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63 views8 pagesD and F Block Elements
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/ 8
Chapter 8
The d and f-Block Elements
Answer the following Questions :
1
Chromium, the frst element in Group 6 is a Seely-gray, lustrous, hard metal, The name of this element is
derived from the Greek word chroma meaning colour because many of its compounds are intensely coloured.
This element was ciscovered by Louis Nicolas Vauguelin in the mineral crocoite (lead chromate)
“The caagrem indicating the standard potential values connecting species of an element present in ferent oxdation
states is known as Latimer diagram. In such a diagram, the most oxidized form of an element is represented
at the extreme left, and in successive species the oxidation numter of the element goes on decreasing from
left to right. The numerical values of E* (volt) are written above the lines joining the successive species. Latimer
ciagram for chromium is presented below (All data rofer to pH = ‘)
0203
Cr,OF (MI) 2855 rv) > Gro) 24 Gray A Ertl) 222 Er
orenge ved greon violet bho
-744
(@) Calculate the values of X and Y in the above Latimer diagram.
(©) With appropriate calculations, show Cr (IV) disproportionate to Cr Il) and Cr (VI).
(©) (Cr,03-]/{(Cr>"] system is used as an oxidising agent. Write the balanced chemical equation for this half
cell reaction
(2) Caleulate the change in the potential of the above system, ifthe pH is chenged from 1 to 3 (T = 298 K)
(E(Cr,0,7 CP") = 1.33. (note: With change in pH inthis range, assume thal [Cr,0,2 Jand [Cr] practicaly
remain constant)
(@) 100 cm? of 0.4 N potassium dichromete is titrated with 0.1 N Fe({l) solution. Calculate the potential ofthe
system when 100 em? of 0.1 N Feil) is added.
(pH = 4, E° = Fe"Fe® = 077 V)
In Chrome plating, a layer of chromium is electroplated on a metal object. In this process, chromium
trioxide (CrO,) is used as the source of chromium. In a typical setup, an electrolytic cel was filed with
180 L solution containing chromium trioxide (in this solution, chromium troxide exists as chromic acid
H_CrO,). The elecirolysis was carried out for 8 hrs with a current of 2000A. The object that acted 2s
cathode gained 350g of chromium at the end of 8 hrs. At cathode, in addition to deposition of chromium,
another reaction involving liberation of a gas also took place. Hence, the effiency for the electradeposition
of chromium was less than 100%.
Write balanced equation forthe half cal reaction resulting in deposition of chromium at the cathode, Using
this equation and the given data, calculate the percent efficiency for the electrodeposttion of metalic
chromium,
‘Aakash Educational Services Limited - Regd. Ofice : Aakash Tower, 8, Pusa Road, New Delhi-110005 Pr.017-47623458 (Levelt) ‘The d and Block Elements 17
@) Write balanced chemical equations for the half cell reactions involving liberation of gases at cathode and
anode respectively. Using these equations, calculate the volume of the gases liberated at the cathode and
the enode (T = 298 K end P = 1019 = 105 Nim?)
() An insecticide formulation contains copper (ll) oleate Cu(C H,,0,), (Molar mass = 626). 9.9 g sample
of the insecticide preparation was wet-ashed with a sulfurc-nitic acid mixture to destroy its organic
components. The copper in the sample was then precipitated as the basic chromate, CuCrO, 2Cu02H,0,
with an excess of potassium chromate. The solid was fitered, washed free of excess reagent, and then
redissolved in acid:
2(CuCrO, 2CuO.2H,0)\s) + 10 H" (ag) -» 6Cu*(aq,) + Cr,0,* (a9,) + 9H,0
Titration of the liberated dichromate required 15.7 mL of 0.232 M Fe**. Calculate the percentage of
copper (Il) oleate in the sample.
2 Colourtess salt (A) gives white ppt (B) with NaOH; ppt (B) dissolves in excess of NaOH to form (C). On passing
HS gas into (A) solution whte ppt (D) appears. (A) also gives white pot (E) with AgNO, solution. Identify (A)
to €).
