Chapter 4
Chapter 4
Chapter 4
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TN Board
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Students get through the TN Board 12th Chemistry Important Questions Chapter 4 Transition
and Inner Transition Elements which is useful for their exam preparation.
Question 1.
Write the electronic configuration of (a) Cr+3, (b) Cu+, (c) CO+2, (d) Mn+2, (e) Pm+3, (f) Ce+4, (g)
Lu+2, (h) Th+4.
Answer: 3rd Std TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
Question 2.
To what extent do the electronic configuration decide the stability of oxidation states in the
first series of transition elements. Illustrate your answer with an example.
Answer:
In a transition, the series the oxidation state which leads to exactly half filled or completely
filled ‘d’ orbitals are more stable. For example, the electronic configuration of Fe(z = 96) is
[Ar] 3d6 4s2. It shows +2 and +3 oxidation states. The +3 oxidation state is more stable
because it has the configuration [Ar] 3d5.
Question 3.
Explain why transition elements have many irregularities in their electronic configuration.
Answer:
In the transition elements, there is a little difference in the energy of (n – 1 )d and ns orbitals.
The incoming electron may occupy either of these orbitals. Hence, there is irregularities in
their electronic configurations.
Question 4.
Name the oxometal anoins of the first series of the transition metals in which the metal
exhibits the oxidation state equal to its group number.
Answer:
Cr2O7-2 (dichromate) and CrO4-2 (Chromate):
Group number
3rd Std of Cr=Oxidation state of Cr = 6 TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
MnO4– (permanganate):
Group number of Mn=Oxidation state of Mn=7
VO4-3(vanadate ion):
Group number of V = Oxidation state of V = 5.
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Question 5.
What are the stable oxidation states of the transition elements with the electronic
configuration in their ground states of their atoms 3d3, 3d5, 3d8, and 3d4.
Answer: 3rd Std TN Text English
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Question 6.
For M+2/M and M+3/M+2 systems, the E° values for some metals are as follows:
Cr+2/Cr = -0.9V; Cr+3/Cr+2 = -0.4V
Mn+2/Mn = -1.2V; Mn+3/Mn+2 = +1.5 V
Fe+2/Fe – -0.4V; Fe+3/Fe+2 = +0.80V
Use this data to comment upon:
(i) the stability of Fe+3 in acid solution as compared to Cr+3 or Mn+3 and
(ii) the case with which iron can be oxidised as compared to a similar process for either
chromium or manganese metal.
Answer:
(i) Higher the reduction potential of species, greater is the tendency for its reduction to take
place. Therefore, Mn+3, with the highest reduction potential would be readily reduced to Mn+2
(Mn+3 + e → Mn+2) and hence is least stable. Thus, from the values of reductions potential, it
is clear that the stability of Fe+3 in acidic solution is more than Mn+3, but less than that of
Cr+3.
(ii) Lower the reduction potential or higher the oxidation potential of a species, greater the
case with which its oxidation will take place. Thus, the order of tendency to undergo
oxidation is Fe < Cr < Mn.
Note: Oxidation and reduction potentials have the same magnitude but opposite in sign.
3rd Std TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
Question 7.
How is the variability of oxidation states of transition metals different from that of non-
transition metals? Illustrate with examples.
Answer:
In transition elements, the successive oxidation states differ by unity. For example,
manganese shows all oxidation states +2 to +7. On the other hand, non-transition metals
exhibit variable oxidation states which differs by two units.eg: Pb(II) and Pb (IV); Sn(II) and
Sn(IV).
Question 8.
How would you account for the following?
(i) Many of the transition elements and then compounds can act as good catalysts.
(ii) The metallic radii of the third (5d) series of transition elements are literally the same as
those of the corresponding members of the second series.
(iii) There is a greater range of oxidation states among actinoids than those of lanthanoids.
Answer:
(i) The catalytic activity of transition elements is attributed to the following reasons:
Because of their variable oxidation states transition metals form unstable intermediates
and provide a new path of lower activations energy for the reaction.
In some cases, the transition metal provides a suitable large surface area with free
vacancies, on which reactants are absorbed.
(ii) This is due to filling of 4/orbitals which have poor shielding effect or due to lanthanoid
contraction.
(iii) This is due to comparable energies of 5f, 5d and 7s orbitals in actinoids.
Question 9.
Calculate the number of unpaired electrons in the following gaseous ions.
Mn+3, Cr+3, V+3 and Ti+3 Which one of these is the most stable in an aqueous solution?
Answer:
Mn+3 = [Ar] 3d4 – 4 unpaired electrons
Cr+3 = [Ar] 3d3 – 3 unpaired electrons
V+3 = [Ar]3rd 2 – 2 unpaired electrons
3dStd TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
Ti+3 = [Ar] 3d1 – 1 unpaired electron
Cr+3 is most stable as it is half-filled t2g level.
Question 10.
The electronic configuration of chromium and copper are [Ar] 3d5 4s1 and [Ar] 3d10 4s1
respectively instead of [Ar] 3d4 4s2 and [Ar] 3d9 3s2. Explain.
Answer:
The electronic configuration [Ar] 3d5 4s1 and [Ar] 3d10 4s1 is more stable than the other
because of the extra stability of half filled and completely filled ‘d’ orbitals. This extra stability
is due to the symmetrical distribution of electron density.
