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TAR GET IIT JEE 2007

INORGANIC CHEMISTRY
XII(ABCD)

d -BLOCK COMPOUNDS

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TRANSITION ELEMENTS:

Definition'. They one often called 'transition elements' because their position in the periodic table is
between s-block and p-block elements
Typically, the transition elements have an incompletelyfilledd-level. Since Zn group has d10 configuration
and are not considered as transition elements but they are d-block elements.

General Characteristics'.
(0 Metallic character: They are all metal and good conductor of heat & electricity
(ii) Electronic configuration: (n-l)d1-10ns1-2
Sc H V Cr Mn Fe Co Ni Cu Zn
1 1
others are I 4s 4s
as usual { 3d 5
3d10
(iii) MP. Cr -> Maximum Zn lowest m.p.
Mo 6 no. of unpaired e"s Cd due to no unpaired e"
W are involved in metallic bonding Hg for metallic bonding
(iv) Variation in atomic radius:
Sc -> Mn Fe Co Ni Cu Zn

decreases remains increases

same again
(v) Variable oxidation states possible

SciTi V Cr M n Fe Co Ni Cu Zn
1 +1
i+2:+2 +2 +2 +2 +2 +2 +2 +2!
+ 3 +3 +3 +3 +3 +3 +3 +3
+4 +4;+4 +4 +4 +4 +4
+5 +5 +5 ;
:+6:+6 +6
+7

Colour: (aquated)

Sr3+ -—> colourless

Ti4+ -—»colourless
Ti3+ -—> purple
V4+ _—> blue
V3+ -—> green
V2+ -—> violet
Cr2+ - > blue
Cr3+ -—> green
Mn3+- > violet
Mn2+- > pink
Fe2+ -—> green(light)
Fe3+ -—> yellow
Cn2+ -— » pink
Ni2+ -—> green
Cu2+-—> blue
Zn2+ - > colourless

fe Bansal Classes d-Block Compounds [4]

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CHROMATE -DICHROMATE
Residue(Fe203)

» Filtrate(Na 2 Cr0 4 )
' Dissolve in water
and filtered
10Q0 13QQ C
Preparation:-^ 4FeCr204 + SNa^Og + 70 2 °" ° > SNa^rC^ + 2Fe203 + 8C02
red hot in presence of air
(chromite ore)
[Lime (CaO) added with Na^Og which keeps the mass porous so that air has access to all parts
and prevents fusion]
Then, ZNa^rC^ + H 2 S0 4 > N a ^ O ^ + N a ^ r ^ + I^O
conc. It's solubility Hence, suitable temp, is to be
upto 3 2°C increases / employed to crystallise out
and then decreases * Na 2 S0 4 first.
Then N a ^ r ^ is crystallised out as N a ^ Q ^ O ^ ^ O on evaporation.
(red crystal)

Ques. In laboratory K 2 Cr 2 0 7 is used mainly not NajC^O-y. Why?

S ol. N a ^ r ^ is deliquescent enough and changes its concentration and can not be taken as primary standard
solution whereas K^Ci^C^ has no water of crystallisation and not deliquescent.

How to get K2Cr207 : Na 2 Cr 2 0 7 + KC1 double > K 2 Cr 2 0 ? + 2NaCl

, , decomposition
hot conc.
NaCl crystallises outfirstandfilteredoff. Then less soluble K2Cr207 crystallised
out on cooling

Ques. How to standardise Na2S203 solution in iodometry?

Sol. K2Cr207 is primary standard => strength is known by weighing the salt in chemical balance and
dissolving in measured amount ofwater.
Then in acidic solution add. KI
Cr 2 0 7 2 - + 14H+ + 61- > 2Cr3+ + 3I2 + 7H 2 0
This I2 is liberated can be estimated with S2032~.
Other props & test of Cr0 4 ~- Cr207~ : Already done
* Similarities between hexavalent Cr & S-compounds:
(i) S0 3 & Cr0 3 — > both acidic.
(ii) S > S0 4 ", S 2 0 7 ~, Cr > Cr0 4 ~, Cr 2 0 7 "
9 9
(iii) Cr0 4 & SOf are isomorphous

(iv) S02C12 & Cr02Cl2 oh" ) S04~ & CrO^ respectively.