3. In this diagram, the most stable oxidation state is
Nott mano"
‘Mno,
‘Oxidation state
(1) Me @ mn @)Mno,* (4) Mn
4. Iron belongs to a class of metals called transition metals that are generally hard, capable of forming alloys like
steel and exhibit magnetic properties. Transition metal chemistry is dominated by coordination complexes and
variable valence. Iron, its alloys, and its coordination complexes are of high industrial and biological importance.
@ (The main ores of iron are compounds of iron with
(1) Oxygeninitrogen
2) Cxygenisuiphur
(G) \Nitrogenisulphur
(8) Nitrogen/hlorine
(ii) Soluble iron present in ground water causes siow turbicity in water and "yellowing" of white cotton
Glothes washed with such water. This happens because
(1) Iron gots oxidized by aerial oxygen from iron(II) to iron (Il), which is hydrolyzed
{@) ‘ron (I) present in ground water forms a complex with cellulose of white cotton clothes
(@) Solube iron sats get reduced by cellulose present in cotton clothes, causing ecloraton
(4) Iron catalytically oxidizes cellulose to generate conjugated double bonds
(i) Anhydrous ferric chioride (FeCl,) can be used
(1) As a desiccant for organic solvents
(@) As a catalyst for Friedel-Craft reaction
(8) AS a primary standerd for meking solution with known iron
(4) For fortification of food te control iron deficiency anemia
‘Aakash Educational Services Limited - Regd. Ofice = Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456 18 The d and fBlock Elements (Level)
®
©
@
e)
@)
O)
0
5 @)
Rust stains containing iron (It) can be removed by oxalic acids (H,C,O,). as iron forms a soluble coordination
complex with oxalic acid, Write appropriate chemical formula for the complex and give its IUPAC name.
In iron compcund, iron is present in a bivalent or a trivalent state, Write the valence shell electronic
configurations of Fa, Feil) and Fel!
In an aqueous solution of FeSO,7H,0, iron exists as an octahedral complex. Write the structure of this
octahedral complex.
In an octahedral ligand environment, the d orbtals of iron spit. Show the spliting pattem of d orbtals of
iron for the octahedral complex mentioned in (4) Show the electronic configuration of the split d orbitals.
Strorg ligands like CN- enforce pairing of spin. civing rise to a iow-spin complex. What will be the electronic.
configuration of the split d-otbitals of ron in [Fe(CN} I?
What is the spin-only magnetic moments (in Bohr Magnetons] in high-spin and low-spin octahedral iron)
complexes?
Write balanced chemical equations with colours ofthe products forthe reactions that take place when
{An aqueous solution of Fe(II) is added to en aqueous solution of [Fe(CN),I*
{i)_An aqueous sclution of Fell) is added to an aqueous solution of [Fo(CN),J
fii) An aqueous sclution of Fel) is added to an aqueous solution of [Fe(CN),J+:
The specs formed in reacton (i) and (ij are intensely coloured. This is due to
(1) Presence of unpaired electrons in the species [Fe(CN),*
(2) Intramolecular election tansfer between Feil) and Feil)
(8) Intermolecular election transfer between Fel) and Fal)
(4) Formation of conjugate double bends in the complex formed
Iron in haemoglobin can reversibly bind with oxygen, forming oxyhaemoglobin. In both oxyhaemoglobin
and deoxyhaemogiobin, iron is essentially bivalent, However, oxyhaemogbbin is diamagnetic, wherezs
deoxyhaemoclobin is paramagnetic, Iron has a larger bonding radus in deoxyhaemoglobin than in
oxyhemoglobin because
(1) In paramagnetic deoxyhaemoglobin, two adjacent Fe(!!) units of similar magnetic polarity repel each
other, leacing to larger bonding radius
[2) In deoxyhaomegiobin, Fe(l) is high spin, The larger spinning speed of the Fell) ions keops the igands
ata larger distance
(3) In deoxyhaemegiobin, thet, orbitals of Fe(l) are fully occupied with electrons, causing larger repulsion
of the metal ion with ligands
(4) In deoxyhaemoglotin, there are two electrons ine, orbitals of Feil), enforcing greater repulsion with
ligane electrons
Complexes of iron exist with different numbers of unpaired electrons. For the given complexes, write the
number of unpaired electrons and state whether they are high spin or low spin species.