Question 11.
The melting and boiling points of Zn, Cd and Hg are low why? (or) Why Zn, Cd and Hg are
soft and have low melting points?
Answer:
In Zn, Cd and Hg, all the electrons in the ‘d’ orbitals are paired. Hence metallic bonding
present in than are weak. Hence, the attraction between the constituent atoms are weak, i.e.,
they have low melting and boiling points.
Question 12.
Account for the trend in melting points of 3d series.
Answer:
The melting point first increases as the number of unpaired ‘d’ electrons available for
metallic bonding increases, reaches a maximum and then decreases, as the ‘d’ electrons pair
up and becomes unavailable for metallic bonding. The maximum melting point is in the
middle, where the transition metal has d5 configuration. This results in the formation of
strong metallic bonding, which results in the maximum melting point in the middle of the
series.
Question 13.
Explain why manganese has a lower melting point than chromium.
Answer:
3rd Std configuration of chromium is [Ar] 3d5 4s1 and that of manganese
The electronic TN Text is [Ar] 3d5
English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
4s2 i.e., in manganese-all the ‘d’ orbitals are singly filled and the 4s orbital is completely filled.
As the ‘d’ electrons are more tightly held by the nucleus, the electrons are not available for
bonding resulting in weaker metallic bonding in manganese compared to chromium.
Question 14.
The second and third members of each group of transition elements have similar atomic
radii- Explain.
Answer:
This is due to lanthanide contraction by members of 4f series, which occupy a position
between lanthanum (at. no. 57) a first member of 3rd transition series and hafnium (Z = 72),
the second member of third transition series.
The pairs of elements Zr – Hf, Nb – Ta, Mo – Wo, possess nearby atomic radii and almost
have the same properties.
3rd Std TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
Question 15.
The atomic radii of the elements in a transition series do not vary much while they do vary in
case of ‘s’ and ‘p’ block elements explain.
Answer:
In transition elements two effects are operating, viz nuclear charge effect and screening
effect which oppose each other. Due to an increase in nuclear charge from member to
member in a transition series the atomic radii tend to decrease. At the same time, the
addition of extra electrons in (n – 1 )d orbital provides the screening effect. As the number of
‘d’ electrons increases, the screening effect increases and this tends to increase the size.
Due to these opposing tendencies, there is a small change in the atomic radii in a transition
series.
In ‘s’ and ‘p’ block elements, the extra electron is added to the same ‘s’ or ‘p’ subshell which
does not exert a screening effect and hence, the atomic radii considerably in a period due to
an increase in nuclear charge.
Question 16.
How would you account for the following?
(i) The atomic radius of metals of the third (5d) series of elements are virtually the same as
those of corresponding members of the second (4d) series.
(ii) Chromium is a typical hard metal while mercury is a liquid.
Answer: 3rd Std TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
(i) Due to lanthanoid contraction.
(ii) Chromium has five unpaired electrons in the ‘d’ subshell (3d5 5s1). Hence metallic bonds
are very strong. In mercury, all the ‘d’ orbitals are fully filled (3d10 4s2). Hence, metallic
bonding is weak and thus it exists as a liquid.
Question 17.
How would you account for the irregular variation of ionisation enthalpies (first and second)
in the first series of transition metals?
Answer:
Reason for irregular variation of first IE: Generally moving from left to right in a period IE
increase because of increase in nuclear charge. The irregular trend is observed, when an
electron is removed, the relative energies of 3d and 4s orbitals are altered. Thus there is a
reorganisation of energy accompanying ionisation. This results in the release of exchange
energy which increases as the number of electrons increases in the ‘d’ configuration and also
from the transfer of ‘s’ electrons into ‘d’ orbitals. Chromium has the first low IE because of
the loss of one electron gives a stable configuration (d5). Zn has high IE because the electron
has to be removed from 4s orbital of the stable configuration (3d10 4s2)
Reason for irregular variation of second IE: After the loss of one electron, the removal of the
second electron is difficult. Hence, second IE is much higher and in a general increase from
left to right. Cr and Cu show much higher values because the second electron has to be
removed from the stable configuration. Cr+(3d5) and Cu+(3d10).
Question 18.
Compare the stabilities of Ni+4 and Pt+4 from their ionisation enthalpy values.
Answer:
IE Ni Pt
I 737 864
II 1753 1791
The smaller the magnitude of the ionisation energy, the more stable is the compound in a
particular oxidation state. Nickel (II) compounds are more stable than Pt(II) compounds
while Pt(IV) compounds are more stable than Ni(IV) compounds. The sum of the first two
and first four IE of nickel and platinum are given below.
Since the first two ionisation energies is less for nickel than platinum, Ni(II) compounds are
more stable than platinum.
On the other hand, Pt(IV) compounds are more stable than Ni(IV) compounds as the seem of
the first four IE values are less than for Pt the Ni.
Question 19.
The silver atom has completely ‘d’ orbitals (4d10) in its ground state. How can you say that it
is a transition element?
Answer:
The electronic configuration of Ag (z = 47) to 4d10 5s1. In addition to +1, it shows an
oxidation state of +2 (eg: Ag2O, and F2). i.e., d9 configuration i.e., the ‘d’ orbital is
incompletely filled. Hence, it is a transition element.
Question 20.
Which of the 3d transition metals exhibit the largest number of oxidation states? and why?
