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S.NO.
TOPIC
PAGE NO
1. INTRODUCTION
3. GENERAL CHARACTERISTICS
4. COLOUR
5. COMPLEX FORMATION
6. CHROMATE -DICHROMATE
9. ZINC COMPOUNDS
10 .COPPER COMPOUNDS
10
11
12
d & f - block
d & f - BLOCK
1. INTRODUCTION
In these elements the last electron enters (n1)d orbitals of atom of an element is called d-block
elements.
3. GENERAL CHARACTERISTICS
(i) Metallic character: They are all metal and good conductor of heat & electricity
(ii) Electronic configuration: (n1)d110ns12
(iii) M.P. Cr Maximum
Zn lowest m.p.
Cd due to no unpaired e
Mo 6 no. of unpaired e s
decreases
remains increases
same
again
(v) Variable oxidation states possible
Sc Ti V Cr Mn Fe Co Ni Cu Zn
1
1
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)
Sc3+ colourless
Ti4+ colourless
Ti3+ purple
V4+ blue
V3+ green
V2+ violet
Cr2+ blue
Cr3+ green
Mn3+ violet
Mn2+ light pink
Fe2+ light green
Fe3+ yellow
Co2+ pink
Ni2+ green
Cu2+ blue
Zn2+ colourless
d & f - block
4. COLOUR
Substances appear coloured when they absorb light of a particular wavelength in the visible region of the
spectrum and transmit light of other wavelengths. The colour which we see is the colour of the transmitted
wavelengths. In other words, the colour of the compound observed by us is the complmentary colour
of the colour absorbed by the compound.
In the s- and p-block elements there cannot be any d-d transitions and the energy needed to promote s
or p electron to a higher level is much greater and may correspond to ultraviolet region, in which case the
compound will not appear coloured to the eye.
Relationship between colour and wavelength
Wavelength absorbed in nm Colour absorbed
Colour observed
<400
UV region
White/colourless
400435
Violet
Yellow-green
Indigo
Yellow
435480
Green-blue
Orange
480490
Blue-green
Red
490500
Green
Purple
500560
Y
ellow-green
Violet
560580
Yellow
Indigo
580595
Orange
Green-blue
595605
Red
Blue-green
605750
Infra-red
White/colourless
> 750
Magnetic Properties: When a substance is placed in a magnetic field of strength H, the intensity of the
magnetic field in the substance may be greater than or less than H.
diamagnetic, Substances which are weakly repelled by a magnetic field
paramagnetic the substances which are weakly attracted bythe magnetic field and lose their
magnetism when removed from the field .
Paramagnetism is expressed by magnetic moment,
n(n 2) B.M.
n = number of unpaired electrons
B.M. = Bohr Magneton, unit of magnetic moment
5. COMPLEX FORMATION
In the case of transition metals in low oxidation states, the electrons in the d orbitals become involved in
bonding with ligands.The bonding between the ligand and the transition metal ion can either be
predominantly electrostatic or covalent or in many cases intermediate between the two extremes. Some
of the typical complexes of the transition meals are [Fe(CN) 6]3 ,[Ni(NH 3) 4]2 ,[Cu(CN) 4 ]3 ,
[Cu(NH 3) 4]2 etc.
Formation of alloys :
Transition elements have almost similar atomic sizes. Therefore , these elements can mutually
substitute their positions in their crystal lattice. The alloys are hard and have high melting points as
compared to the most metal.
Catalytic Properties: Many transition metals and their compounds have catalytic properties.
some example
TiCl 3
Used as the Ziegler-Natta catalyst in the production of polythene.
V2O 5
MnO 2
d & f - block
Fe
6. CHROMATE -DICHROMATE
Preparation :
4FeO . Cr2O3 + 8Na2CO3 + 7O2
chromate ore
Rosting
in air
The roasted mass is extracted with water when Na2CrO4 goes into the solution leaving behind insoluble
Fe2O3. The solution is treated with calculated amount of H2SO4.
2Na2CrO4 + H2SO4 Na2Cr2O7 + Na2SO4 + H2O
The solution is concentrated when less soluble Na2SO4 crystallises out. The solution is further concentrated
when crystals of Na2Cr2O7 are obtained. Then a hot saturated solution of Na2Cr2O7 is treated with KCl
when reddish orange crystals of K2Cr2O7 are obtained on crystallisation.