Complex No. of unpaired electrons Spin state
[Fe(cn)it
IFe(cn).f
(Feo,
Fe(toyg
‘Aakash Educational Services Limited - Regd. Ofice : Aakash Tower, 8, Pusa Road, New Delhi-110005 Pr.017-47623458 (Levelt) ‘The d and FBlock Elements 19)
() The oxygen taken during respiration in human beings is carried through the blood stream with the help of.
haemoglobin. The latter is a tetramer containing four heme (iron-porphyrin) units. The oridation state of
iron in deoxyhaemogiobin is +2 and itis a high spin paramagnetic species. On binding with oxygen, the
iron in haemoglobin changes its coordination sphere from 5 to 6. This results in the change in magneto
property. The value of magnetic moment in each unit of oxyhaemoglobin is
©) {Clg is. tow spn ocahedral complex, this is because
(1) The central metal ion i in higher oxidation state
@ tr belongs to third tansiton series.
(©) CF despite being a weak igene, inthis cate acta a8 a strong ligand.
(@) tis a complex anion with -2 charge
(ii) Drawa simple labeled cystal field spliting diagram for [IrCl,J* showing distribution of electrons in the
split c-orbitals,
(6) The flock elements, lanthanides and actinides, are characterized by gradual filing of the 4f and 5f sub-
shell respectively
‘The most common oxidation state of lanthanides is 3+. This oxidation state of lanthanide ions arises due
to the loss of two 6s electrons and one 5d electron in 4/150 orbital. Besides 3+, some lanthanides like Ce,
Sm and Eu also show other oxidation states.
Give the chemical equations for tne general reactions of lanthanides (Ln) with (1) water and (ll) acid, and of
cerium (Ce) with (i) oxygen and (iv) fuorine,
6 Write the equations.
(0. Acidfied solution of K,Cr,0, turns green when sodium suiphite is added to it
(i) Potassium ferricyanide is added to ferrous sulphate
(ii) Silver chloride is treated with aqueous sodium cyanide
(¥) Zincis exposed to moist ait.
7. Explain the following,
(Alte acd is always added in the preparation of aqueous ferrous sulphate solution,
(Aqueous solution of mercuric chloride and stannous chioride cannot exist together.
(ii) Ferris iodide is very unstable but ferric chloride is not.
(W) Ho@ and Hg, salts are cotouriess generally.
8B Colourless salt (A) 4, (B) + (C),., dissolves both in acid and alkali solution. Gas (C) turns Ime water milky
‘and scidified K,Cr,0, solution green. Ammoniacal solution of (A) gives white ppt (D) with H,S gas. identify (A),
(8), (C) and (0).
2 tently @, © ard © and wrte chemical equations,
we
Pyrotsite*""___ dark green —“®° + purge SS
Trevor ora” oatk aroen cryaais
‘0,
©
‘Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456, 20° The d and fBlock Elements (Level)
10
1
12,
13,
4,
6
ldontty ®. ©. ©. © inthe flow diagram and write equations
os
©+O+ eesisue
Heatea strongly
crromate
A solution
tghtgren sot
desdvesin H'SO,
but no gas is evolved
FET ppl] + SS G «bold win Hos
Paragraph for Q. Nos. 11 and 12
Conversion of M to M’(aq) depends upon a number of factors like heats of atomisation, ionisation energy and
hoat of hydration. Consider the thermochemical data of four motals P, Q, R and S.