Answer:
Manganese (z = 25) shows a maximum number of oxidation states. This is because its
electronic configuration is 3d5 4s2. As 3d and 4s are close in energy, it has a maximum
number of electrons to lose or share (all the 3d electrons are unpaired) Hence, it shows
oxidation state +2 to +7.
Question3rd
21.Std TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
Why is the highest oxidation state of a metal exhibited in its oxide or fluoride only?
Answer:
Oxygen and fluorine have small sizes and high electronegativity. Hence they can oxidise the
metal to its highest oxidation state.
Question 22.
What may be the stable oxidation state of the transition element with the following ‘d’
electronic configuration in the ground state of their atoms? 3d3, 3d5, 3d8 and 3d4.
Answer:
The maximum oxidation state corresponds to the sum of the ‘5’ and ‘cf electrons in Upto Mn.
After that there is an abrupt decrease in the stability of the higher oxidation state.
Question 23.
Why are Mn+2 compounds are more stable than Fe+2 compounds towards oxidation to +3
state?
Answer:
The electronic configuration of Mn is 3d5. Which is half-filled and hence stable. So, the third
ionisation enthalpy is very high, i.e., 3rd electron cannot be removed easily. In the case of
Fe+2, (3d6), it can lose one more electron to attain the stable (d5) configuration.
Question 24.
Explain briefly how +2 oxidation state becomes more and more stable in the first half of first-
row transition elements with increasing atomic number.
Answer:
The sum of IE1, and IE2 increases. Thus, the standard reduction potential becomes less and
less negative. Therefore, the tendency to form M+2 ion decreases. The greater stability of +2
state, say for Mn, is due to half-filled (d5) configuration and that for Zn is due to completely
filled ‘d’ orbitals. That for nickel is due to the highest negative enthalpy of hydration.
3rd Std TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
Question 25.
To what extent do the electronic configuration decide the stability of oxidation states in the
first series of transition elements? Illustrate your answer with an example.
Answer:
The stability of the oxidation state in the first transition elements are related to their
electronic configuration.
The first five elements of the first transition series up to Mn in which 3d subshell is not more
than half-filled, the minimum oxidation state is given by the number of electrons in the outer
s – subshell and the maximum oxidation state is given by the sum of outer ‘s’ and ‘d’
electrons.
Question 26.
Explain why E°(Mn+3/Mn+2) couple is more positive than for E°(Fe+3/Fe+2) (At.no.of Mn = 25;
Fe = 26).
Answer: 3rd Std TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
The electronic configuration of Mn+2 is Mn+2 = [Ar] 3d5; Mn+3 is 3d4 and that of Fe+2 = [Ar]
3d6; Fe+3 is [Ar] 3d5.
Thus Mn+2 has a more stable configuration than Mn+3 while Fe+3 has a more stable
configuration than Fe+2. Consequently, large third ionisation enthalpy is required to change
Mn+2 to Mn+3. As E° values is the sum of the enthalpy of atomisation, ionisation enthalpy and
hydration enthalpy, therefore E° for Mn+3/ Mn+2 couple is more positive than Fe+3/Fe+2.
Note: The large positive E° for Mn+3/ Mn+2 means that Mn+3 can be easily reduced to Mn+2
(Mn+3 + e → Mn+2) i.e., Mn+3 is less stable, i.e., Fe+3 can be reduced to Fe+2 (Fe+3 + e → Fe+2
but ion easily. Thus, Fe+3 is more stable than Mn+3.
Question 27.
The E°values in respect of the electrodes of chromium (z = 24), manganese (z = 25) and iron
(z = 26) are: Cr+3/Cr+2 = – 0.4V, Mn+3/Mn+2 = 1.5V; Fe+3/Fe+2 – 0.80V. On the basis of the
above information compare the feasibilities of further oxidation of their +2 oxidation states.
Answer:
Cr+3 + e -> Cr+2: E° value is -0.4V. The negative value means Cr+3 is more stable or Cr+2 is less
stable. Mn+3 + e → Mn+2: E° value is 1.5V. Fe+3 + e → Fe+2: E° value is 0.80V. Greater positive
value for Mn+3/Mn+2 than that for Fe+3/Fe+2 shows that Mn+2 is more stable than Fe+2.
Hence, the stability of +2 oxidation state is in the order Cr+2 < Fe+2 < Mn+2 or oxidation of
their +2 state is in the order Cr+2 > Fe+2 > Mn+2.
Question 28.
The E°(M+2/M) value for copper is positive 0.34V. Explain why?
Answer:
E°(M+2/M) for any metal is related to the sum of the enthalpy change taking place in the
following steps.
Copper has a high enthalpy of atomisation and low enthalpy of hydration. Thus, high energy
required 3rd
to transform
Std Cu(s) to Cu+2(aq) is not balanced by its hydrationTNenthalpy
Text Hence E°
English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
(Cu+2/Cu) is positive.
Question 29.
Which is a stronger reducing agent Cr+2 or Fe+2 and why?
Answer:
E°(Cr+3/Cr+2) = -0.41V and E°(Fe+3/Fe+2) is 0.77V.
In general, for the reduction reaction Mn+ + ne → M,
Larger the value of standard reduction potential, greater the extent to which Mn+ is reduced
to M. i.e., Mn+ acts as an oxidising agent. Compare
Cr+3 + e → Cr+2 E° = -0.41V
Fe+3 + e → Fe+2 E° = 0.77V.
