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Published on: 05/08/2019
The d- and f- Block Elements
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1.
How would you account for the following:
(i) With the same \(d\)-orbital configuration \((d^{ 4 })Cr^{ 2+ }\) is a reducing agent while \(Mn^{ 3+ }\) is an oxidizing agent.
(ii) The actinoids exhibit a larger number of oxidation states than the corresponding members in the lanthanoid series.
(iii) Most of the transition metal ions exhibit characteristic in colours in aqueous solutions.
2.
A mixed oxide of iron and chromium, FeO. Cr2O3 , is fused with sodium carbonate in presence of air to form a yellow coloured compound (A). On acidification, the compound (A) forms an orange coloured compound (B) which is a strong oxidizing agent. Identify
(i) the compounds (A) and (B)
(ii) Write balanced chemical equations for each step.
3.
Why are transition elements known as d - block elements?
4.
A substance is found to have a magnetic moment of 3.9 B.M. How many unpaired electrons does it contain ?
5.
The chemistry of the actinoid elements is not so smooth as that of the lanthanoids. Justify this statement by giving some examples from the oxidation state of these elements.
6.
Compare the stability of +2 oxidation state for the elements of the first transition series.
7.
Write complete chemical equations for:
(i) Oxidation of Fe2+ by Cr2O72- in acid medium.
(ii) Oxidation of S2O32- by MnO4- in neutral aqueous medium.
8.
Predict which of the following will be coloured in aqueous solution. Ti3+, V3+, Cu+, Sc3+, Mn2+, Fe3+ and Co2+. Give reason for each.
9.
Which trivalent cation is largest in the lanthanoid series?
10.
Actinoid contraction is greater from element to element than lanthanoid contraction. Why?
11.
(a) Given below are the electrode potential values, Eo for the some of the first row of transition elements:
| Element | EoM2+/M (V) |
|
V(23) Cr(24) Mn(25) Fe(26) Co(27) Ni(28) Cu(29) |
-1.18 -0.91 -1.18 -0.44 -0.28 -0.25 +0.34 |
Explain the irregularities in these values on the basis of electronic structures of atoms.
(b) Complete the following reaction equations:
(i) Cr2O72-+Sn2++H+\(\longrightarrow \)
(ii) MnO4-+Fe2++H+\(\longrightarrow \)
12.
Highest oxidation state of manganese in fluoride is +4 (MnF4) but highest oxidation state in oxides is +7 (Mn2O7 ) because ............ .
fluorine is more electronegative than oxygen
fluorine does not possess d - orbitals
fluorine stabilise lower oxidation state
in covalent compounds, fluorine can form single bond only while oxygen forms double bond
13.
Which of the following statements is not correct ?
Copper liberates hydrogen from acids
In its higher oxidation states, manganese forms stable compounds with oxygen and fluorine
Mn3+ and Co3+ are oxidising agents in aqueous solution
Ti2+ and Cr2+ are reducing agents in aqueous solution
14.
The magnetic nature of elements depends on the presence of unpaired electrons, Identify the configuration of transition element, which shows highest magnetic moment.
3d7
3d5
3d8
3d2
15.
Generally transition elements form coloured salts due to the presence of unpaired electrons. Which of the following compounds will be coloured in solid state ?
Ag2SO4
CuF2
ZnF2
Cu2CI2
16.
Electronic configuration of a transition element X in +3 oxidation state is [Ar] 3d5. What is its atomic number ?
25
26
27
24
17.
Name a member of lanthanide series which is well known to exhibit + 4 oxidation state :
Ce
La
Lu
Pr
18.
KMnO4, oxidation number of Mn is
+ 2
+ 4
+ 6
+ 7
19.
Which of the following statement about transition elements is incorrect ?
They show variable oxidation states
All the ions are coloured
They exhibit diamagnetic and paramagnetic properties
They exhibit catalytic property
20.
Which of the following ixidation states is the most common among the lanthanoids ?
4
2
5
3
21.
Irregular trend in the standard reduction potential value of the first row transition elements is due to
regular variation of first and second row enthalpies
irregular variation of sublimation ethalpies
regular variation of sublimation ethalpies
increase in number of unpaired electrons
22.
Uranium
23.
Thorium
24.
Lanthanum
25.
Cu2+
26.
Lanthanoid
1.
(i) The high melting points of transition metals are due to strong metallic bonds between the atoms of these elements. This is because of involvements of a greater number of electrons in the interatomic metallic bonding from (n-l) d orbitals in addition to ns electrons.