Element. 4H, AH, Baya MP
P 431 736 1750 2121
a 120 908 1730 2089
R 39 745 1960 2121
8 418 762 1560 x
The correct order of ease of conversion of M'? to M for the spacies P, Q and R varies as (based on above
data only)
(1) P>Q>R @ PeR>Q () R=P>Q (@) R>Q>P
IF metal ion S* has more electron accepting tendency than O%* then find the minimum value of X for which
this is possible (based on above data only)
(1) ~ 2030 @) ~ 2245 (@) 2190 (4) ~ 2345
Paragraph for Q. Nos. 13 and 14
Iron cromite (FeCr,0,) on reaction with sodium carbonate n presence of 0, forms chromium containing compound
IM. The solution of compound Mis tered and acidified with sulphuric acid to give a chromium containing crystalline
compound N. if solution of N reacts with KCI then forms chromium containing compound O.
Colour of solution of compound M is
(1) Yellow @) Orange (@) Black (4) Green
Select the correct statement.
(1) Compound 0 is more soluble than N in water
@) Oxidation number of chromium in’M, N and Ois seme
@) Colour of N and O are different
(4) Compound cannot be used as primary standard in volumetric enalysis
Potassium Permanganate (KMInO,); chameleon mineral or Candis crystals is an inorganic compound which
‘dissolves in water to give an intensely pink or purple solution. The evaporation of this solution leaves prismatic
purplish-black glistening crystals. On a small scale potassium permanganate is prepared from the
‘isproportonation of potassium manganate in acidic medium,
(@ Write a balanced equation for this reaction.
(b) Draw the Lewis det structures of manganate and permanganate species. State which of the species is
paramagnetic. Calculate the spin only magnetic moment for the paramagnetic species.
(©) When concentrated HySO, is added fo KMnO, it gives @ greenish oily dimanganese heptaoxide.
(0) Write the balanced equation for this reaction,
(i) Draw the structure of dimanganese heptaoxide.
‘Aakash Educational Services Limited - Regd. Ofice : Aakash Tower, 8, Pusa Road, New Delhi-110005 Pr.017-47623458 (Levelt)
@
®
®
‘The d and Block Elements 21
On standing, the above oxide decomposes to form manganese dioxide. Write a balanced chemical equation
‘or the reaction
The Latimer Diagram for a series of manganese species in acidic medium (pH = 1) Is given below. The emt
values (E") shown are standard reduction potentials in volt.
Mno; 222, Hino; £32209, Mino, E098 Mind BEET yy? EE ig
In acigic medium, solid MnO, is converted to Mn? and MnO,
()) Write balanced equations for the half cell reactions involved and the overall reaction,
(ii) Using the Latimer diagram, calculate the standard electrode potential for each half call reaction and
for the overall call reaction.
(i) Calculate K for the overall reaction
In an acidic medium MnO; is a strong oxidizing agent and is thus often used in redox titration,
Medical shops sell 6% (wiw) aqueous solution of HO, as a disinfectant. X g of this H,0, solution was,
titrated using KMnO, (0.02 M) solution in an acidic madium. Tho sample required 16.0 mL KMIn0, solution,
Write balanced equation for the reaction involved in the titraton. Calculate the amount of H,0, in grams
that was titrated. (Show the relevant steps)
The Frost Diagram (also known as oxidation state diagram) of an element (X) is a plot of voltequivalent
(NE*) for a couple X(N)X(0) against oxidation number (N) of the element. Such a plot can be constructed
‘rom Latimer diagram, The Frost diagram for manganese species in. acidie and basic condition is given
below.
6
5 MnO,
4
3
2
= has
1 —
0
q
A
Mno,
2
3
MOH) in
4 KOH. Hr, NNO;
(Oxidation Number (N) ->
Using the given diagram fil in the blanks,
(i) The slope of the line joining two successive pointe ie equal to Of the relevant couple.
[ii) The most stable oxidation state of manganese in acidic condition is and in basie condition
is
(li) In basic conditon, he species of manganese that wil alsproportionate is
{\) In acidic condition, the two pairs of manganese epeciae that will comproportionete (opposite of