The negative value indicates that Cr+2 is readily oxidised to Cr+3 i.e., it is a stronger reducing
agent than Fe+2.
Question 30.
Explain the terms paramagnetism and diamagnetism with suitable examples.
Answer:
1. A paramagnetic substance is one that is weakly attracted into a magnetic field and a
diamagnetic substance is one that is repelled by a magnetic field.
2. The paramagnetic behaviour arises due to the presence of one or more unpaired
electrons, while a diamagnetic substance is due to the presence of paired electrons.
3. For example Sc+3 has no unpaired electron and hence diamagnetic whereas Ti+3 has
one unpaired electron and hence paramagnetic.
Question 31.
Calculate the magnetic moment of the following ions.
Answer:
3rd Std TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
Question 32.
Explain how transition metals and their compounds act as catalysts.
Answer:
Transition metal has energetically available ‘d’ orbitals that can accept electrons from
reactant molecule or metal can form a bond with reactant molecule using its ‘d’ electrons.
For example, in the catalytic hydrogenation of an alkene, the alkene bonds to an active site by
using its π electrons with an empty ‘d’ orbital of the catalyst.
The σ bond in the hydrogen molecule breaks and each hydrogen atom forms a bond with a ‘d’
electron on an atom in the catalyst. The two hydrogen atoms then bond with the partially
broken π3rd
-bond
Std in the alkene to form an alkane. TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
Question 33.
Give examples wherein transition metal compounds act as catalysts in various industrial
processes.
Answer:
1. In the manufacture of sulphuric acid from sulphur trioxide, vanadium pentoxide is used
as a catalyst.
2. Hydroformylation of olefins
Question 34.
What is an alloy? How are they formed?
Answer:
An alloy is a mixture of two or more metals. They are formed when molten metals are mixed
together and allowed to crystallise, eg: ferrous alloys, gold – copper alloy, chrome alloys etc.
Question3rd
35.Std TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
Explain why transition metals have a tendency to form alloys.
Answer:
For the formation of alloy, the following conditions have to be met.
1. Both the solute and the solvent must have the same crystal structure.
2. Their valence and their electronegativity difference must be close to zero. Transition
metals satisfy these conditions. Their atomic sizes are similar and one metal atom can
be easily replaced by another metal atom from its crystal lattice to form an alloy.
Question 36.
What are interstitial compounds? Give examples.
Answer:
An interstitial compound or alloy is a compound that is formed when small atoms like
hydrogen, boron, carbon or nitrogen are trapped in the interstitial holes in a metal lattice.
They are usually non-stoichiometric compounds. Transition metals form a number of
interstitial compounds such as TiC, ZrH1.92, Mn4N etc., The elements that occupy the metal
lattice provide them new properties.
Question 37.
Mention the properties of interstitial compounds.
Answer:
Question 38.
What are complexes or coordination compounds? Give a brief account of complexes formed
by transition metals.
Answer:
Complexes or coordination compounds are these in which a transition metal ion accept a
pair of electrons, from a fixed number of compounds in which the central atom can denote a
pair of electrons and form coordinate covalent bonds.
eg: [Fe(CN) ]4-. In this complex, Fe+2 ion accepts lone pair of electrons TN
3rd 6Std from
Textthe English
cyanide ion
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
and form 6 coordinate covalent bonds. Transition metal ions form complexes due to their
small size and high charge and have vacant ‘d’ orbitals to accept electron pairs denoted by
other groups.
Question 39.
Give a brief account of oxides formed by transition metals.
Answer:
1. The metals of the first transition series form oxides with oxygen at high temperatures.
2. The oxidation state of the metal in the oxides vary from +1 to +7.
3. The highest oxidation state in the oxides of any transition metal is equal to its group
number eg: +7 in Mn2O7. Beyond group 7. No higher oxides of iron above Fe2O3 are
known.
4. All the metals except scandium form oxides of the formula MO which are ionic in nature.
As the oxidation number of the metal increases, ionic character decreases, eg: Mn2O7 is
covalent even CrO3, V2O5 are covalant and have low melting point.
5. In general, the oxides in the lower oxidation states of the metals are basic and in their
higher oxidation states they are acidic. Whereas in the intermediate oxidation states
they are amphoteric.
Question 40.
Classify the following oxides as acidic, basic and amphoteric
(a) Mn2O7, (b) CrO3, (c) Cr2O3, (d) CrO.
Answer:
7→
(a) Mn2O3rd Stdacidic
4th 5th 6th 7th 8th 9th 10th 11th 12th TN Text English
Guide Books Grammar
(b) CrO3 → acidic
(c) Cr2O3 → amphoteric
(d) CrO → basic.
Question 41.
Give example and suggest the reason for the following:
(i) The lowest oxide of transition metal is basic, the highest is acidic.
(ii) A transition metal exhibits higher oxidation states in oxides and fluorides.
(iii) The highest oxidation state is exhibited in oxo anion of a metal.
Answer:
(i) The lower oxide of a transition metal is basic because the metal atom has a low oxidation
state whereas the highest oxide is acidic due to a higher oxidation state for example, MnO is
basic while Mn2O7 is acidic.
