dBloek
# Tntroducion
) d-block elements are 6Ften catled ag trangitton eloments because
their position in periodie table is between the &-block and p-blbc¢
elements.
iy Their properes are transttonal betuween the highly reactiue metallic
eJements s s- block (uhich form fonic compounda) and the elements
of p-block (whtch Porn co valet compounds).
fled
310 lypically the trangitton elements have an Rnconpletely
d-orbital. The generad electrontc nt-2
coniguahn Transtfon
oP d-block element is (n-i)o eQenet
where n ls the oter most ghell. The element whose atom
) Group t2 (the ztnc qroup) elements hawe Around tate or in oe
Completely led d- orbttala in the ground Common oxidation
&tate as wel) ag fn thetr common Stateg, hag partly P9led
oxf datfon states. not egardpo au d-sub Shel) i.e. hauing
ttansion elementS electrons between to 4.
u) PalladBum hos electronic conttguration
vdn, Cd and Ha are Inuolued in tran sition gertes but ane cauled
non- trangiion elemets due to comnpletely Uled d-orbtals.
AstSeries
So T V Cr Mn Fe Co Ni Cu Zn
21 22 23 24 25 26 27 29 30
4s 2 2 2 2
3d 6 7 10
2nd Series
Mo Te Ru Rh Pd Cd
Zr Nb
41 42 43 44 45 46
Ag
47 48
|Z 39 40
N 2 1 1
4d 4 6 10 10 10
3rd Series
La Hf Ta W Re Os Pt Au Hg
Z 57 72 73 74 75 76 77 78 79 80
2 2 2 2 2
4 6 7 9 10 10
iv
#Popentes
V Metatlic Charater.
D- block elements show typf ca metal1tc behauiour o high
tensile
v3trength, malleabiity, dueility. electti cal and ther na! cond ucti vity.
metallic Justte and
nd cryatatse
Crystalise in beclcep /hep structures.
They Cure Uery had and haue high arthalpy o atomtzatton cund
o volatiltty. except or copper. Hardness fnereases with the number
o# Unpaired electrons. Henee, Cr, Mo and ware very hard metals
among d-block elements. he Aroup-(2 lements (n, cá and Ha) how
the exCeption In this regard aJso.
900
800
Series 3
700
600
Series 2
500 4d
400
Series 1
300
200
100
Atomic number
Merting and Poiling Ponts:
) Meltng and boling points o* d- blo ck
f 9-biock eenents. elements more than tht
Reaan- Stronger metat lic bond Formed by
) Tn n, cd aund Ha there is no
preyent
unpaire d d-ea crog
d-orbital, hence due to absence unparred eletron pregert fo
Covalent bond metina gnd
boiling potrt are very Jow in Berieg. (Uoloile metals Zn, Cd and Hq)
m) In 3d Sertea Sc to cC melting and þoiling pnt
Ma to Zn metng and botng pot nt decre ayeg inereases then
y Hs the number sf uo Daired d-electron increages, the number
Ts expectto
COvalent bond andl bond enerau betseen the otomthe
n y where ea ch of d-orbrta
t0 inceoge up t0 Cr-No-w covalent
ony onpaied electron and the opportunity Por
Sharings
is Qneatest.
weak
) Mn and Te have comparotively low meting potnt, due to
metallic bond because table ha Pled (a) (oniguration and
hgh IP.
v) Lowest rmelting point Hg 38°C):
Highest meting potnt h (340Ý)
2000
t/°C
Point
Melting 1900
1672 1530 Co 1455
1500 sc T 1710 Fe
\Mn 1495 Ni
1397 1083
1244
Cu
10004
420>Zn
500
VI VI
Graphic representation m.p. of 3d-series elements
) Dengtty
)The otomic valumes of the trangttion olements ae loo compared
with the elements of group and 2 This is because the
fnereased ePectve nuc>ear charge. Consequerty the densitfes the
transti on metals are higb.
) Across a pertod rom lett to right atomic volumes doreaye and
atomte mosses fnceaye.Hence the donsitie fhcreage aoross o period.
(zn hc Jouer denat y bec awse o it Jarge atomic vlune
i)3d<4d<<5d order donsity in agroup.
i) Maxinum denstty: Ir0s
o.
qIontsatt on enera ces
b Ioni satio n Enthalpies
¿ D They have high Iº as compared to group t and gro Up 2 mekals
due to the?r hgh Zep
t)The rst ioni zotlon energs of zn, Cd and Ha
are very hgh
beca use st tthefr oly fLed Ch-) ng
confiqurarion.
Vaßabie oxidation States
)The transition metalg exhibit a Large number o oxidatton
States. These different oxidaton states are elated to the eletroruc
ConPauration o hetr otoms.
