1v,u"' . • .

covalent
1·um dfcbromate (K2Cr207)
~ don, It is prepared from chromite ore (Fe0.Cr20 3) in three steps:
• Pre~ with Na2co3 and quick lime and extracting with water to get Na2cr0 (4 FeO.Cr
4 0
(l) fuSJ.118 8 NazCIO4 + 2 Fe203 + 8 CO2). 2 3 +8 N¾Co
+ 7 Oz- . 3
.. Treating with cone. H2S04 to convert NaiCr04 to NaiCr20 7 and separatmg out less soluble N
• ~ctional crystallisation (2 Na2Cr04 + H2S04 NaiCt20 7 +_ N~so4 + tt2o). a2S04by
.. Treating with KCl to convert NaiCr207 to K2Cr20 7 and separating out less soluble orange c
(uzCr by fractional crystallisation (NaiCr20 7 + 2 KCI >K2Cr2o 7 + 2 NaCl). tysta)s of
K2 2O7
Whiteheat •
Pn,perttes. (i) 4 K2Cr20 7 4 ~Cr04 + 2 Cr293 + 3 0 2
(ii) K2Cr2O7 + 2 KOH >. 2 K2Cr04 + H20
2 K2Cr04 + H2S04 > K2Cr207 + K2S04 + H20 •
Base
2~ + H 0 ;:::==:::
Thus, Cr. 0
2 7 2 2Cr042- + 2H+
Acid
(Orange) (Yellow)

2 K2Cr20 7 + 8 H2S04
(iv) Oxidizing properties :
Mol.wt.
K2Cr20 7 + 4 H2S04 > K2S04 + Cr2 (S04)3 + 4 H20 + 3 (0), Eq. wt. =
(dil) . ..• 6
2 KI + H2SO4 + (0) ___.> K2So4•+ H2O + 12
2 FeS04 + H2S04 + (0) >Fez(S0~3 + H20
H2S + (0) .• H2O + S
NaiS03 + (0) N82S04
NaN02 + (0) NaN03

(v) Chromyl chloride test

Heat
~Cr20 7 (s) + 4 KCI (s) + 6 H2S04 )

·(cone.) Chromylchloride
(Reddish brown vapour)
o~- + 2 H+ ·+ 4 H20 2
(vi) With 8 20 2• Cr2 2 Cr05 + 5 H20
(Deep blue)
Reason for colour of cr0t and Cr2o~-. Cr in both has oxidation state+ 6 and hence d 0 configuration.
Hence, colour is not due to d-d transition but due to charge transfer (from 0-atom to Cr changing 0 2- to <r
1d Cr (VI) to Cr (V)).
0
~tassium pe~anpnate (KMnO~
Preparauon. It 1s prepared from the mineral pyrolusite (Mn02) in two steps : • f
(z? Conv~~i~n of Mn02 into ~Mn04 (potassium manganate) by fusing with KOH or XiC03 in presence 0

att or OXIdizmg agent like KN0 , KCI0 etc.

3 3
 1 _ 2MnO2+4KO H+02 )2K2MnO4+2 H20 -. . ··-· .
•
_
'.,;-J ·i ;;~•,. 3 ?dJ10 2 + 6 KOH + KCl03 . ) 3 K~MnO 4 + KCl + 3 u o _. ' _' • • • • .·
2
4
,,.~~ QP(lalioD of ~~~ ~~~4c~:nuc 8!1i :~o~ ~~(}Oytc, or elec~Iytically (by electrolysis)
(ii) - 2 . 4 2 + 2 K 2Co
3
IC.iMnO4 2 K+ +. Mnoi-, H 2O ? H~ + OH-, • .- •
., ; .
... ..0 42---.> MnO4 + e- (at anode) and ff+:_.. e--~ 1 H
IY.I.U 2 2 ( at ~athode))
•• 513K r •
_.:. ..-.rdel: (i) 2 KMnO4 (s) > K2MnO4 + MnO2+ o2 . '
,.....--- Rcdheat
_. , 2 ~MnO4 (s) 2 K 2Mno3 + o2
' (Pot. manganite)
. Cold - .
. r.r:\'2 0Aft04 + 2 ~2S04 (cone.) , ... ~207 + 2 I_GISO4 H2O
1 ,,., . • Warm
• -1 fCMD04 + 6 H2S04 (co~c.) > 21:(2SO4 + 4 MnSO4 + 6 H O + 5 0
(iii) ()lldlwJn8 pmperties ,, .• . • • .. , . _2 _ • _ 2
..,__,,solution:
JfelM'-
2 KMnO4 + H 2O • ) 2 KOH+ 2 MnO2 -~ (O,), Eq. wt. = Mol. wt. J
. . - .,. •
.• • • -. •
6
,,. , I . - • ..