(ii) A transition metal exhibits a higher oxidation state in oxides and fluorides because
oxygen and fluorine are highly electro negative elements, small in size (and strongest
oxidising agents). For example, osmium shows an oxidation state of +6 in O5F6 and
vanadium shows an oxidation state of +5 in V2O5.
(iii) Oxo metal anion have the highest oxidations state, eg: Cr in Cr2O7-2, has an oxidation
state of +6, whereas Mn in MnO4– ion has an oxidation state of +7. This again due to the
combination of the metal with oxygen which is a highly electronegative and oxidising
element.
Question 42.
Indicate the steps involved in the preparation of (i) K2Cr2O7 from chromite (ii) KMnO4 from
pyrolusite
Answer:
(i) K2Cr2O7 from chromite are
K2Cr2O7 3rd
is separated
Std by fractional crystallisation. TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
(ii) KMnO4 from pyrolusite are
KMnO4 is prepared from pyrolusite. MnO2 with KOH in the presence of an oxidising agent like
KNO3. This produces dark brown potassium manganate which disproportionates in a neutral
or acidic solution to give purple permanganets.
Question 43.
Give chemical oxidation and electrolytic oxidation of MnO4-2 to MnO4–.
Answer:
Chemical oxidation: In this method potassium manganate is treated with ozone (O3) or
chlorine to get potassium permanganate.
Question 44.
What happens when potassium dichromate is heated? Give equation.
Answer: 3rd Std TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
It decomposes to give green Cr2O3 and oxygen.
Question 45.
Discuss the action of alkali on potassium dichromate.
Answer:
When an alkali is added to an orange-red solution of potassium dichromate, a yellow solution
results due to the formation of chromate.
Question 46.
What is the effect of pH on a solution of potassium dichromate?
Answer:
In aqueous solution
In acidic medium (i.e., decreasing pH), the equilibrium shifts backwards and the colour is
orange-red. In a basic medium, (i.e., increasing pH) the equilibrium will shift forward and the
solution is yellow.
Question 47.
Draw the structure of the dichromate ion.
Answer:
Question 48.
Write the ionic equation to show that K2Cr2O7 is an oxidising agent in an acid medium.
Answer: 3rd Std TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
Question 49.
Complete and balance the following equation: (all in acid medium)
Answer:
Question 50.
Describe the chromyl chloride test.
Answer:
When potassium dichromate is heated with any chloride salt in the presence of Conc. H2SO4,
orange-red vapours of chromyl chloride (CrO2Cl2) is evolved. This reaction is used to confirm
the presence of chloride ions in inorganic qualitative analysis.
3rd Std TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
The chromyl chloride vapours are dissolved in sodium hydroxide solution and then acidified
with acetic acid and treated with lead acetate. A yellow precipitate of lead chromate is
obtained.
Question 51.
Mention the uses of potassium dichromate.
Answer:
Question 52.
Draw the structure of MnO4– ion.
Answer:
Permanganate ion has tetrahedral geometry in which the central Mn7+ is sp3 hybridised.
Question3rd
53.Std TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
What happens when:
(i) potassium permanganate is heated.
(ii) is heated with cold conc. H2SO4
(iii) is heated with hot conc. H2SO4?
Answer:
(i) It decomposes to form potassium
manganate and manganese dioxide.
2KMnO4 → 2K2MnO4 + MnO2 + O2
(ii) It decomposes to form manganese heptoxide which subsequently decomposes
explosively.
Question 54.
How does potassium permanganate act as an oxidising agent in the neutral medium?
Explain with examples.
Answer:
In neutral medium, KMnO4 is reduced to MnO2.
MnO4– + 2H2O + 3e → MnO2 + 4OH–
(i) It oxidises H2S to sulphur
Question 55.
Write an ionic equation or the half-reaction for the oxidising action of KMnO4 in an alkaline
medium.
Answer:
MnO4– + 2H2O + 3e → MnO2 + 4OH–
Question 56.
What is Bayer’s reagent? Mention its use.
Answer:
Cold dilute alkaline KMnO4 is known as Bayer’s reagent. It is used to oxidise alkenes into
diols. For example, ethylene can be converted into ethylene glycol and this reaction is used
as a test for unsaturation.
Question 57.
What is the action of acidified KMnO4 on
(i) ferrous salts,
(ii) Potassium iodide,
(iii) Oxalic acid
(iv) Sulphide ion,
(v) nitrite ion,
(vi) Sulphite ion.
3rd Std TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
Answer:
(i) It oxidises ferrous salts to ferric salts
Question 58.
Mention the uses of potassium permanganate.
Answer:
In basic medium:
In neutral medium:
Question 60.
What are inner transition elements?
Decide which of the given atomic numbers are the numbers of inner transition elements: 29,
59, 74, 95, 102, 104.
Answer:
The ‘f’ block elements i.e., in which the last electron enters the ‘f’ sub shell are called inner
transition3rdelements.
Std These include lanthanides (58 – 71) and actinidesTN
(90 – 103).
Text Thus, the
English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
elements with atomic numbers 59,95 and 102 are inner transition elements.
Question 61.
The chemistry of actinoid elements is not so smooth as that of lanthanoids justify then
statement by giving some examples from the oxidation state of these elements.