OH
(v) S03C1- & Sr03Cl~ ~ > S0 4 " & Cr04~

(vi)
fl
CrO, & P(SO.) has same structure - Cr - 0 - Cr - 0 - Cr -
? H
II II II .
0 0 0

fe Bansal Classes d-Block Compounds [4]

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MANGANATE & PERMANGANATE

Preparation ofManganate(Mn04 ):-

K0H
Mn02 > MnOf [2Mn02 +.4K0H + 0 2 > 2K2Mn04 + 2H 2 0]
reen
Ain S n c e o f air S Mn0 2 + 2KOH + KNG>3 > K 2 Mn0 4 + KN0 2 + H 2 0
melt
3Mn02 + 6KOH + KC103 » 3K2Mn04 + KC1 + 3H 2 0
ifK0H
> K2Mn04(isomorphrous
USCd
Green soln. withK2S04)

. .. used isomorphrous with

alkail
Na2S04.10H20

In presence of KC103 & KN0 3 the above

reaction is more faster because these two on
decomposition provides 0 2 easily.

* Manganate is also obtained when KMn04 is boiled with KOH.

b led
4KMn04 + 4KOH °' > 4K2Mn04 + 2H 2 0 + 0 2

Props : The above green solution is quite stable in alkali, but in pure water and in presence of
acids, depositing Mn02 and giving a purple solution of permanganate.
3K2Mn04 + 2H 2 0 ^ 2KMn04 + Mn0 2 I + 4KOH
purple drak brown

Prob.: E° 2 = 2.26 V ; E° 2 = - 0.56 V

MnO^ / M n 0 2 MnO|"/MnO~

Prove that Mn0 4 will disproportionate in acidic medium.

Another Method of Prep". : 3K2Mn04 + 2H2S04 > 2KMn04 + Mn0 2 I + 2K,S0 4 + 2H 2 0

or 3K2Mn04 + 2H 2 0 + 4C0 2 > 2KMn04 + Mn0 2 + 4KHC03
1
But in the above method - of Mn is lost as Mn02 but when oxidised either by Cl2or by 0 3
2K2Mn04 + Cl2 » 2KMn04 + 2KC1 [Unwanted Mn0 2 does not form]
OR
2K2Mn04 + 0 3 + H 2 0 > 2KMn04 + 2KOH + 0 2

Prop.: 2KMn04 ^ K 2 M n 0 4 + Mn0 2 + 0 2

Oxidising Prop, of K M n 0 4 : (in acidic medium)

(i) MnO " + Fe+2 + H+ — > Fe+3 + Mn+2 + ^ O

(ii) MnO ~ +1" + H+ > Mn+2 +12 + H 2 0

(iii) MnO " + I ^ O j + H+ > Mn+2 + 0 2 + H 2 0

fe Bansal Classes d-Block Compounds [4]

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H®
(iv) MnO" + SO2 •> Mn+2 + H.SO4
(v) MnO~ + NO" + H+ > Mn+2 + NO" + H 2 0

(vi) MnO ~ + H 2 C 2 0 4 + H+ » Mn+2 +C0 2 + H^O

(vii) MnO" + H2S >Mn2+ + S ^ + H 2 0

* (1) It is not a primary standard since it is difficult to get it in a high degree of purity and free from traces of
Mn02.
*(2) It is slowly reduced to Mn0 2 especially in presence of light or acid
4MnO~ + 4H+ » 4Mn02 + 2H 2 0 + 30 2
Hence it should be kept in dark bottles and standardise just before use.
(viii) 2KMn04 + 16HC1 — > 2KC1 + 5C12 + 8H20 + 2MnCl2

Oxidising Prop, of KMn0 4 in alk. medium :

2MnO~ + 20H~ > 2Mn0 4 " +H 2 0 + 0. Then 2Mn04~ + 2H 2 0 —-> 2Mn02 + 40H" + 20
(i) 2KMn04 + H 2 0 + KI » 2Mn02 + 2K0H + KI0 3
(ii) 2KMn04 + 3HC02K —-> 2Mn02 + KHC03 + 2K2C03 + H 2 0
(iii) 2KMn04 + 3H ? 0 2 — » 2K0H + 2Mn02 + 2H 2 0 + 30 2

Oxidising Prop, in neutral or weakly acidic solution:

(i) 2KMn04 + 3MnS04 + 2H 2 0 '" presence Zn+ or Zn

" ° > 5Mn02 + K 2 S0 4 + 2H2S04
or Mn0 4 + Mn+2 + 2H 2 0 » 5Mn02 + 4H+
In absence of Zn ions, some of the Mn+2 ion may escape, oxidation through the formation of insoluble
+2

Mnn[MnIV03] manganous permanganite.