(O)., Eq..•wt.•• = Mol. wt.

T

.. ,._JntJp-,..,;on: 2 KMnO4 + 2·KOH ) 2 K-UnQ

2'""'~ 4
+HO~+
2
IIJl(IIII""-
; I. • 1

,
ID~of~~~.~ ~~~-~~c;>~ ··+H20, • ~MnO
. . , . . . '
2 +2KOH+(O)
.. . .
= •. • •

:cWreaetion : •• :_, ::·, r 2 KMnO~ H2O ) Mn0i·+·2 KOH+ 3 (0), Eq. wt. + = Mol. wt.
6
*ie,o.,IMP..Q4i s called Baeyer's reagent. it oxidizes olefinic compound to glycols, ~~g.,
•
.
.
' ....
1 • , •• ·,; _::
. . . .
CH ~CH
~ - ·, ! · _.; .,• •:_: . . ·
,..

• ••• •

Li-Cff2 - CH2 + H 2O + (0) >, I · , ·2. _,_. -: I . 2 ., . . . .

J'::~.·,..,;.- __ ;;.:_J . ·:-.-·:.. OH OH •. • . _ . f • _., • : • # •

Acidicmdium: 2KMn04 +3 ffiSO4 (dil.)-~> K 2SO4 +2Mnso4 + 3 H 2o + 5 (O),Eq. wt.= Mol. wt.
• -••- : ·-. . H 2S + (0) _ ) H 2o + S . •.; .. _. _. . 5 ·
SO2 + ffiO + (0) >H 2SO4 .. • :· •.
. . _ . KN02 + (0) , > KNO3
CiH2O4 (oxalic acid) + (0) . • >2 CO2 + H 2O
2 FeSO4 + H 2 SO4 + (0) .> Fe2(SO,4)3 + H 2O
2 KI + H 2 SO4 + (0) ) :KiSO4 + H 2O + 12
2 HX + (0) > H 2 0 + X2 : . . ...
CH3CH2OH + (0). >CH3CHO + H2O ,•_ . .
Why KMn04 cannot be used In presence of HCI or HNO 3 in tltratiom? Oxygen produced from KMn04
+ H~ only oxidizes the reducing agent but is also partly used for oxidation of HCI to CI . HNO 3
itself is
an oxidizing agent. • · • ~. • 2

lftllon for colour of MnO4 • Mn in MnO4 is in oxidation state·+ 7 with do configuration. Hence, colour
ia not due to d--d transition but due to charge transfer (from O to Mn) changing Mn from 7 to +6.
1 14
IIIIMNCII and Actlnoids ((-block elements/Inner transition elements). General B.C. = (n - 2)/ -
40-l ns2. Lanthanoids (58 - 71, La- Lu) are elements in which 4/orbi~ are progressively fill~
90 - 103 Ac - Lr) are elements in which 5/ orbitals are progressively filled. Lanthano1ds
alao called rare earths. Actinoids are radioactive and show many oxidation states and hence
·catec1.
"' ' .
I t l I;

- 71, La - Lu) E.C. = [Xe] 4/ 1- 14 5d0- 6i1-_

1
 ~~
.- . . ~--- • • ,,-:nn :ncz-- .,...~· ---~-~ ~ ... - 1 1 1 1 ; . ·m •

8154 thanolds, Typical is + 3 but + 2 and + 4 are also found. However th nd to change
Eu2+ and Yb 2+ are reducing agents while Ce4+ and 1b4+ are te
on states o~I•~+
12 Oxidad
to+ 3. 1bat is why :~ee n 4/ and 5d, they show limited number of oxidation states. izmg agents. Due
to 1arge energy g(' dii of lanthanoids - Lanthanoid contraction. The small regular de .
g Atomic and ~.onfclanrathanoids is called lanthanoid contraction. The small net decrease is d~retas~tncreas m atolllic
.
• •c radii o bich outweighs the 1mpeu hi Id' b f I • e o .
1•
and 1ont
..&
ect s e 1ng y -e ectrons . Due to this contrac tio . e Ill
nuclear chargef ;e 3rd transition series (after La) are nearly same as those of 2nd series in th:, atonuc radii
. . • . . same grou
0 f elements o white metals . Most of the trivalent m tal. p.
cteristics of lanthanoids. (z) They are silvery I . e tons
14• Some cbara .. 'th f I h
s ave same co our as with (14- x)f-electrons. are
ured d e to/-/transitton. Those w1 . x -e ectron . . . .
colo u 3 14 all show paramagnetism due to presence of unpaired electrons M
. Ex t La3+ , .tO) and Lu + (f ),
00~ V.
-~