Answer:
Lanthanoids show a limited number of oxidation states viz +2, +3, +4 out of which +3 is most
common. This is because of the energy gap between 4f and 5d sub shells. The dominant
oxidation state of actinides is also +3 but they show a number of oxidation states also eg:
uranium (Z = 92) and polonium (Z = 92) show +3, +4 and +5 and +6, neptunium (Z = 94)
shows +3, +4, +5 and +7 etc., This is due to small energy diffidence between 5f, 6d and7s
subshells.
Question 62.
What is the last element in the series f actinoids? Comment on the possible oxidation state
of the element.
Answer:
Last actinoid: Lawrencium (Z = 103).
Electronic configuration; [Rn]86 5f14 6d1 7s2. possible oxidation state = +3.
Question3rd
63.Std TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
Name of the members of the lanthanoid series which exhibit +4 oxidation state. Try to
correlate this type of behaviour with the electronic configuration of these elements.
Answer:
+4: Ce(Z=58), Pr(Z=59), Nd(Z=60), Tb(Z=65), Dy(Z = 66)
+2: Nd(Z = 60); Sm(Z = 62); Eu(Z = 63), Tm(Z = 69); Yb(Z = 70)
+2 Oxidation state is exhibited when lanthanoid has the configuration 5d0 6s2. So that 2
electrons one easily lost. +4 state is exhibited when the electronic configuration left to close
to 4f0 (eg: 4f0, 4f1, 4f2) or close to 4f7 (eg: 4f7 or 4f8)
Question 64.
Write the electronic configuration of the elements with atomic numbers 61, 91, 101 and 109.
Answer:
Question 65.
Compare the chemistry of actinoids with that of lanthanoids with special reference to
(i) electronic configuration
(ii) Oxidation state
(iii) Atomic and ionic radii
(iv) Chemical reactivity
Answer:
(i) The general electronic configuration of lanthanoids is [Xe]54 4f1-14 5d0-1 6s2 where as that
of actinoids in [Rn]86 5f1-14 6d0-1 7s2. Thus lanthanoids belong to 4f series whereas actinoids
belong to 5f series.
(ii) Lanthanoids show limited oxidation states (+2, +3, +4) out of which +3 is most common.
This is because of the large energy gap between 4f and 5d subshells. On the other hand,
actinoids show a large number of oxidation states because of a small energy gap between
5f, 6d and 7s subshells.
(iii) Both show a decrease in the size of their atoms or ions in the +3 oxidation state. In
lanthanoids, this decrease is called lanthanoid contraction, whereas in actinoids it is called
actinoid 3rd
contraction.
Std However, the contraction is greater from elementTN
toText
element in
English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
actinoids due to poor shielding of 5f electrons than that by 4f electrons in lanthanoids.
(iv) Chemical reactivity of lanthanoids
1. They react with boiling water to give a mixture of hydride and oxide.
2. They combine with most of the non-metals at high temperatures.
3. All these metals are attacked by hydro chloric acid, but the effect of nitric acid is very
small due to the formation of a protective oxide layer on their surface.
4. Alkalies have no action on actinoids.
Question3rd
66.Std TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
The +3 oxidation state of lanthanium (Z = 57), gadoliniun (Z = 64) and lutetium (Z = 71) are
especially stable. Why?
Answer:
This is because that is the +3 oxidation state, they have empty, half-filled and completely
filled 4f sub shell respectively.
Question 67.
The outer electronic configuration of two members of the lanthanoid are as follows:
(i) 4f1 5d1 6s2 and (ii) 4f7 5d0 6s2
What are their atomic numbers predict the oxidation state exhibited by these elements in
their compounds?
Answer:
Complete Electronic configuration of the (i) lanthanoid:
[Xe]54 4f1 5d1 6s2: Atomic number = 58
The element is cerium.
Complete Electronic configuration of the (ii) lanthanoid:
[Xe]54 4f7 5d0 6s2: Atomic number = 68.
The element is Europium (Eu).
Oxidation state of 1st lanthanoid +2(4f2) +3(4f1) and +4(4f0)
Oxidation state of the 2nd lanthanoid:
+2(4f7) and +3(4f6)
Question 68.
Give an explanation for each of the following observations.
(i) The gradual decrease in size (actinoid contraction) from element to element is greater
among actinides than that among lanthanides.
(ii) The actinoids exhibit a greater range of oxidation states than the lanthanoids.
(iii) Zv and Hf have identical sizes.
(iv) Ionisation enthalpies of Ce, Pr and Nd are higher than Th, Pa and Cl. Why?
(v) Ce+4 is used as an oxidising agent in volumetric analysis.
Answer:
(i) This is due to poor shielding by 5f electrons from element to element in actinoids than by
4f electrons in lanthanoid series.
(ii)This is because there is less energy difference between 5f and 6d orbitals belonging to
actinoids3rd
than
Std the energy difference between 4f and 5d Orbitals in the TN
case
Textof lanthanoids.
English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
(iii) This is due to lanthanoid contraction.
(iv) It is because at the beginning, where 5f orbitals begin to be occupied they will penetrate
less into the inner core of electrons. The 5felectron will therefore be more effectively
shielded from the nuclear charge than 4f electrons of the corresponding lanthanoids.
Therefore the outer electrons are less firmly held and they are available for bonding in the
actinoids.
(v) Ce+4 has a tendency to attain +3 oxidation state and so it is used as an oxidising agent in
volumetric analysis.
