CHAPTER

d- and f- Characteristics of
44 Block Elements
(Transition and Inner-transition
Elements)
d-block Elements: Transition Elements
What are d-Block Elements ?
The definition of d-block elements has already been given in chapter 3
Whny are d-Block Elements Called Transition Elements ?
The d-block elements are called transition elements because they exhibit
transitional behaviour between highly reactive ionic-compound forming s-block
elements (electropositive elements) on one side and mainly covalent-compound
elements (electronegative elements) on the other side)
forming p-block Table.
Position of d-Block Elements in the Periodic
located in between s-(ionic-compound forming elements)
d-block elements are
elements) block elements
as shown in Fig
and p-lcovalent-compound forming table and
a r e located in
the middle of the periodic because
elements
44.1. Thus these of the periodic
table. It is
4) and subsequent periods of
occur in fourth (n elements that the properties
=

and p-block Thus

of their inclusion
in between s- and p-block
elements.
between those of s-
intermediate (VIIB), 8, 9,
4-block elements
are
(IVB), 5 (VB), 6 (VIB), 7
3 (IIIB), 4
the elements of groups to this block.
and 12 (TIB) belong
10 (VII), 11 (IB)
p-Block Elements
-Block Elements

d-Block Elements

(Transition Elements

Form covalent

how intermedhate properties compounds

Highly p-block
and
reactve b e t w e e n s-

metals and elements

LL
form iont
compounds
table
the periodic
elements in
d-block
Position of
Fig. 44.1.

1347
1348
Modern Inorganie Chemistry
Electronic Configurations of d-Block Elements.
omplete and valence-shell
o Zn (Z 30; (6)Y (Z configurations
=
of d-block elements namely la) Se
39) to Cd (Z= 48); (c) La(Z 57),
=
g Z =80); and (d) Ac (Z- 89), KulZ Hf (Z =72) =

ven in chapter 3.(From these 104), Ha (Z= =

105)
havebealready bn
configurations these points may
oms ol d-block elements two outermost noted f) Tn
partially illed while shells [i.e. nth and (n-1th
the remaining inner-shells [i.e. 1st, shells] are
Completely filled. ) With the
exception of Cr, Cu, Nb, 2nd..n-2Nh
Mo, Ru, Rh, Pd,
shells]
and Au, in the atoms of
these elements the ns-orbital is completely filled (ns
Ag,
cOnnguration) and the differentiating electron enters (n -)d
vialence- shell configuration of most of these elements orbital Thus the
Group TB) to (n
1xd ns varies from (n-1k'. na
(Group IIB) configuration. The
-

groups IlIB, IVB, VB, VIB, VIIB, IB and VIII, elements of the
IIB
belong this block as is evident
rom their
configurations. fi) It may be noted from the valence-shell
of the atoms of
these elements that in the elements like
Cr, Cu, Nb, Mo, Ru,
configurations
Pd, Ag, Pt and Au one or both the
electronsfrom ns orbital get shifted to
Rh,
orbital and hence such elements have one or no electron in ns
orbital
(n-1d
two electrons in ns (instead of
orbital). This type of shifting makes
filled and such (n-1)d orbitals are the
(n-)d orbitals half-filled or
completely
stable than other (n-1)d orbitals. Thus the
shifting
more
orbital to (n-1d orbital gives more stable of one
or both the
from ns electrons
configuration to the atom.
Cassification of d-Block Elements.
Based on whether the differentiating electron goes to 3d, 4d, 5d or 6d
d-block elements have been classified into four series viz. orbitals,
3d, 4d, 5d and 6d series
as discussed in chapter 3.