) The existence f the ransition elements tn diferert oxidation
States is due to the partict pation o fner (n-1)d -elecrons ih
addrton to outer ns -electrons because, the ene rgies the ns and
h-y d-sub-shelLs ae neary game.
itt) O:PPere nt oxtdoton states of ftrst transiton series.
Element Outer electronic Onidaion tote.
ConAquration
Sc 3d
3dg t2,t3, t
t 2, t3, ty, t
Cr 385 4s t 2, +3, (tu)t5) to
2
Mn 3d us t2,+3,+4,(tS), t6, t7
2
fe 3 us t2,t3, (t4),ts), (t6)|
Co 3d +2, t 3, (t4)
t2,+3, +4
Cu 3 t1, +2
t 22
* Oxidation states givên io
arentheis are Untatlo
tv)Ia general oxidatlon &tate ot d-bl ock elenerts fis alven a1
minimum oxido tion ote = umber st ' electrons
Oxi dation Sta-te = nuber S lettong t Unoi e ' mpximUm
elttron,
(0s,Ru)
yHYgher oxidation state in d-boock = t& metal Carbonyls
OXidation 8tate in
lransition elementtt ghow Zero
eg- CNi Cco), Cre (co)s].
o otdasion sta '.
vi) Rolative gBabiIlts
+3
<Sc
stabu coniqurayion
t6 înert gau
<wts
Stable configuraton
Mn<yot2 d in a
golution
<et d is more stob lo tha
of irst four I.Ps
bouts to gum
On the bts
Pt <Pyto
c htgher oxtdlatton state
vim) On nm ouing in a pertod stabilits
docreayes.
the group stabilits of higher oxidatton
Ôn movng down
Btate fncreae. t6
egi- "ro, < Moo < Wo,
MnO, < Tco < Reo,
D)Clectrode Potertials
au
enthalpy.the other factors &uct
In additon to forzotion erthalPy etc. dtermine the tabílity
of SUbirdtion, hydrotion
enthalpy
POrticuar gouton. This Can be explained in
oxid ation gtate in
of e The oki daton potential a
electrode potertiau value.
terms o thoir
proces:
metal fwoLurea the folouwing
thee teps
Ihis prOCeAS takes pla ce În
AH
M MTla)
hyß Cii)
Mo
The oxi dation pobentia! whhch gives the tendency o the oeral
Change to ocour, depend upon th net eect of heje 3 steps.
The overall energy is H= Asus H + Ht
that means oxtdotion will be eay.
I SRP s tVe thot moau seducion will be eayy
*IMPORTANI EXAMPLES :
’ tue only or
Por uCu among 3d elernen
elements becawse
hydratton energy aog,
cute is not eno gh
Compens ote for &ublimasfaon energg, TE and [E, for a
2.
2
that mean tct acts a redudng aget because Cts has
haf led Stale confgurati on.
y b) eo -tve
Mit t
+3
thot means Mn ats a odistng agent due to steb
Trends in stobiity & higher oxidation state
The highest oxidation tates are 8hown goaraly among hades
and odes o ttanaition elaments.
@In halide f tranition elements
)The transition elemert eact itn haloge Qt high temperatu re
transttion mAtol alldes.
to form
D 3ince thuorine fs the moct electronegative ele mert, the trangitign
metals how highet oxidation Btaes wrth Pluorine. The highest
Oxidation stateg are ound n TiX, (tetrahalide, X E, CL,Br and I,
iiD he 7 oxfdation stote Por Mo fs not ghown by ginple
the Oxtd ation 8tate
halides. However, MnoE s knowo in whtch
G Mn is +4.
oxidatHon
9he tendency o iuorfne to gtabillge the highert
State ts
ts doe o efther higher lattfce erthaipy
covalent
Cos Or igher bond enthalpy terrns tor the higher
Compounda. Eg ' Ve and aY
u) Qu oides ane relati vely Unstable fn their low oxidatHon States.
for example,vanadtum forn onls Ux, (x- 1. Br orL) and
form uX (X= Ci,Br. I), 0o the other hand
Co pper Can forn
cOPper (u) hautdes are known xcept the todoe. This ts becae
Cu oxtdises I to I,
Cu, I,(s) tI,
) Tt has been observed that many copper lr) compounda ae
nstable fn aqueous golutton and they Undergo disproportion.