Question 69.
Account for the following:
(i) Europium (II) is more stable than cerium(II)
(ii) Actinoid ions are generally coloured.
Answer:
(i) Europium has stable configuration i.e., [Xe] 4f7 5d0 6s0.
(ii) Unpaired electrons are present in their ions which undergo f-f transition.
Question 70.
On the basis of lanthanoid contraction, explain the following:
(i) Nature of bonding in La2O3 and Lu2O3.
(ii) Trends in the stability of oxosaltes of lanthanoids from La to Lu.
(iii) Stability of complexes of lanthanides.
(iv) Radii of 4d and 5d block elements.
(v) Trends in the acidic character of lanthanoid oxides.
Answer:
(i) As the size decreases, the covalent character increases. Therefore La2O3 is more ionic
and Lu2O3 is more covalent.
(ii) As the size decreases from La to Lu, the stability of oxo salts also decreases.
(iii) Stability of the complexes increases as the size of the lanthanoid decreases.
(iv) Radii of 4d and 5d block elements are will be almost the same.
(v) Acidic character of the oxides increases from La to Lu.
Question3rd
71.Std TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
What is meant by the term Lanthanoid contraction? What is it due to and what consequences
does it have on the chemistry of lanthanides in the periodic table.
Answer:
Lanthanide contraction: The steady decrease in atomic and ionic radii with an increase in
atomic number is known as lanthanide contraction.
Causes of lanthanide contraction: As we move along the lanthanoid series, for every
additional proton in the nucleus, the corresponding electron goes into 4f sub shell, there is
poor shielding of one electron by another in the sub shell due to the shapes of these orbitals.
This imperfect shielding is not able to counterbalance the effect on the increased nuclear
charge. Thus, the net result is a decrease in size, with an increase in atomic number.
Consequences:
1. 5d series elements have nearly the same radii as that of the 4d series.
2. The basic strength of hydroxides decrease from La(OH)3 to Lu(OH)3
1. The correct order of decreasing second ionisation enthalpy of Ti(22), V(23), Cr(24) and
Mn(25) is:
(a) Cr > Mn > V > Ti
(b) V > Mn > Cr > Ti
(c) Mn > Cr > Ti > V
(d) Ti > V > Cr > Mn
Answer:
(a) Cr > Mn > V > Ti
Hint: Electronic configuration of the given elements are
Ti = [Ar] 3d2 4s2; V = [Ar] 3d3 4s2 Cr = [Ar] 3d5 4s1; Mn = [Ar] 3d5 4s2
Their effective nuclear charge increases from Ti to Mn. Hence their first IE increases in the
same order, i.e., Mn > Cr > V > Ti. However after the removal of first electron, chromium
attains the stable configuration [3d5] and hence, it has very high second IE. For the remaining
elements the trend remains the same. Thus, the second IE will be in the order.
Cr > Mn > V >Ti
2. The electronic
3rd Std configuration of Cu(II) is 3d9 whereas that of Cu(I) is TN
3d10 . Which
Text of the
English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
following is correct?
(a) Cu(II) is more stable.
(b) Cu(II) is less stable.
(c) Cu(I) and Cu(II) are equally stable.
(d) Stability of Cu(I) and Cu(II) salts depends on the nature of copper salts.
Answer:
(a) Cu(II) is more stable.
Hint: Though Cu(I) has 3d10 configurations Cu(II) is more stable. This is due to greater
effective nuclear charge of Cu(II). i.e., to hold 17 electrons instead of 18 electrons is Cu(I).
4. Why HCl is not used to make the medium acidic in oxidation reactions of KMnO4 in acidic
medium?
(a) Both HCl and KMnO4 act as oxidising agents.
(b) KMnO4 oxidises HCl, to Cl2, which is also an oxidising agent.
(c) KMnO4 is a weaker oxidising agent than HCl.
(d) KMnO4 acts as a reducing agent in the presence of HCl.
Answer:
(b) KMnO4 oxidises HCl, to Cl2, which is also an oxidising agent.
5. KMnO4 acts as an oxidising agent in acidic medium. The number of moles of KMnO4 that
will be needed to react one mole of sulphide ions in acidic solution is:
2
(a) 5
3
(b) 5
(c) 4
(d) 1
5
Answer: 3rd Std TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
(a) 2
Hint:
5
mol of KMnO4 ≡ 1 mol of H2S
6. Which one of the following ions is the most stable in aqueous solution:
Note: Atomic No: Ti = 22, V = 23, Cr – 24, Mn = 25.
(a) Mn+2
(b) Cr+3
(c) V+3
(d) Ti+3
Answer:
(b) Cr+3
Hint: Out of the given species, Cr+3 has the highest negative reduction potential. Hence, it
cannot be reduced to Cr+2 and therefore is the most stable in aqueous solution.
Alternatively, Mn+3 = [Ar] 3d4, Cr+3 = [Ar] 3d3, V+3 = [Ar] 3d2, Ti+2 = [Ar] 3d1. In Cr+3, all the three
electrons enter the lowest energy 3d1(t2g ) orbitals. The lowering of the energy is maximum
and hence the stability is maximum.
9. Large number of oxidation states are exhibited by actinoids than these by the lanthanoids,
the main reason being:
(a) more energy difference between 5f and 6d than between 4f and 5d orbitals.