K2Cr2O7 is preferred to Na2Cr2O7 because Na2Cr2O7 is hygroscopic but K2Cr2O7 is
not.
* Other props & test of CrO2
& Cr 2O 2
:Already discussed
4
7
* Similarities between hexavalent Cr & S-compounds:
(i) SO3 & CrO3 both acidic.
d & f - block
2
2
OH
(iv) SO3Cl & CrO3Cl
SO 4 & CrO4
O
O
O
||
||
||
Cr
O
Cr
O
Cr
MnO 42 / MnO 2
= 2.26 V
Eo
MnO 42 / MnO4
= 0.56 V
d & f - block
1
But in the above method of Mn is lost as MnO2 but when oxidised either by Cl2 or by O3
3
2K2MnO4 + Cl2 2KMnO4 + 2KCl [Unwanted MnO2 does not form]
OR
2K2MnO4 + O3 + H2O 2KMnO4 + 2KOH + O2
(iv) NaBiO3 / H+
(I) MetallicAg
d & f - block
Explain
added
Pale yellow
ppt.
Heating effect:
C
2AgNO3 212
2AgNO2 + O2
C
2AgNO2 500
2Ag + 2NO + O2
(viii)
d & f - block
9. ZINC COMPOUNDS
(1) Zinc oxide, ZnO (Chinese white or philosopher's wool)
Its found in nature as zincite or red zinc ore.
Preparation :
(i) 2Zn + O2 2ZnO
(ii) ZnCO3
(iii) 2Zn(NO3)2
(iv) Zn(OH)2
ZnO + CO2
2ZnO + 4NO2 + O2
ZnO + H2O
(a) Physical Properties : It is white powder becomes yellow on heating again turns white on cooling ,
insoluble in water, sublimes at 400C.
(b) Chemical Properties :
(i) ZnO + H2SO4 ZnSO4 + H2O
(iii) ZnO + 2NaOH Na2ZnO2 + H2O
(iv) ZnO + H2
(v) ZnO + C
400 C
Zn + H2O
Zn + CO
ZnCl22H2O
Zn(OH)Cl + HCl + H2O
d & f - block
parallel reaction
ZnS + O 2 ZnO + SO 2
2
ZnS + 4O3 ZnSO4 + 4O2
70C
280C
3970C
Props. 1] ZnSO47H2O
ZnSO46H2O ZnSO4H2O ZnSO4
1
O + SO2 + ZnO
2 2
Uses: 1] in eye lotion
2] Lithophone making (ZnS + BaSO4) as white pigment
CuCO3.Cu(OH)2
2CuO + H2O + CO2 (Commercial process )
Malachite Green
(native Cu-carbonate)
1
O
2CuO
2 2
(ii)
(iii)
Cu(OH)2
CuO + H2O
(iv)
C
2Cu(NO3)2 250
2CuO + 4NO2 +
O2
CuO is insoluble in water
Readily dissolves in dil. acids
CuO + H2SO4 CuSO4 + H2O
HCl CuCl2
HNO3 Cu(NO3)2
It decomposes when, heated above 1100C
4CuO 2Cu2O + O2
CuO is reduced to Cu by H2 or C under hot
condition
CuO + C Cu + CO
CuO + H2 Cu + H2O
Properties: (i)
(ii)
(iii)
(iv)
CuCl2 :
Preparation:
Properties:
d & f - block
CuSO4 :
Preparation:
Properties:(i)
(ii)
take places
CuSO43H2O
CuSO4H2O
Pale blue
Bluish white
CuSO4(anh.)
white
(iii)
(iii)
Properties: (i)
(ii)
(iii)
FeS2 + 2H2O +
10
d & f - block
(iv)
It is a reducing agent
(a) Fe2+ + MnO 4 + H+ Fe3+ + Mn2+ + H 2O
(b) Fe2+ + Cr 2O 72 + H+ Fe3+ + Cr3+ + H 2O
(c) Au3+ + Fe2+ Au + Fe3+
(d) Fe2+ + HgCl2 Hg 2Cl2 + Fe3+
white ppt.
