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Mastering Transition Elements Concepts Now

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In this post, we will discuss the theory and questions of transition elements and inner-transition elements.

Transition Elements or d-Block Elements

Those elements which have partly or incompletely filled (n-1)d orbital in their elementary state or in any of their common oxidation state are called as transition elements.

Question: Why d-block elements are called as transition elements?

Answer: The d-block elements are called as transition elements because their properties are intermediate between the properties of highly electropositive s-block elements and highly electronegative p-block elements.

Question: Why Zn, Cd, Hg and Uub (Cn) are excluded (not included) from transition series?

Answer: According to definition of transition elements Zn, Cd, Hg and Uub are to be excluded (removed) from transition series as they have completely filled (n-1)d orbital i.e. the configuration is (n-1)d10 in their elementary state or any of their common oxidation state.

Position of transition elements in periodic table

Figure: Representation of transition elements (d-block) and inner-transition elements (f-block)

Note:

General Electronic Configuration of Transition elements

Electronic configuration of 3d series of transition elements

Atomic NumberElementSymbolExpected Electronic ConfigurationObserved Electronic Configuration
21ScandiumSc[Ar] 3d1 4s2[Ar] 3d1 4s2
22TitaniumTi[Ar] 3d2 4s2[Ar] 3d2 4s2
23VanadiumV[Ar] 3d3 4s2[Ar] 3d3 4s2
24ChromiumCr[Ar] 3d4 4s2[Ar] 3d5 4s1
25ManganeseMn[Ar] 3d5 4s2[Ar] 3d5 4s2
26IronFe[Ar] 3d6 4s2[Ar] 3d6 4s2
27CobaltCo[Ar] 3d7 4s2[Ar] 3d7 4s2
28NickelNi[Ar] 3d8 4s2[Ar] 3d8 4s2
29CopperCu[Ar] 3d9 4s2[Ar] 3d10 4s1
30ZincZn[Ar] 3d10 4s2[Ar] 3d10 4s2

Question: Write observed electronic configuration of elements from first transition series having half filled d-orbital.

Answer: The observed electronic configuration of elements from first transition series having half filled d-orbital are:

24Cr: 1s2 2s2 2p6 3s2 3p6 3d5 4s1

25Mn: 1s2 2s2 2p6 3s2 3p6 3d5 4s2

Question: Write observed electronic configuration of elements from first transition series having completely filled d-orbital.

Answer: The observed electronic configuration of elements from first transition series having completely filled d-orbital are:

29Cu: 1s2 2s2 2p6 3s2 3p6 3d10 4s1

30Zn: 1s2 2s2 2p6 3s2 3p6 3d10 4s2

Question: What are the general characteristics of transition elements?

Answer: The general characteristics of transition elements are:

Question: Transition elements show variable oxidation state. Explain.

Answer: Oxidation state is an apparent or actual charge along with sign present on an atom in a compound. All the transition metals except the last member of each series show different oxidation states due to their metallic nature. In case of transition elements, electrons from (n-1)d orbital and ns orbital of the atom can be used in a bonding. The difference of energy between (n-1)d orbital and ns orbital is very small, therefore, electrons from both the shells can be used for bonding. Hence, transition elements show variable oxidation state.

Question: Explain why is Fe3+ more stable than Fe2+.

Answer: The electronic configuration of Fe2+ is 1s2 2s2 2p6 3s2 3p6 3d6. The electronic configuration of Fe3+ is 1s2 2s2 2p6 3s2 3p6 3d5. In Fe3+ ion 3d orbital is half filled. We know that half filled orbitals are more stable. Hence, Fe3+ is more stable than Fe2+.

Question: Explain why is Mn2+ more stable than Mn3+.

Answer: The electronic configuration of Mn2+ is 1s2 2s2 2p6 3s2 3p6 3d5. The electronic configuration of Mn3+ is 1s2 2s2 2p6 3s2 3p6 3d4. In Mn2+ ion 3d orbital is half filled while in it not in case of Mn3+. As we know that half filled orbitals are more stable. Hence, Mn2+ is more stable than Mn3+.

Question: Write the different oxidation states of manganese. Why +2 oxidation state of manganese is more stable?