2t
2Cu
CopPer in t oxidatÉ on State is more table than f ti
basis o much
Oxidaton gtate . This Can be explat ned on the
tanger negattve hydration enthalpy (ana H of Cu (a) than Cu!
foization
which fs BuPficiently hiah to compengate 8econd
enthalpy f coppe.
b) In metal oxides and oxOCations -
)The ablity of oxygen to 8taize the ghet oxidation tate ts
n thair
denonstroteo in thair oxfdes. The highest oxtdation Stater
OXideg conddes with th qroup number.for example, the highest
Oxidatfon St0te f B Oundium o Qroue z is +3 in its oxideg
Sc, 0, whereas the highest oxidotton &ate ot aganese of
roup
) Besdes the odes, OxOCation of he metols also stobige
oxidatfon States. for exampie, v u Vo,U ay Uozt and T
TOT.
)Tt may be noted that the ablity
abtu of oxygen to sHabtise thoe
ngh oxf doton State exceedg thatf loor?ne. For exaplu,
manganeye torms hghest fiuortde as Mf, whereas the hghet
Ortd& ts Mn,Oa . Thisis due to the Pact thau oxggen has abiity
to Form muple ods to etale.
T3The transition elemente n the t2 and t3 oxtdation 8tat
mostJy states,
orm onic bond wherecu ufth higher odatBonbonda
tho ond are exsentlally Covale nt g. Sn NnO au ant
Cov aled.In thae igher odes the adic characHer ?s predomiart
Thus Cr gives H,Cro, andl H,Cr, O, and Mn,0 giver HMna,
and w
N, O s however am photertc though mainly actdic
aukales
Mogneste Propeuies -
Mag neHc Momert
Unpalred
Ton Conkiquration electron )
Calculoted Observe d
S8t
J.+3 1.45
2-84 2. 46
2
3-84 3.86
3d4
Mot 3ds S.q2
6
fe t 3d 4.40 S.3-S.S
3 3.87 4y-s. 2
2t
2 2-84 29 - 3.4
1.43 1--22
et
When a magnetic ield is app1fed o Substances mainly
two t9Pe magnatic behawi our is observed
i) Paramagnetio ubsance - The Bobsto nce which ar attralted by
magne4fc ¥teld ae cole d por amQ0n0tic gobstances and this
Chaater arlse due o tho Dreence funpoi red electros în the
Honlc orbitcl.
i) Diamagnete Subatoncer- The abbstance which ue repe)lod by
magnetic Preld are alLed diamagnette 8ubstances and hés
characr artsey due to the preenco f poired elactonu tn
the a+omic orbitay.
hae
Most f tho ttaniton mete fon or thatr compound d' to d
Unpoined electrons Pn dSub-shela (Prom conPA qur atfon
nd tho ne fore, thay g ve rige to paramagnatt C Charaer.th
80in d
i) Tho magnatf momend autse Ondu Prom th
can be cou cu ated rom tho relat On
electto Ths
n= number o Unpal red elocrory
) Formatton of Tntersttial Conpound
Compounde witth elemerH Buch
Transttton metas form fnterstitia! of the
as nydrogen, boron,caubon and trogen. The gmau ato m Spacel
get ttapped in vacant belouw.
hon-meta ltc elemert (H,8,C,N, to) motal
trangtton
the otomu as 8hown
af the latti ce,
e-g- we, fe,c,130-1. 80Vo.s6
Peoperstes
They are
- generally non- stochiometric comp ound
2) Nefthg typicall foric nor typcally covalent.
3) Harder than pure metal
pure metau.
y High meltfng potnt than
S) They retoin netaite conduciuty
) They are chernjcaly fnart.
Tronilion ma
Trepped atou in
in0ersial Sie
d-block metal1 or their compound ad a catalyst in many
Peatton due to
yPossibt.Ifty of vari able oxidaton Stat.
9' Pregence of Pree valeneies over metau &uface (adsorpfon poue)
it) Preserce f vacard d-orbttau.
Vs So, (contact process)
Oy -
explanatfon o this cataytic acion can be gien
V,st So,
2u,04 t O, ’2V,0.
Other examplar catalyst re ; naly divided ton (tn Hober procen
Ntckel (n catalyte hydr og enati o)
1. Alloys aue homogereos lolid 8alutfonu in which thetha atorng
atom
o o meta ae distributtd randomy Bing among
o thu othor mda.
those Qtomy whch hane
2 The alloys e gee
wtun
formed
about 152. f
t
byach other.
ach othe.
mesallic radti
3. Transitt or metals orm aa large number o alloys becawse
in Size and thureore the
ttansition metals are qui te gfmilar
meta caun gubst tute tthe dom of other metel
tomy of ono
in ts Crystau dattte.
4. The olloys So formned Very hard and haue otn gh
melting pofrts.