(ii) Lanthanoids show limited the number of oxidation states, such as + 2, + 3 and + 4 (+ 3 is the principal oxidation state). This is because of the large energy gap between 5d and 4f subshells. On the other hand, actinoids also show principal oxidation state of + 3 but show a number of other oxidation states also. For example, uranium (Z = 92) exhibits oxidation states of + 3, + 4, + 5, + 6 and + 7 and neptunium (Z = 93) shows oxidation states of + 3, + 4, + 5, + 6 and + 7. This is because of the small energy difference between 5f, 6d and 7s orbitals
(iii) Most of the transition metal ions are colored both in the solid state and in aqueous solutions. The color of these ions is attributed to the presence of incomplete (n - 1) d-subshell. The electrons in these metal ions can be easily promoted from one energy level to another in the same d-subshell. The amount of energy required to excite the electrons to higher energy states within the same d-subshell corresponds to the energy of certain colors of visible light. Therefore, when white light falls on a transition metal compound, some of its energy corresponding to a certain color is absorbed causing promotion of d-electrons. This is known as d-d transitions. The remaining colors of white light are transmitted and the compound appears colored. For example, hydrated cupric compounds absorb radiations corresponding to red light and the transmitted color is greenish-blue (which is complementary color to red color). Thus, cupric compounds have greenish-blue color.
2.
\(4 FeO. Cr_2O_3 + O_2\longrightarrow 2 Fe_2O_3 + 4 Cr_2O_3\)
\(\underline{4 Na_2CO_3 + 2 Cr_2O_3 + 3 O_2 \longrightarrow 4 Na_2CrO_4 + 4 CO_2 \times 2}\)_________________
\(4 FeO. Cr_2O_3 + 8 Na_2CO_3 + 7 O_2\longrightarrow\underset{Sodium\ chromate} {\underset{{A}}{8 Na_2CrO_4}} + 2 Fe_2O_3 + 8 CO_2\)
\(2 Na_2CrO_4 + H_2SO_4 \longrightarrow\underset{(B)\\sodium\ choromate} {Na_2Cr_2O_7} + Na_2SO_4 + H_20\)
3.
Transition elements are called d - block elements because the last electron enters (n - 1) d - orbital, i.e., d - orbital of the penultimate shell.
4.
Using formula
\(\mu=\sqrt{n(n+2)} B \cdot M ., n=3\)
5.
Lanthanoids primarily show three oxidation states (+2, +3, +4). Among these oxidation states, +3 state is the most common. Lanthanoids display a limited number of oxidation states because the energy difference between 4f, 5d, and 6s orbitals is quite large. On the other hand, the energy difference between 5f, 6d, and 7s orbitals is very less. Hence, actinoids display a large number of oxidation states. For example, uranium and plutonium display +3, +4, +5, and +6 oxidation states while neptunium displays +3, +4, +5, and +7. The most common oxidation state in case of actinoids is also +3.
6.
Elements (+ 2 state ) 21Sc2+'22Ti2+ 23V2+ 24 Cr2+ and 25Mn2+have more stable +2 oxidation state and the outer electronic configuration are 3d1 , 3d2 , 3d3 , 3d4 and 3d5, respectively. In all the elements listed, the removal of two 4s electrons (in Cr2+, 1e- from 4s and 1e- from 3d), the 3d-orbitals get gradually occupied. Since, the number of empty d-orbitals decreases or the number of unpaired electrons in 3d-orbitals increases with increase in atomic number of cations, so the stability of the cations (M 2+) increases from Sc2+ to Mn.
7.
(i) 6Fe2++Cr2O72-+14H+\(\rightarrow \)6Fe3++2Cr3++7H2O
(ii) 8MnO4-+3S2O32-+H2O\(\rightarrow \)8MnO2+6SO42-+2OH-
8.
Ti3+, V3+, Mn2+, Fe3+ and Co2+ are coloured due to presence of unpaired electrons, they can undergo d-d transitions others Cu+, Sc3+ are colourless due to absence of unpaired electrons.
9.
La3+ is largest in lanthanoid series.
10.
In actinoids, 5 f-orbitals are filled. These 5 f-orbitals have a poorer shielding effect than 4 f-orbitals (in lanthanoids). Thus, the effective nuclear charge experienced by electrons in valence shells in case of actinoids is much more than that experienced by electrons in valence shells in case of lanthanoids. Hence, the size contraction in actinoids is greater than that in lanthanoids.
11.
(a) It is due to irregular variations in sum of first and second ionisation energies and sublimation energies. It is also due to stability of electronic configuration.
(b) (i) Cr2O72- + 3Sn2+ + 14H+➝ 2Cr3+ + 3Sn4+ + 7H2O
(ii) MnO4- + 5Fe2+ + 8H+ ➝ SFe3+ + Mn2+ + 4H2O
12.
(d)
in covalent compounds, fluorine can form single bond only while oxygen forms double bond
13.
(a)
Copper liberates hydrogen from acids
14.
(b)
3d5
15.
(b)
CuF2
16.
(b)
26
17.
(a)
Ce
18.
(d)
+ 7
19.
(b)
All the ions are coloured
20.
(d)
3
21.
(b)
irregular variation of sublimation ethalpies
22.
( )
is an actinoid
23.
( )
is a rare earth
24.
( )
shows an oxidation state of +3
25.
( )
1.8 BM
26.
( )
Production of iron alloy
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