(b) more reactive nature of the actinoids than the lanthanoids.
(c) 4f orbitals more diffused than 5f orbitals.
(d) less energy difference between 5f and 6d than between 4f and 5d orbitals.
Answer:
(d) less energy difference between 5f and 6d than between 4f and 5d orbitals.
10. Irregular trend in the standard reduction potential value of the first row transition
elements is due to:
(a) regular variation of first and second row enthalpies.
(b) irregular variation of sublimation enthalpies.
(c) regular variation of sublimation enthalpies.
(d) increase in number of unpaired electrons.
Answer:
(b) irregular variation of sublimation enthalpies.
3rd Std TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
11. Match the property in column I with the metals in column II.
12. Match statements given in column I with the oxidation states given in column II.
14. Which of the following statements regarding cerium (atomic no.58) is incorrect?
(a) The common oxidation states of cerium are +3 and +4.
(b) +3 oxidation state of Ce is more stable than +4.
(c) The +4 oxidation state of Ce is not known in solution.
(d) Cerium (IV) acts as an oxidising agent.
Answer:
(c) The +4 oxidation state of Ce is not known in solution.
17. The spin only magnetic moment of Fe+2 (in Bμ) is approximately:
(a) 4
(b) 1
(c) 5
(d) 6
Answer:
(c) 5
Hint: Fe+2 = 3d6 4s0. It has 4 unpaired electron.
19. Metallic radii of some elements are given below: Which of these elements will have
highest density?
Element Fe Co Ni Cu
(a) Fe
(b) Ni
(c) Co
(d) Cu
Answer:
(d) Cu
mass
Hint: Density = volume
As we move from Fe to Cu mass increases and volume decreases. Hence, density increases.
Increase in mass of Cu dominates over small increase in volume.
20. The magnetic nature of elements depends on the presence of unpaired electrons.
Identify the configuration of transition element which shows highest magnetic moment:
(a) 3d7
(b) 3d5
(c) 3d8
(d) 3d2
Answer:
(b) 3d5
Hint: 3d5 has maximum number of impaired electron.
21. There are 14 elements in actinoid series which of the following elements does not belong
to this series?
(a) Cl
(b) Np
(c) Tm
(d) Fm 3rd Std TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
Answer:
(c) Tm
Hint: Actinoid series is with atomic numbers 90 to 103. Thulium (Tm) has atomic number 69.
22. Gadolinium belongs to 4/series. Its atomic number is 64. Which of the following is the
correct electronic configuration of gadolinium?
(a) [Xe] 4f7 5d1 6s2
(b) [Xe] 4f6 5d2 6s2
(c) [Xe] 4f8 6s2
(d) [Xe] 4f9 5s1
Answer:
(a) [Xe] 4f7 5d1 6s2
Hint: [Xe]54 4f7 5d1 6s2 due to extra stability of half filled 4f sub shell.
23. Highest oxidation state of manganese in fluoride is +4(MnF4) but the highest oxidation
state in oxides is +7(Mn2O7) because:
(a) fluorine is more electronegative than oxygen.
(b) fluorine does not possess ‘d’ orbital.
(c) fluorine stabilises lower oxidation state.
(d) in covalent compounds, fluorine can form only single bonds white oxygen can form
double bonds.
Answer: 3rd Std TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
(d) in covalent compounds, fluorine can form only single bonds white oxygen can form
double bonds.
25. Assertion: in any transition series the magnetic moment of M+2 ions first increases and
then decreases.
Reason: in a transition series, the number of unpaired electrons increases and then
decreases.
(a) if both assertion and reason are true and the reason is the correct explanation of the
assertion.
(b) if both assertion and reason are true but the reason is not the correct explanation of
assertion.
(c) if the assertion is true, but the reason is false.
(d) if both assertion and reason are false.
Answer:
(a) if both assertion and reason are true and reason is the correct explanation of the
assertion.
26. Match
3rdthe
Std ions in list I with their corresponding property in list II. TN Text English
Guide 4th 5th 6th 7th 8th 9th 10th 11th 12th Books Grammar
(a) (i) – (B) & (C); (ii) – (A) & (D); (iii) – (B) & (C); (iv) – (C)
(b) (i) – (C); (ii) – (A) & (B); (iii) – (D); (iv) – (B) & (C)
(c) (i) – (B) & (C); (ii) – (B); (iii) – (A) & (D); (iv) – (B)
(d) (i) – (D); (ii) – (C); (iii) – (B); (iv) – (A), (D)
Answer:
(a) (i) – (B) & (C); (ii) – (A) & (D); (iii) – (B) & (C); (iv) – (C)
29. In which of the following pairs are both the ions coloured in an aqueous solution?
(a) Ni+2, Ti+3
(b) Ni+2, Cu+
(c) Sc+3, CO+2
(d) Sc+3, Ti+3
Answer:
(a) Ni+2, Ti+3
Hint: Ni+2 = [Ar] 3d8 t2g6 eg2. It has 2 unpaired electron in e level. Hence it is coloured.
Ti+3 = [Ar]3d1 one unpaired electron and hence coloured.
30. When manganese dioxide is fused with KOH or K2CO3 in air, it gives:
(a) potassium permanganate
(b) manganese oxide
(c) manganese heptoxide
(d) potassium manganate
Answer:
(d) potassium manganate
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