moment, µeff = /4S (S + 1) + L (L + 1) B~M. where S =. spin quantum number and L = orbital quantum
<

number. ·
3 3
(iii) They form basic hy~oxides. As si~e dCC!eases from La + ~o Lu +, th~ cov~ent charact
er of hydroxides
increases and hence basic strength decreases. Thus, La(OH)3 1s most basic while Lu(OH)3 is least basic.
15. Uses of lanthanoids. ~ey used ~nly as ~oys. The most co~o n being misc~ metal (Ln = 95%, Fe::
111_ s c Ca, AI= traces). It 1s used m making Mg based
alloy. It 1s a pyrophoric alloy (emits spark wh
70
5 ' ' en
' used in making bullets, she11s, lighter flints etc.
struck),
1 14 1 2
16. Actinoids. (8~ 103, ·Ac:... Lr) E.C. =. [Rn] 5/ - 6(/)- 7s ·, •.,.: \

17. Oxidation states of actin~ids. Lile~ lanthanoids, most_ common is+ 3. They._also show oxidation state
of
+ 4, + s, + 6 and+ 7, e.g., m Th, Pa, U and Np respectively. They show a large number of oxidation states
because of very small ener~ _g~p 5~ ~<!? s •. _ _; .. . . _ .;
18. Ionic radii and Actinoid contraction. It 1s similar to lanthano1d contraction but contraction is greater
due to
poor shielding ef!~t of 5/ ~l~~ons: f urthe~,~ 5f.o~bitals._ ex~nd !n space__beyond 6s ~d 6p orbitals whereas
4/ orbitals are buned deep. •
are
19. Some characteristics of actinoids. They 3 silvery white metals. Their cations are coloured
due to J-°J
transition. Ac3+ (5/°), Cm3+ (5 f 1) and Th :'" (5 f?) are colourless. They are strongly paramagnetic. They
have higher tendency to form complexes than lanthanoids due to higher charge and smaller size of their ions.
20. Uses of actinoids. Th is used in atomic reactor and treatment of cancer. U and Pu are used as fuel in nuclear
~[reactor:-'\ I'/. , .,( .:•:· ',:
..
' , •• •

-·-- ---- - •• .I
r 'lf, • ..,. ' - ' ~ VL \'~'8.~~u.&ILM &.\o

\AN'fflAN~U)$·.-ANJi"At;pNcill)s~ -< _ -
_u,...., _

·_ .. •. ,. .
_..,. _ • - - - __

\._;'-~\\: 00\Dfi.'B.lSON O'i

S\m\\ad\\es. AF. both \al\tha.noids and actlnoids inVOive filling of /-orbitals. they show similanttes m
mmi te~~\s io\\o-ws •. ••:.
~o\\\ s\\o'W main\~ an oxidation state of +3.
 ts/4~
(ii) Both are electropositive ~d very reactive.
( iii) Both exhibit magnetic and spectral properties.
(il!) Actinoids exhibit actinoid contraction like lanthan oid contrac tion shown by lanthanoids.
Differences. They show differences in some of their characteristics as follows :
• LANTHANOIDS • ACTINOIDS

( i) Besides +3 oxidation state, they show +2 (i) Besides +3 oxidation state, they show higher
and +4 oxidation states only in few cases. oxidation states of +4, +5, +6, +7 also.
. (ii) Most of their ions are colourless. ( ii) Most of their ions are coloured.
(iii) They have less tendency towards complex ( iii) They have greater tendency towards complex
formation. formation.
(iv) Lanthanoid oxides and hydroxides are less basic. (iv) Actinoid oxides and hydroxides are more basic.
(v) Do not form oxocation ( v) Form oxocations e.g. UQ~+, PuQ~+ and UO!
(vi) Except promethium, they are non-radioactive (vi) They are all radioactive. •
( vii) Their magnetic properties can be·explained (vii) Their magnetic properties cannot be
easily. explained easily, as they are more comple x.)