(ii) 8KMn04 + 3Na2S203 + HjO > 8Mn02 + 3Na2S04 + 3K2S04 + 2K0H

** Conversion of Mn+2 to MnO 4 :

(i) Pb02 (ii) Pb 3 0 4 + HN0 3 (iii) Pb 2 0 3 + HN0 3 (iv) NaBi03 / H+
+
(v) (NH4)2S208 / H (vi) KI0 4 / H
Prep": Properties ofAg, AgN03, AgBr, Ag2S203

Dry or

(I) Metallic Ag

Not affected dil. HC1

Ag/Ag+. <
E" +
E°. ....
H,/H
Hence in presence of 0 2 .
A g reacts with dil.HCl
4Ag + 4HC1 + 0 2 » 4AgCl|+ 2H20

fe Bansal Classes d-Block Compounds [4]

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In the same way in presence of 0 2 , Ag complexes with NaCN / KCN.

4Ag + 8KCN + 2H 2 0 + 0 2 > 4K[Ag(CN)2] + 4KOH

(II) AgN0 3 : (i) Prep".: already done.

Properties.: (i) It is called as lunar caustic because in contact with skin it produces burning sensation
like that of caustic soda with the formation offinelydevided silver (black colour)
(ii) Thermal decomposition:
2AgN03 2i2°c )2AgNQ2 + 0 2
2AgN02 500°C ^ 2Ag + 2NO + 0 2
Howto separate Ag fromAg- Cu alloy: [Principle: decomposition temperature ofAgN0 3 is much
higher than Cu(N03)2.]
Cu(N03)2 >CuO + N O , + 0 2
- R e s i d u e (CuO)
hnq dissolve.
Ag.Cu 3(':1) > AgNO
hot + 250°C 'n • A g N 0 3 (Crystallised from the solution)
evapouratcd
Cu(N0 3 ) 2 to dryness red hot

Ag

(iii) Props. ofAgN0 3 : [Already done in basic radical]

6AgN03 + 3I2 + 3H 2 0 >5AgI + AgI0 3 + 6HN03
(excess)
(iv) Ag2S04 ^2Ag+ S0 2 + 0 2
B
(V) A(AgN03) > white ppt appears quickly
added
Explain
A ;
B(Na2S203) It takes time to give white ppt.
added

(vi) Ag2S203 + H 2 0 a > Ag2S + H 2 S0 4

AgCl. AgBr. Agl (but not Ag2S) are soluble in N a ^ O j forming
[Ag(S203)2]-3, Na5 [Ag3(S203)4] complexes
(vii) AgBr : AgN0 3 KBr > AgBr i + KN0 3
Pale yellow
PPt-
aq. ngia
(viii) soluble
AgNO dil.HCl. AgCl ^/ffP » Agi + HCl
Ag-J- [4AgCl +2Na2C03 > 4Ag^+ 4NaCl+2C02+02]
K. 7 S 7 O
Ag20 [2AgCI +2NaOH > Ag2C>+ 2NaCl+H20]
glucose
AgO Black
Ag' Agi [Ag20+C6H1206- •2Agl + C5HnC02H]
g l u c o n i c acid

Ag 2 0 + H 2 0 2 -—> 2Ag + I^O + 0 2

K 2 S 2 0 8 + 2AgN03 + 2H 2 0 > 2AgO + 2KHS04 + 2HN0 3

feBansal Classes d-Block Compounds [6]

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AgO supposed to be paramagnetic due to d9 configuration. But actually it is diamagnetic and exists as
Ag1 [Ag ni 0 2 ]

* Reaction involved in developer:

K2Fen(C204)2 + AgBr » KFem (C204)2 + Agi + KBr

ZINC COMPOUNDS

ZnO: It is called as phillospher's wool due to its woolyflocktype appearance

Preparation: 1] 2Zn + 0 2 > 2ZnO
2] ZnC0)33 — Z n O + C0 2
3] iMH2 4-
2Zn(N03)2 — 2 Z n O + 4N0 + 02
4] Zn(OH)>22 — Z7 n O +' H 2 0