General Characteristics of d-Block Elements

Some important characteristics of 3d-series elements are described as follows:
1. Metallic Character
All the transition elements are metals, since the
number of electrons in the
outermost shell is very small, being equal to 2. They are hard, malleable and
ductile. They exhibit all the three types of structures face centred cubic fec),
hexagonal close packed hcp), and body centered cubie (bec). Metals of VIII and
IB groups are softer and more ducuite tnan other metals. It appears that covalent
and metallic bonding both exIst in the atoms of transition metals. The presence
d-orbitals favours covalent bonding. These metals
p
are good conductor
electricity.)
of heat and
Volumes and Densities.
2. Atomic
volumes and densities the elements of
mmic o 3d-series are
given
below Bc Ti V Cr Mn Fe Co Ni Cu Zn
Elements

Atomic volume : 15.0 1.66 8.3 T.2 T.3 7.1 6.7 6.6 7.1 9.2
3.0 4.5
4.5 6.1 7.2 7.4 7.8
(em (glem")3.0 8.9 8.9 8.9 7.1
Density
 hracteristacs of d- and f Block
Jhlock elements Elementa
ihe (n-1d
electrons in.
ns
sub-shell is filled 1349
oments compare
hese elements
compared to leads
to the and the
he donsities of d-block those of the comparatively increased nuclear
LA
IA and IA elemen elementa
elements. This is are neighbouring low atomic
and
charg o
volumes
-
very high in p-block
3. Melting and understandable comparison to those elementa
The melting and Boiling Points
because of their of
group
boiling decreasing volumes
given below points of the
elementa of Lst
transition
Elements Sc Ti V
series are

Boiling point Cr Mn Fe Co Ni
rC) 2730 3260 3450 Cu Zn
Melting point 2665 2150 3000
2900 2730 2595 906
rC) 1539 1668 1900
1876 1245 1536
It is evident from the values that 1495 1453 1083 419.5
the d-block elements have high melting and
bouling points. It shows that they are held
the table that the melting and by strong forces. It can be seen
boiling points
the series. In this region the elements havehave highest values in the middle
from
maximum number of
electrons available for bonding. The elements also exhibit the
unpaired
dates in this region. The trend in highest oxidation
melting and boiling points shown by 3d-series
elements is also followed
by 4d and 5d-series elenents. However Zn, Cd and Hg
have relatively low values (melting and boiling points for these metals are
in= 419.5C, 906° C; Cd = 320.9C, 765 C and Hg =-38.4 C, 357C
he reason of these low values is that these metals have completely filled d-orbitals respectively
t h no unpaired electron (Zn = 3d.4s with n = 0, Cd - 4 d 4 with n=0 and
d 6swith n = 0) that may be available for coralent bonding amongst the
ms of these metals and is responsible for high melting and hoiling points
Generally the melting and boiling points of d-block elements increase on
of Ag lower than those of Cu
g a group. Melting and boiling points
are
n
. T h i s can be explained on the basis that both Cu and Au have greater
state than +1, suggesting that in these
t o acquire higher oxidation
for metalie bonding i8 to a greater extent
involvement of d-orbitals
fhans in heAg
h
4. Atomic (Covalent) Radii.
elements are given below
atomic (covalent) radii of d-block
Sc Mn Fe Co Ni Cu
Ti Cr
144 A 1.32 1.22 1.18 1.17 1.17 1.16 1.15 1.17 1.25

Te Ru Rh Pd A Cd
Y Zr Mo
Nb 1.25 1.25 128 1.34 148
A 1.30 1.27
145 1.34
La H W Re Os Ir Pt Au Hg
Ta
88 A 144 1.34
1.30 128 1.26 1.27 1.30 134 149
Positlen d- Block elemends
d-Block alements ase located dn betueen s-
and p- bloCk ecements Thuse
hesa elermonts a Looatad
in e middl the posuiodic table and occuw in fous th
Cn 4) and suhseguent petiods f the peuedic tahle . t
=