(v)
FeO(Black):
Prepn :
Props:
FeCl2:
Prepn:
It is stable at high temperature and on cooling slowly disproportionates into Fe3O4 and
iron
4FeO Fe3O4 + Fe
Fe + 2HCl heatedin FeCl2 + H2
a current of HCl
OR
Props:
2FeCl3 + H2
2FeCl2 + 2HCl
(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 1000C and vapour density indicates the presence of Fe2Cl4.
Above 1300C density becomes normal
(iv) It oxidises on heating in air
12FeCl2 + 3O2 2Fe2O3 + 8FeCl3
(v) H2 evolves on heating in steam
3FeCl2 + 4H2O Fe3O4 + 6HCl + H2
(vi) It can exist as different hydrated form
FeCl22H2O colourless
FeCl24H2O pale green
FeCl26H2O green
FeCl3:
Prepn: Anhydrous ferric chloride is prepared by heating metallic iron in a stream of dry chlorine gas.
(i) FeCl3 solid is almost black. It sublimes at about 300C, giving a dimeric gas.
(ii) FeCl3 dissolves in both ether and water, giving solvated monomeric species.
(iii) Iron (III) chloride is usually obtained as yellow-brown lumps of the hydrate FeCl36H2O.
(iv) This is very soluble in water and is used both as an oxidizing agent, and as a mordant in dyeing.
(v) FeCl3 is also used in the manufacture of CCl4.
11
d & f - block
General Characteristics:
1. Electronic Configuration
[Xe] 4f n 1 5d 0 6s 2 or [Xe] 4f n 5d1 6s 2
2. Oxidation state: They readily form M 3 ions some of them also exhibit oxidation state of +2 and +4.
3. Colouration: Ions of Lanthanides and actinides are coloured in the solid state as well as in aqueous
solution because of absorbation of light due to ff transition since they have partly filled f-orbitals.
12
d & f - block
5. Colour. The lanthanide metals are silvery white metals and the trivalent lanthanide ions are coloured
both in the solid state and in the aqueous solution.
6. Magnetic properties. La3+ (4f0) and Lu3+ (4f14) having no unpaired electron do not show
paramagnetism while all other tripositive ions of lanthanides are paramagnetic.
7. They have low ionisation energy and are highly electropositive. Their ionisation energy values are
quite comparable with those of alkaline earth metals particularly calcium.
8. These metals do not have much tendency to form complexes.
9. The lanthanides are highly reactive. This is in agreement with the low values oftheir ionisation energies
and electronegativity.
10. The solubilityof compounds of lanthanides follow the same order as group 2 elements. Their fluorides,
oxides, hydroxides, carbonates are insoluble in water. However halides (except fluorides), nitrates,
acetates are soluble in water.
General Characteristics ofActinides 5f Block Series Second Inner Transition Series
1. These are silvery white metals with high melting and boiling points.
2. Besides the most common oxidation state of +3, actinides show +4, +5 and +6 oxidation states in
certain elements.
3. All the actinides are radioactive in nature.
4. All the actinides are highly electropositive and as such are strong reducing agent.
5. Actinides have a strong tendency towards complex formation and form oxocations like UO22+,
PuO22+, UO+ etc.
6. Most of the cations of actinides are coloured.
7. Actinides show actinide contraction i.e., decrease in ionic radii along the series.
13
d & f - block
SOLVED EXAMPLES
Ex.1
Sol.
Ex.2
Sol.
Ex.3
Sol.
Ex.4
Sol.
Ex.7
Sol.
14
d & f - block
Ex.8
Sol.
Ex.9
Sol.
Q.13
Sol.
Q.14
Sol.
15
d & f - block
Ex.17 For the first row transition metals the E values are:
E
V
Cr
Mn
Fe
Co
Ni
Cu
2
0.91
1.18
0.44
0.28
0.25
+0.34
(M + /M) 1.18
Explain the irregularity in the above values.
Sol. The E (M2+/M) values are not regular which can be explained from the irregular variation of ionisation
entthalpies (iHl+ iH2 ) and alos the sublimation enthalpies which are relatively much less for maganese
and vanadium.
Ex.18 The E (M2+ /M) value for coppers is positive ( + 0.34V), What is possibly the reason for this ?
Sol. E (M2+/M ) for any metal is related to the sum of the enthalpy change taking place in the following steps:
M(s) + aH M(g)
(a H= Enthalpy of atomisation)
2+
M(g) + iH M (g)
(a H= Ionization enthalpy)
2+
2+
M (g) + aq M (aq) + DhydH
(hydH = Hydration enthalpy)
Copper has high enthalpy of atomisation and low enthalpy of hydration . So E (Cu2+/Cu) is positive.