Purest ZnO : 4ZnS04 + 4Na2C03 + 3H 2 0 > ZnC03-3Zn(0H)2 I + 4Na2S04 + 3C02

white basic zinc
carbonate

4ZnO + 3H 2 0 t + C0 2 t
pure
Properties: 1] ZnO(coId) ^ ZnO(hot)
white yellow
2] It is insoluble in water
3] It sublimes at 400°C
4] It is amphoteric oxide
ZnO + 2HC1 > ZnCl2 + H 2 0
ZnO + H 2 S0 4 > ZnS04 + H 2 0
ZnO + 2NaOH » Na2Zn02 + I^O
5] ZnO > Zn by H2 & C
ZnO + H2 >400°C ) Zn + H 2 0
ZnO + C > Zn + CO
6] It forms Rinmann's green with Co(N03)2
2CO(N03)2 > 2CoO + 4 N 0 2 + 0 2
CoO + ZnO » CoZn02 or CoO-ZnO
Rinmann's green

Uses: (1) As white pigment. It is superior than white lead because it does not turn into black
(2) Rinmann's green is used as green pigment
(3) It is used as zinc ointment in medicine

[4]
fe Bansal Classes d-Block Compounds

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ZnCl2

Preparation: ZnO + 2HC1 > ZnCU + H 2 0

ZnC03 + 2HC1 > ZnCl2 + H 2 0 + C0 2 \ It crystallises as ZnCl 2 -2H 2 0
Zn(OH)2 + 2HC1 > ZnC^ + 2H 2 0

Anh. ZnCl2 cannot be made by heating ZnCl2-2H20 because

ZnCl22-2H
-2H22(0 — Z n ( O H ) C l + HCl + H 2 0
Zn(OH)Cl — Z n O + HCl
To get anh. ZnCl2: Zn + Cl2 >ZnCl2
Zn + 2HCl(dry) » ZnCl2 + H2
or Zn + HgCl2 >ZnCl2 + Hg
Properties: (i) It is deliquescent white solid (when anhydrous)
(ii) ZnCl2 + H2S >ZnS
" + NaOH > Zn(OH)2 > Na^ZntOH^]
" + NH4OH » Zn(OH)2 excess > [Zn(NH3)4]2+
Uses: 1] Used for impregnating timber to prevent destruction by insects
2] As dehydrating agent when anhydrous
3] ZnO-ZnCl2 used in dental filling

ZnS0 4 -
Preparation:—>
Zn + dil H 2 S0 4 —-» ZnS04 + H2
ZnO + dil H 2 S0 4 -—» ZnS04 + ^ O
ZnC0 3 + dil H 2 S0 4 > ZnS04 + H 2 0 + C0 2
ZnS + 20 2 » ZnS0 4
3
parallel reaction
ZnS + - O,2 > ZnO + SO,
2
2
ZnS + 40 3 > ZnS04 + 40 2

39 70 c >7Q C >280 c
Props. 1] ZnSQ4-7H2Q - ° > ZnSQ4-6H2Q ° > ZnSQ4-H2Q ° > ZnS04
1 >800°C
- 0 2 + S0 2 + ZnO

Uses: 1] in eye lotion

2] Lithophone making (ZnS + B aS 0 4 ) as white pigment

fe Bans al Classes d-Block Compounds [8]

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COPPER COMPOUNDS
CuO
Preparation:(i) CUC03.CU(0H)2 — -> 2CuO + H 2 0 + C0 2 (Commercial process)
Malachite Green
(native Cu-carbonate)

© 2Cu + 0 2 > 2CuO & Ci^O + - 0 2 > 2CuO

(iii) CU(OH)2 — C u O + H 2 0
(iv) 2CU(N03)2 250°C ) 2CNO + 4 N 0 2 + 0 2

Properties:—» (i) CuO is insoluble in water

(ii) Readily dissolves in dil. acids
CuO + H2S04 > CuS0 4 + HjO
HC1 > CuCl2
HN0 3 > CU(N03)2
(iii) It decomposes when, heated above 1100°C
4CuO > 2CU20 + 0 2
(iv) CuO is reduced to Cu by Hj or C under hot condition
CuO + C > Cu + CO T
CUO + H 2 -» Cu + H 2 0 t

CuCl 2 :
Preparation:—> CuO + 2HCl(conc.) ->CUC12 + H 2 0
CU(0H)2-CUC03 + 4HC1 — > 2CUC12 + 3H 2 0 + C0 2