s becaus0 e their dndlusish in ketuccn s- and p- block

eleents het te psopetties d- block 0lemens g ase
drtetnediate betucen those gs- and p-bleck elmerts Ths
the clements fgreup3 4.5, b, 7, S.,2, /0, 1,12 belong to
this blok
oLaseificatien d-BlOCK elements
Based on whether the difjoxentiotihg etectron goes t
6d orbizals, d- block elomart.s have ben
3d, ad,5d or
Classifed inte 1our Soies iz, 2 4d, 5d and bd sexues
 3-Slk Eleents
0Why e d-Boc damenis lkd Danaan Eeneus
The d-bick eiemoris o alled
tarsite elser becas
they ohubit t70anaeiral beoviou tetueen highly reactive
nic cepsand joming -biDCK clmcnes C Gectae
pOREiue cncnts) en e Side ondmalnly CEuRient ceimpturd
ftumung P- bleck eanare s Coku ngakie earavte) en de d ads

Eazaic adigan0i d-H Eenepts

onpltte and valau-shll orfigntios
4 d-block dianerts
nly Sc ide 2-30)
y39) to 49)
2a(T) to Hf (72)
Hg(8o) to AC(99)
t Ha (es)
u(104) a paveially
d block dencorts
tue Gute rnee chelis
atos
Shel a Gpleey filled
uh 70rairg urn PL and Re un th
fled h, Ri, By,
ht onptisn cz.Cu,fve, Ho,E, the
d
h-s ohital ë ornpirtoly uglad ard
onors due ouncrts dhs the
ertssth-Dd etital Thus
thee tanent SVaLCS
clttëven
dre z ertiating g mest

valerce-shcl
corqu atien
cer4iguoatisra
from Ch-1)d'. vaitra-sholl
duKE
frn the cunents
hat an d
t
heted

may
be
c6
dTent
and
Au
o r both r b i t a l
ard
aterna Ph br)d
Pd, Ag, w
chiftcd
t e o r b l t a

Ru, Rh, tu
C7,Cu,
Nb, Mo, cvhi
tal. gt chctco
in
half-
ns no
o
fp cra orutals
have
L e u o n s
-Dd ve
e u m e n s

the c r b i t o l e

cuch mtd
arte C-Ud
hfurg
4 and
such

type pld Th
T c e m p a t
mmitals
th-)d
ty str
flt
dran
t a l

0 r e
 Classiecatiepgd-8cc alorents
Based en uhsther t s diffeurnaicting caci goes io

5d, 4d, sdor bd cxiutals, d-bieck ouris hauc be, dasijced

Lo faur sedcs uz d, 4d, sd and bd ceues as déstus5ed in

6eoal Chasactekustics d-Blck elements

So Lmpcriart dhatackoustiCS 3d-secies clnmots aa
dusoabed 25 folaus

Mekallic 0haxactoy
All t e
t7ahstton elemris aE metais. sun ce tha nuimber 4
E ct2e in bz utex mest dall
vey ali, bung g u
Thay ae
haxd, malieaic and dukle
g exhubit all the
3.types q SEucHuaes fatt artr ed Ctuhic (fc),
agenai close packad Chp), and tha
Metaisg vl 418 bedy cerdeved cuhic Cbc),
gveups ak SepeT and more dutile cthan tetur
metals
It
Qppeas that ovalirt and me|allic
bending bete Gist
tn dhe Qfoms ansitien neials The
pesonte uniued d-
CThitals favas pvalent
behdung These metals e
good
Cerciuckor 9 heat 4
ectnicity
2 Aemc veLumes
7he
and densitiCs
alenic voluns and densities
5ene ad seies
elerarts givn y
SC 15
7-2 7-2
Mh 73 74
In d-bltdk
dernent s Ch-) d Subshel es filied ad te
UnCTecsed huucihay chage the ce cEEh 4n Thu lnads to
#e Cempasatively Jcu aiomic
1o bese y the
vetunes Casc cltints CBmpaed
the
haighbeunng S- and P- blek camintS
dunsities f d-bock denints Ee
40 tese voy high an
grop 1 h4 1A ernarts Cempavsio
becaiuse Tha s
thir deceasurg elume destan dable
 Melking and BRlug pelrts
7he meltug ana bcug peits oy da Clerernts 0@
Shewn MMe
a730 1539
TI 60 bb8
C 2k5 (8 76
t 1s evidont fem t e vales d t the d- bleck dlrerts

Iave hagh maliug d beiing pobnds 1t shous that thy ou

hald by Strong foces.