The high energy to transform Cu(s) to Cu2+(aq) is not balanced by it s hydration enthalpy.
Ex.19 (a) Complete the following chemical equation of for reactions:
(i) MnO4 (aq) + S 2O 32 (aq) + H 2O(l)
(ii) CrO7 (aq) + H2(g) + H+ (aq)
(b) Give an explanation for each of the following observation:
(i) The gradual decrease in size (actinoid contraction) from element to element is greater among the
actionod is than that among the lanthanoids (lanthanoids contraction).
(ii) The greatest number of oxidation states are exhibited by the members in the middle of a transition series.
(iii) With the same d- orbital configuration (d4) Cr2+ ion is a reducing agent but Mn3+ ion is an
oxidisng agent.
Sol. (a) (i) In neutral or faintly alkaline solutions
MnO4 + 2H 2O + 3e MnO 2 + 2H 2P + 4OH] 8
S2O32 + 10OH 2SO 42 + 5H 2O + 8e] 3
8Mn O32 + 10OH + H 2O 8 MnO 2 + 6SO 42 + 2OH
(ii) In acidic solutions
Cr2O72 + 14H+ + 6e 2Cr3+ + 7H 2O
H2S S + 2H+ + 2e] 3
Cr2O72 + 3H 2S+ 8H+ 2Cr3+ + 3S + 7H 2O
(b) (i) This due to poor shielding by 5f electrons from element to element in actinoid than by 4f
electrons in lanthanoids series.
(ii) This is due to involvement of both (n1) d and ns electrons in bonding, which are unpaired in
maximum number at the middle of series.
(iii) Cr2+ has the configuration d4 and easily changes to Cr3+ which has half t 2g configuration and
hence move stable. Therefore Cr2+ is reducing. On the other hand, the change from Mn3+ to
Mn2+ results inthe halffilled, d5 configuration whichhas extra stability. Therefore Mn3+ in oxidising.
16
d & f - block
Sol.
(iii) the members in the actinoid series exhibit a large number of oxidation states than the
corresponding members in the lanthanoid sereis.
(a) (i) In acidic medium:
MnO4 + 8H+ + 5e Mn2+ + 4H 2O] 2
C2O42 2CO 2 + 3e] 5
2MnO4 +5C 42 + 16H+ 2M n2+ + 10 CO 2+ 5H 2O
(ii) In acidic medium
Cr4 O72 + 14H+ + 6e 2Cr3+ + 7H 2O
Fe2+ Fe3+ + e ] 6
Cr4 O72 + 6Fe2+ +14H+ 2Cr3+ + 6Fe3+ + 7H 2O
(b) (i) On moving from titanium to copper in general atomic mass increases where as atomic size
decreases, therefore density increases in general
(ii) The frequent metal-metal bonding in compounds of heavy transition elements is due to their
high enthalpyof atomization.
(iii) Thisisdueto verysmall energygap between5f, 6dand 7sorbitals inthe actinoids series.
2Mn2+ + 10CO 2 + 8H 2O
2Cr3+ + 7H 2O
Fe3+ +e] 6
2Cr3+ +6Fe3+ + 7H 2O
17
d & f - block
Ex.22 (a) What may be the possible oxidation states of the transition metals with the following d-electronic
configuration in the ground state oftheir atoms.
3d3,s2,3d5,4a2 and 3d6 4s2. Indicate relative stability of oxidation states in each case.
(b) Write steps involved in the preparation of
(i) Mn2CrO4 from chromite ore and
(ii) K2MnO4 from pyrolusite ore.
Sol.
(a)
Electronic
conf iguration
3d24 s2
Element
Possible O.S.
Vanadium
+ 2, +3, + 4, + 5
+5
3d 4 s
Manganese
+ 2, +3, + 4, + 5,
+2 +7
Iron
+ 2, +3, + 4, +6,
+2 +3
3d 4 s
Mo re Stable O.S.
(b) (i) Chromite ore is fused with sodium carbonate in excess of air.
4FeCr2O4 + 8Na2CO3 + 7O 2 8Na 2CrO 4 + 2Fe 2O 3 + 8CO 2
chromite ore
Sod. chromate
(ii) Pyrolusite ore (MnO2) is fused with KOH in the presence of O 2 or oxidising agent such as
KNO 3.