Properties:—> (i) It is crystallised as CuCl^HjO of Emerald green colour

©
dil. solution in water is blue in colour due to formation of
[Cu(H20)4]2+complex.
(iii) conc. HC1 or KC1 added to dil. solution of CuCl2 the colour changes
into yellow, owing to the formation of [CuCl4]2-
(iv) The conc. aq. solution is green in colour having the two complex ions in
equilibrium 2[CU(H20)4]C12 ^ [Cu(H20)4]2+ + [CuClJ 2 + 4H 2 0
(v) CuCl2 > CuCl by no. of reagents
(a) CuCl2 + Cu-turnings — 2 C u C l
(b) 2CUC12 + H 2 S0 3 + H 2 0 > 2CuCl + 2HC1 + 2H2S04
(c) 2CUC12 + Zn/HCl » 2CuCl + ZnCl2
(d) CuCl2 + SnCl2 > CuCl + SnCl4

** CUFj^HjO > light blue Anh. CuCl 2 is dark brown mass obtained
CUC12-2H20 > green by heating CUC1 2 -2H 2 0 at 150°C in presence
CuBr2 > almost black ofHClvap.
150°C
Cul2 does not exist CUC12-2H20 CuCl2 + 2 ^ 0
HClgas

fe Bansal Classes d-Block Compounds [4]

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CuSO4
Preparation:CuO + H2S04(dil) > CuS04 + J^O
CU(OH)2 + H2S04(dil) > CuS04 + 2 ^ 0
CU(0H)2-CUC03 + H2S04 (dil) CuS04 + 31^0 + C0 2
1
Cu + H2S04 + - 0 2 > CuS04 + H,0 [Commercial scale]
(Scrap)
Cu + dil. H2S04 > no reaction {Cu is a below H in electrochemical series}

Properties:—> (i) It is crystallised as CuSO^SHjO

© On
exposure 100°C :
CUS0 4 -5H,0
z
P
" CuS0 4H-3H 2 0 - CUS04-H20
^ enloresence
Blue take places Pale blue Bluish white

230°C

CuS04(anh.)
white
-'800°c: |750°C
CuO + so 2 +^o 2 CuO + S 0 3

(iii) Revision with all others reagent

feBansal Classes d-Block Compounds [10]

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IRON COMPOUNDS

FeS0 4 -7H 2 0:
Preparation:—> (i) Serap Fe + H 2 S0 4 » FeS0 4 + J^T
(dil.)
(ii) From Kipp's waste
FeS + I^SO^dil) » FeS0 4 + H 2 St
7
(iii) FeS2 + 2 ^ 0 + - 0 2 > FeS0 4 + H ^
Properties :-> (i) It undergoes aerial oxidation forming basic ferric sulphate
4FeS0 4 + H 2 0 + 0 2 -> 4Fe(0H)S0 4
FeS0 4 -7H 2 0- 3QQ°c ) FeS0 4
high
(ii) »Fe 2 0 3 +S0 2 +S0 3
anh. white temp.
(iii) Aq. solution is acidic due to hydrolysis
FeS0 4 + 2H 2 0 ^ Fe(OH)2 + H 2 S0 4
weak base
(iv) It is a reducing agent
(a) Fe2+ + Mn04~ + H+ > Fe3+ + Mn2+ + H 2 0
(b) Fe2+ + Cr 2 0 7 2 " + H+ — * Fe3+ + Cr3+ + H 2 0
(c) Au3+ + Fe2+ — » . Au + Fe3+
(d) Fe2+ + HgCl2 » Hg2Cl24 + Fe3+
white ppt.
(v) It forms double salt. Example (NH 4 ) 2 S0 4 -FeS0 4 -6H 2 0

FeO(Black): Prepn: FeC 2 0 4 FeO + CO + CO,

in absence of air

. Props:-* It is stable at high temperature and on cooling slowly disproportionates

into Fe 3 0 4 and iron
4FeO Fe 3 0 4 + Fe
FeCl2:
heated in
Preparation:Fe + 2HC1 > FeCLjL + H~Z
a current of HCl

OR
2FeCl3 + H2 A 2FeCl2 + 2HC1
Properties:—> (i) It is deliquescent in air like FeCl3
(ii) It is soluble in water, alcohol and ether also because it is
sufficiently covalent in nature
(iii) It volatilises at about 1000°C and vapour density indicates the
presence of FcjC^. Above 1300°C density becomes normal
(iv) It oxidises on heating in air
12FeCl2 + 30 2 » 2Fe203 + 8FeCl3
(v) H2 evolves on heating in steam
3FeCl2 + 4 ^ 0 > Fe 3 0 4 + 6HC1 + H2
(vi) It can exist as different hydrated form
FeCl2-2H20 > colourless
FeCL^HjO > pale green
FeCU^HoO » green

fe Bansal Classes d-Block Compounds [4]

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