Gtencralty ths maltng Ohd boiling poirits d biock
UetSduErease eh descoholig 9velup. Moltug na beuln9
PeLrEs ) Ag e deuwon dhan dhese CL and Au Thus can be
expialnad eh te basL6 hat both cà and Au have greater

tondarncg acguy hughey oidatib state han + l, uggestirg

that dn these motals ia dnvolienent y d vbit aks tor mitalilic
bercling to a greater ecten than in ng

AAemic Radi (Covalent)

Fo example
Sc144 "
Y 62n"
La 168 A
AS & eVidert these Vallues erally decrease Bh moving9
frem det to ughd dh e peuod This s due to the fact that
3 th nukoa Chaxge aincreases with ncreastng Qlornic rautmber
acogs auy Soues, the attratiten f be clutbOns touaols the huceeus
UcTeQseS Qd Uus hcease in ot/acuen Jeads te a deca ease tn

the Tadti values acrB8 a eachpeucds howoventhey oe

feu exceptiohs The atemic sundi ef eemants fem C7 te Cu a
Voy cloxe o ohe aneth he is oxplained as folueus
dn
AS we move lCreysdhe poiod, thoe s an hccase
ucey chaKg uhich dende tt pull the 49 olect 1eh Anuascls hea

ty hucteus
 Te Lt thds to educe tha SuZe Ht the same tin the
addi ten 4Cca CLetaesto the 3d orht Lal also provids
a Stocening eifect whuch shieids B 4s-Clucbens f7em thu
tnunsct pull e the pestbive hucluus Gn hese elettaons Thss
SCreenig ohfcct increases as thu nunber g extia olecichs
being adlded to ad-07bital increass 7hs eHect oPpestsha Ure
Uh size Thus tero ase pexatig tuo effots rnoly soecning
ejectand hucteax Chnge efggt ühth epp0ses eath Gthu
a e voy shight Vasuiations in the attmlc radius fen Cr to Cu

QHe BAseved
In a paxdiculax soics the atomio uacics ctaire o
V ad incgonses
munurnum value for te elonerts gacup
end of a soLlOS
agan touaxds t
Tohic Radii
The onic socii fUllow te sane trord as the atornic
the
Tt may be seon h a t #e iadii y he dens having
hd in atomic
Same chaHge Cvalency)dec7ease with dhe ucrease

rLurnbor
Tohisatieh Potentats
Tha ierisntien potenbial valuos y mogt ef the d-block
Clements Lies in betwcon these f and p- bleCk elorTorts
This rrintes that dhe d bleck elerertscoe less eloctrepestttve
than s-blck elernonis and rove o than p-block elernents
Thus d-block ekements do net fom iohic compeulndls s0
6aacly os tho alkall and alialine casth matals do Unute s- block

ements, d-block lments fon ovalarnt compemis as wo0l

The ishusaton potertals e ad sotues olernents uncrease
Qs we moe acrops dhe snies frern lopt to sught
 FFexent Oxidation states Vaabta Valeny
Th oun oxidoton suate pegEned s vatancy Mot
t h 1apsitten etals Shou Col DAidaton States o
vasdable Vadiricy d thei cmpeund Oxidatton Stake Seun
y d block etnerts ae tl,t2,t3,t4,t 5,t6,47.
The uso of
Shaung diffownk oxdtien tates is
thai thosc
elomonts Jave seueal (h-1)d and hs Cectohs and that the
ebxngics y n-1)d and ns 0Yhttals ae fairiy cloe do
cachethe
Hee (n-1)d elcephs ae as castly ost a4 ns oybitas occtrer
Ameng the clarents 3d ceies, Mn Sixwstha naunun
humbee oxidatien states because tt is at Mn a t the hurnber of
uryauedelectrens io 3d o bit u maxiin, Un pcCCading teuacis
tight eft of Mhclocveases
Nith hi exouptien a a t 45) , the muninun oxicdatpn
State Shoun by tha cmunts ad- seues equal dto the
hunbey 4 eluctehsuh 4s 0hltal
ExCopting s Cersents e976Lp 1B. edsr chmentc 9heuw
maximum Oxidatten State which b hevOx mee thah thei7 group