2MnO2 + 4KOH + O 2 2K 2MnO 4 + 2H 2O
Pyrolusite ore
Postassium magnate
18
d & f - block
EXERCISE - I
Q.1
Q.2
Q.3
Q.4
Q.5
Q.6
Q.7
Q.8
Q.9
Q.10
Q.11
Q.14
Q.15
Q.16
19
d & f - block
Q.17
Q.18
Q.26
Q.19
Q.20
Q.27
Q.28
Q.21
Q.22
Q.23
Q.30
Cu
0.34V
20
d & f - block
EXERCISE - II
Q.11
Q.1
Q.2
Q.3
Q.4
Q.5
Q.6
NaOH
Q.14
Q.15
dissolves in NaOH
[C]
Pass H 2 S
Q.7
Q.8
Q.9
Q.13
Q.10
21
d & f - block
EXERCISE - III
Q.8
Q.9
Q.10
.solvent
Acidified chromic acid + H2 O2 Org.
X + Y , X and Y are
(A) CrO5 and H2O
(B) Cr2O3 and H2O
(C) CrO2 and H2O
(D) CrO and H2O
Cr2O 27
Q.11
Q.12
Q.13
Q.14
Q.15
Q.2
Q.3
2NH 3 ( g) ;
2CrO 2
, X and Y are
4
respectively
(A) X = OH, Y = H+
(B) X = H+, Y = OH
(C) X = OH, Y = H 2O 2
(D) X = H2O2, Y = OH
Q.4
Q.5
Q.6
Q.7
22
d & f - block
Q.16
Q.23
Q.17
Q.24
(A) Mo
(C) Tc
(B) Ta
(D) Pm
(A) Zn, Hg
(C) Co, Fe
Q.18
Q.19
Q.20
Q.21
(B) Zn, Fe
(D) Mg, Fe
Q.26
Q.27
Q.28
Q.29
Q.22
23
d & f - block
Q.31
Q.32
Q.33
Q.34
Q.35
Q.36
Q.37
Q.39
Q.40
Q.41
Q.42
Q.43
Q.44
Q.45
24
d & f - block
Q.47
Q.48
Q.49
Q.50
Q.51
Q.52
Q.53
Q.54
Q.55
Q.57
Q.58
Q.59
Q.60
25
d & f - block
ANSWER KEY
EXERCISE - II
Q.1
Q.2
Formation of MnO4
Q.3
NH3 - strong ligand causes pairing of electrons. So complex is diamagneitc. F is a weak ligand and so
pairing is not possible.
[Al (OH)3 and NaAlO2; Zn(OH)2 and Na2ZnO2] also [Zn(NH3)4]2+
Q.4
Q.5
Q.6
[A] = ZnCl2; [B] = Zn(OH)2; [C] = Na2ZnO2; [D] = ZnS; [E] = AgCl l
Q.7
Q.8
Q.9
Q.10
Q.11
Q.12
Cl is a weak ligandso no pairing of electrons. CO is a strong field ligand and, therefore, causes
pairing of electrons.
Q.13
Q.14
In the first case, a double salt is formed. In the second case, a complex is formed. So no test.
Q.15
Q.16
EXERCISE - III
Q.1
Q.2
Q.3
Q.4
Q.5
Q.6
Q.7
Q.8
Q.9
Q.10
Q.11
Q.12
Q.13
Q.14
Q.15
Q.16
Q.17
Q.18
Q.19
Q.20
Q.21
Q.22
Q.23
Q.24
Q.25
Q.26
Q.27
Q.28
Q.29
Q.30
Q.31
Q.32
Q.33
Q.34
Q.35
Q.36
Q.37
Q.38
A,B,C
Q.39
B,C,D
Q.40
A,B
Q.41
A,B
Q.42
A,B
Q.43
B,C
Q.44
A,B,C
Q.45 A,B,C
Q.46
A,B,C
Q.47
A,B
Q.48
B,C
Q.49
A,C
Q.50
A,B
Q.51
A,B,C,D
Q.52
A,B
Q.53
A,B,C
Q.54
A,B
Q.55
B,C
Q.56
Q.57
Q.58
Q.59
Q.60
26