Answer: The different oxidation states of manganese are +2, +3, +4, +5, +6 and +7. The electronic configuration of Mn2+ is 1s2 2s2 2p6 3s2 3p6 3d5. In Mn2+ ion 3d orbital is half filled. We know that half filled orbitals are more stable. Hence, +2 oxidation state of manganese is more stable.

Question: What are the physical properties of first transition series?

Answer: The physical properties of first transition series are:

Atomic and Ionic Radii

From left to right in transition series, the nuclear charge increases by one unit at a time. The last filled electron enters a penultimate (n-1)d subshell. However, d orbitals in an atom are less penetrating or more diffused and, therefore d electrons offer smaller screening effect. As a result, effective nuclear charge also increases as the atomic number increases along a transition series. Hence, the atomic radii decrease gradually across a transition series from left to right.

Check out: Unique Guide to Organic Conversions (Cheat Sheet included)

Ionisation potential or Ionisation Energy or Ionisation Enthalpy

Minimum amount of energy required to remove most loosely held outer most shell e in ground state from an isolated gaseous atom is known as ionisation potential.

For an atom M, successive ionisation energy are as follows:

M + IE1 M+ + e

M+ + IE2 M2+ + e

M2+ + IE3 M3+ + e

Order of IE: IE3 > IE2 > IE1

In first transition series (3d series), ionization energy first increases then remains constant and then should decrease but increases at the end due to stability of fully filled configuration of Cu and Zn.

Question: Why ionisation enthalpies of the elements of the third transition seriesare much higher than the first and second series?

Answer: The atoms of elements of third transition series possess filled 4f- orbitals. 4f orbitals show poor shielding effect due their peculiar diffused shape. As a result, the valence electrons experience greater nuclear attraction. A greater amount of energy is required to ionize elements of the third transition series. Hence, ionisation enthalpies of the elements of the third transition series are much higher than the first and second series.

Metallic Character

Melting Point

Magnetic Properties of Transition Elements

Note: Alnico which is alloy of 12% Al, 20% Ni and 50% Co and rest of Fe is used to make permanent magnet.

Question: Pick up the paramagnetic species Cu+, Fe3+, Ni2+, Zn2+, Cd2+, Pd2+.

Question: What will be the magnetic moment of transition metal having 3 unpaired electrons? a) equal to 1.73 BM b) less than 1.73 BM c) more than 1.73 BM

Question: A metal ion from the first transition series has two unpaired electrons. Calculate the magnetic moment.

Coloured Compounds of Transition Elements

A substance shows colour in solid state or in solution form, due to absorption of energy from visible range to promote an electron from lower energy level to higher energy level. d-subshell has five d-orbitals. When ligand comes closer to central metal ion, d-orbitals splits into two different energy levels. The lower energy level consists of dxy, dyz, dxz and higher energy level consists of dx2-y2, dz2. This is called crystal field splitting.

Therefore transition elements which have incompletely filled d-subshell absorb energy to promote 1 or 2 electrons from a lower energy level to higher energy level within the same d-subshell. This is called d-d transition. This energy is absorbed from visible range (wavelength between 4000 to 7800 Ao) and the element shows colour complementary to it.

When light from visible range falls on unpaired electron, then that unpaired electron gets excited and jumps to high energy level. But electron in excited state is not stable. So, it comes down to ground state and releases energy.

Colour shown by compound is complementary colour of colour absorbed by compound.

e.g., when the substance absorbs blue colour, then it appears orange-red, because orange-red is complementary colour of blue. Transition elements which have completely filled or empty d-subshell are colourless.

Question: What are the factors on which colour of the ion depends?

Answer: The factors on which colour of the ion depends are as follows:

Question: Why is Sc3+is colourless while Ti3+ is coloured?

Answer: The electronic configuration of Sc3+ is 1s2 2s2 2p6 3s2 3p6. In Sc3+ ion d-orbital is empty, hence d-d transition is not possible. Therefore Sc3+ is colourless. The electronic configuration of Ti3+ is 1s2 2s2 2p6 3s2 3p6 3d1. In Ti3+ ion d-orbital contains one unpaired electron, hence d-d transition is possible. Therefore Ti3+ is coloured.

Question: Why are compounds of copper (II) (Cu2+) are coloured while those of zinc (II) (Zn2+) are colourless?