humbet
I h gelng down a greup, The highes oxiclation States becoma
Fe axe
ore Stable oy
e9 1 and 13 Cxidatieh States ghcun ly
Ctoble Bkicotten stateS uhile t4 th ast wnstadle Cta
Tha elative Stabiuity vasiods Oridaten States 4a
on tha bosLs thz Seabil ty Y
gwon elument on be explaind
more
dO,d
5 and do onfiquxation fy og M ( 2d 0,45°) t3
the Prcgonte y 3a Drbtal
Ctable than Ti (ad' 43) because
In Ti 10h.
luc
THansiteh elamrts
bends un thuis
aan fom dehlc

CkcuthHien statcs ad he denic chatacte

the bent deoses

Loith tha dncrease dotiehstate

 foznation colcoed compeunds aluroents ea

Nomaliy
the onpeunds y s-4 p-hlock o 7
thu olua
ctodess u h tose anitton rnetals un
ottukcon State aa usually celae

Ti4 (3d, h=o) Colauz Less

TI (3d', h=)- prpla
Fet (sd) Yollco
rea (3d')- Pale gveeh
t ray be seen t a t the ntions Ceg TI,Qu)
07bials (d", d)are
having acant or
completely -pllld d
olrrloss
white those (T",cr*) havirg pttiolly flded
d-07httale at colcurea
other uvrds
In tho catioh having all th
d o7hitals eauctaens n d 0Tbetal
CLctren pais cd an or no

Cete Celou less arbo these having scme all the

eluttnons uppalred in d-0wbitals.ato coloured
Magretie psucpertces
Ih gehegal thuy ae 3 types y maghetism

PHamgnebism
Diamaqnetism
Feromagnatism
RHamagnetisn
This ptopecty B Soun by the Suhstanas uhich, when
placed betu/eon he nagnutic psits alow tbe hagretic lihes
y fooce 0 m g h than stifhey ban h0ugh vac tuum e
a poxamagretic kar wie terd to se Lsolf with its longth pevallel

D tha ptold, uhen t is platad betuech tho magratitc pets

h o0ex uovds a paNanagnetic Suhstana 8 attyacted Jntoa
 hiaghetie feld . Hara/nagretisn 5 Cme abng the tranaite
metal enpteres ie, mest q th ETa2sctLen metals ce paiamagrattc

Ramagretion
his pepesty B ekhbited hy Je substanes uhich alpw
tha vacuum ratex
hs magretc lires fovce dte pass Bmeugh
then reugh themacLves ThLS a auunag/atíc substana is Tepclled

by a
mag hetic ficld, and heno utends bo CE Eself at righMt
the eectren paired
angles flcd The 0ompolds aving all
to do

au dianagretic. 1e diamagrotic CPmpeunds have upalred

5 zeT0
oLteren,and hance their magnenc noment
.

The epecty diamagretism s peod.ued by tho wbtin

netEn euct7ens #he atems,os 0 mBkoCuLeSs t h e
Sumple t ë chatasteristic all subotances tbat entain

paired electonsDiamaghetism exhibited by all aukstan@s

Even paiamgreic substan tes have sams dinmag hebic dhaeace
and ts et magretc mamerts joT pavanngnetic aubgtanas ase
Cbtalnad atter makug due corectiers jor the diamagnetism.
RLamagnetic behavisur 1s diit to small magretic moments uhch
8L dnduuad by the ofPplied magretic field but eloes hot etist