S. . Bronze a (15-40:) + Sn(to-252)
2. Bras Cu (60- 8o2) + tn(20-4o2)
3. Gun metas - (Cut tn tsa) (87:3:lo)
4. German 3ilwer - Cutznt (2;1:1)
S. Nichrome Ci ter fe)
6. Alloys o Bteel
a) Chromium 8teel- Cr 2-)
b) Nickl teel - Ni(3-S)
c) 3tatn less 8tee! - Crl12-14) &Ni (-u2) Cr forru
oxtde layer 4
Protects Iron Prom Rusting
d) Tnvar - NiC36%)
allou which is formed by mixing
) Amalgm sis a BemigoldNi do not Porm amalgam due to large
mta with Hq, ce, to,
AHori
#CoMPOUNOS OF d-B10ck ÉLEMENTS -
) Potass?um termabgonatt (kMno)
Preporatton wfth koH or
by fusing Pyrolusite (Mno,) eitur
Tt is prepored
ofatmospheic Oxygen or any other oxidsi ng
K,Co, in pregenekNO,.
9uch au The fused mas turne 2reen w?th the
Agent pota Ss um manganote, KyMno:
ormation
2Mno, + 4koH t O, 2K,MnOyt 2H,o
2Mno, + 2k,co,tO4 ’2k,Mno, +2(0,
with water and u gow+ion is
Ihe used nas is extracted
chorine or oone or car bon
with a curret ot
now teated permaganat.
rto
di oxtde to conuert manganate
2k, Mn0,t C!
2kMno t 2kOH tO,
2k, MnO, + H,0tO
3k Mno, +2c0, 2kMny+Mn, t 2k, Co,
(disprop ortionatet tn acdit medium)
Cornenadany t ts prepared by Foston df Mno, with koH.
Rollouwed by electrolyttc oxtdaton of manganate.
Pus ed gtth 2
Moo,
MaO, tgreen) Mno, (Pur ple)
In the Aabortory, manganese () cn 84 s oxtdísed
by peroxodi su\ phae to 2-permanganate +10so +16H
2
Ss,08 t8H,02Mn0;
2 Mn
R is orple coloued crystolltne compound. Tt ts moderatly
Souble fn water at room temperatu re.
)Chemica) Poperty:
ePPect on heattng ynou s K, Mao,tMno,tO,
On treatment w?th conc. H2SOy (kMoO, is taken tn excess).
4Poms manganese heptox?de which decom po se erpiostvel y
on heati ng.
Can explosi ve)
KMnoy
"Potasst Un permanganate acts n oxtdfsi ng agcnt tn
perm
aukaine, neutrat
weak aukane, or acidlc BoDtorg
addsted kuno, (Purpk) Neutral or weak akaln
H,S
SOu
Br Bro
fet
Br
I
-2
Mat Ccolourlog )
T) Potassium Dichromate (K,CrO; ):
Preporotion: prejence
The chrornite oe is Yosed wth godiumn arbonate fr
4 Feo. Cr, O, (chromit+ sNa, co tt 30 Fuion, &Na,crO,t 20,0,+8(0
ore) Crey due)
tered and acdi eted
Na, Cro, is
The yellow 8olution too gfve a Sowtfon Arom which orange
wfth 8uiphuric aidl
godium chrormate (Nq , Cr, O4) can be orytalised.
2Na, Cra, tH,So, Na,Cr,0, + No, Sou tH,o
dichromate is more 8ouble han pataustom
Sodym prepared by reofog Solvtion
kr, Cr, O
di chromate 8o Rr,Cr,O4 is
Na,Cr, wth kel. k,Cr,0, t 2Nad
Na,Cr, O, t2kcl ’
primary standard
prefered over Na,Cr, O4
K,Cr, 0, is anaysis (ttrotion) becowse Na,Cr, O+ fs
in volumetric is not.
hygroscopic in nature but K,Cr, O
-2
" CrO;2 OH
Yeslou Orarge
b) Phygtcal Hopertyi compaUnd. TE is
It is oronge-red coloured cråstalline Freeiy Sowb n
modrately sowb in Cold wOter but
melts349°C.
a
not aUeter, Tt
d Chami caJ Voperty i
stronglå heoting, deco mpoter oith
" EPfect & heattng : On
tberattrg oygen.
2K,Cr,O 2k,CrO t Cr,Og 2
In aidic medium K,Cr,O4 Qcs oidising cqont.
AdiReed yr,, (orange)
H,9
SO
-2
}So,?
Snt Snt4
Br
Br
CH,co OH
Cr ts
(g reen)
1. Chromyl chioride Tert Cused to idarily ionic chiorida)
Nocd +k,Gga, t H, So, ’ , , (Red orange vapou)
J NaoH soLution
Na, Cro, CVeslow)
2. Aidited K,C, 0, Solotion reactS uttth H, O in a etaral
Bowt0n to give a doep bwe SobutBon due to thu
orrnat on CrOs.
