi.sung agrts
hils Hese Nb (5) and Ta
(+5) being table 0se het
Lower okidbtton States beome docs Stablo. eh

novlhg douh f7em Vto Ta.

 Tonic ChaHactey
Ionic Chasact f Compsurds y each onent ccccosee

tith he dacrcasecationic Guze hus cinta

Véa) > ve3)s VC+4).
Cxides
These metas ave nreative at 0vdinaHy tm peanture Bt
Bh hating they Sheu
hur eactuvity
h taathg witho te ement gives MDs type parinovide
Varadium also gives V,04 h additton to V,Og
The bauc chanete y Ma0s ypa oaides ncreases frem VUs

T hV2Us
s ampheteic twhtlo Vb, Dg and Ta,Os Less
Qcidin than basic
This ype Vasuotic) in dha basic Chavacc y Ma0s oxuole
ShOuS tat e menilic Chasoceer ey dha. elamont. ihcveases femV so Ta
en
diacrcuding th 97oup.
eleuz q elerierts
3 Sira the conpounds with Joee oxiclotish iates haue iheplte
t: Datitols dase o Celouzed uhle tese wih highe caidkatieh States hae
Cmpketeictiy- flled d crhttals aoee celourless
The perkcaudes hanly Nb,Og and Tms have
4-rhttal
cemple teky fluted
a colcood a0c i heuce,
7ed-0nge dutt te chasuge
tansfc
vanoctium.on hsatung9 ith halogen gues VF VCls VCL4, Vols, VT
halidks uhitu Nb ard Ta gue eniy }X6 pontahalicdi 0 ovalt, velatile
Onct get 0aklly hydotyd
Thdirg hase ehnents to f a the compleaus decoxats
Lolth ahe ncease c SL