tha absena e the fiald

h
feemagreisn
In ase g Spme transttlen metals C Fe, o Ni)
th unpalred electrern splrs au mese pHonoun cod and henco
Such metals paHamagretC than the sther
ceul much mesa

transiten metnls. Such metols as alled fesHO maghettc

u
metols and ts magneHc behavowr Shocun by these metals
Such nmetals can be magnetised
hGun as fenomagretiso
Cotalytic pKegOeies
the dirslein heir Conmpawnds ae
metals and
MeSE Ocate-

uansitlen matals Shou

a Vasicty
as cataliysts
sed uUEh vaiG.
foum Jntesmediate poducts
Gtates and heeby can
 eactanks Thay a9 also capoble
foming intes Htal
Compaunds uhich can adsorb and activate tho TeacHng
Species Thus they ac as cataliysts. Bome eamples y ntouipt

e act as Q atalyst in hydogenatieh roaction

V20g L5 usedt fom catalyeic oxidatlen4 60, to D Ctc.

tonaten Alleys
with eath otar, this
Tsaneition metats fom alloys
B because they have Qlmest sim lay Sizes and the atems
cne metal can easily take up poitlsra un the crystal
Jattio the stter. Thuus we have alap -Ni,
Mnfe ctc. Auloys au usuaby hasides and have highe
metting peurt than he pasvert metals They a more
esistant to cOTodieD than tuir cestituents
 VANARILMPENTOKLDE
Faxegacish ammerium
metasanadate,

t can be Ppased by hatuig

(v) o1ychle7ide, Vodg
e by te nyd volyos ty varadiun
NsVO
NHgVO 2NHy t H
QvOcky+a4,0 60 t bHCE
Rxqportics duda (Va0a) 18

/
duced uith k, hypovanadum
elbtained
VaOgt6K VaO t aK,0
vaadiunm ioicde
w Va0, uduad by H or sulphur,
CVa0a) is ebtainad

Vay+2H
A V 0 g t 2H0

V,OtS Va0s t S0a

8 heated uith Co Metal, V,0- get raducad to
When Vz0s
Vvaradium mekal
5Ca0 1 2V
V0 5 Ca
Uses
V2Os ls used
dn a 70actiprs. seme such eectic
Qs a atalyst humbOX 4
ase
Used un the marifactue
Oudailsn sO2 to 603
HaS04 by (Bhtact pHoCRSs
Cacidotton anthawe to anthraquinere

Mid aon phunarthra.cere phe0nthraguinehe

te

beidabien toluere o benzal dhydt te berzpic auid

vanadium qtass this giass
I h the prephaton y is

pepoed by ating 0.02 Y Vanadium as O bo ondinay

glass ths 9las cuts eut cornplekely the haævnjul ackinlc ay
 Annerium Melybdate
ReeparationCNH4),Mo O
This cempoLund s ebtairad by he troatrnent g MoO,
twith and the selukion to
NH4OH evapoating crystolisatisn
Dces
*Oh the basis ef te above sHaLHens , CNH4), Mo 0 s
LSR in dthe
Jaboratory fo the detectLoh ahd estümatton
PO and AsO ihs. When AS, S, 07 As, Sy 5 boled uwith
one HNO3. osenic Ocid, H3 As O4 s pcduccd with hich
quves a yoliou pccupLtate q anmenkum avsenomely bdate.
CNA) As O 12 MoOg with CNH4),Mo
As Sg t lo tHIVO 2 HgAsO4 + l0 ND,t 2H,0+

As Sg t
10 HNOg 2HgAs04+ lONOt 24h0 + E

HgAsO+ l2 (NH),Mo Ot 21 HND

(NH,)3AsO4. t2 MoDg + 21 NH NOg+ 12H0
Yeltow ppt
*tNH)MoDg s alo sed as
fo a cattalyst
dehydrogenaten in Petreleurn and ceal technelogy
 Lnjure tte eye
In the Prepasatsn ef feauo- banaduum alay which s
Stcels
e manufacture g spedal
used as a Scavenget in