Answer: The electronic configuration of Zn2+ is 1s2 2s2 2p6 3s2 3p6 3d10. In Zn2+ ion d-orbital is completely filled, hence d-d transition is not possible. Therefore compounds of zinc are colourless. The electronic configuration of Cu2+ is 1s2 2s2 2p6 3s2 3p6 3d9. In Cu2+ ion d-orbital contains unpaired electron, hence d-d transition is possible. Therefore compounds of Cu2+ are coloured.

Question: Give reason why zinc salts are white or colourless.

Answer: The electronic configuration of Zn2+ is 1s2 2s2 2p6 3s2 3p6 3d10. In Zn2+ ion d-orbital is completely filled, hence d-d transition is not possible. Therefore, salts of zinc are white or colourless.

Catalytic Properties of Transition Elements

The substance which increases rate of reaction without being consumed in the reaction is called as catalyst. Transition elements and their compounds show catalytic properties due to following reasons:

e.g., a. MnO2 act as a catalyst for decomposition of KClO3 and O2.

b. Finely divided Ni, formed by reduction of the heated oxide in hydrogen is an extremely efficient catalyst in hydrogenation of ethane to ethane at 140°C.

c. Commercially, hydrogenation with nickel as catalyst is used to convert inedible oils into solid fat for the production of margarine.

d. In the contact process of industrial production of sulfuric acid; sulphur dioxide and oxygen from the air react reversibly over a solid catalyst of platinised asbestos.

e. Carbon dioxide and hydrogen are formed by reaction of the carbon monoxide and steam at about 5000C with an Fe-Cr catalyst.

f. Fe and Mo is used as a catalyst in manufacture of ammonia.

g. Co-Th alloy is used in Fischer Tropsch process in the synthesis of gasoline.

Formation of Interstitial Compounds

Interstitial compounds are those which are formed when small atoms like H, C or N are trapped inside the interstitial spaces in the crystal lattice of metal. Interstitial compounds have higher melting point than pure metals because, metal-nonmetal bonds are stronger than metal-metal bonds in pure metals. The properties of interstitial compounds are as follows:

Alloy Formation

A solid solution of two or more metals or of a metal or metals with one or more non-metals is called as alloy or solid solution. All the properties of the pure metals are improved when they form alloys. Transition elements have almost similar atomic sizes. Therefore in molten state, one metal atom replaces other metal atom from its lattice and forms homogeneous mixture of two metals i.e. alloy.

Classification of Alloy

Alloys are classified into two types, namely ferrous alloys and non-ferrous alloys.

Ferrous alloys

Ferrous alloys have atoms of other elements distributed randomly in atoms of iron in the mixture. As percentage of iron is more, they are termed ferrous alloys. Ex:- Nickel steel, Chromium steel, Stainless steel etc. All steels have 2% carbon.

Non-ferrous alloys

Non-ferrous alloys are formed by mixing atoms of transition metal other than iron with a non transition element. Ex:- Brass, which is an alloy of copper and zinc.

Question: What are the uses of alloys?

Answer: 1) Bronze (alloy of copper and tin): Bronze is tough, strong and corrosion resistant. It is used for making statues, medals and trophies.

2) Cupra-nickel (alloy of copper and nickel): Cupra-nickel is used for making machinery parts of marine ships, boats. For example, marine condenser tubes.

3) Stainless steels (Iron alloy composed of chromium and some nickel): Stainless steels are used in the construction of the outer fuselage of ultrahigh speed aircraft.

4) Nichrome (alloy of nickel and chromium in the ratio 80 : 20): Nichrome has been developed specifically for gas turbine engines.

5) Titanium alloys withstand stress up to high temperatures and are used for ultra- high speed flight, fire proof bulkheads and exhaust shrouds. Note:- Alloy of transition metals with non-transition metals: Brass (Cu-Zn) and Bronze (Cu-Sn).

Question: What are the physical properties of d-block elements?

Answer: The physical properties of d-block elements are:

Question: What are the chemical properties of d-block elements?

Answer: The chemical properties of d-block elements are:

Question: What are the differences in properties of d-block elements?

Answer: The elements of first row differ from second and third rows in stabilization of higher oxidation states in their compounds, e.g., Mo (V) and W (VI) compounds are more stable than Cr (VI) and Mn (VIII). Highest oxidation state for elements of 1st row is +7, and in the case of 3rd row +8 oxidation state as in (RuO4) and (OsO4).

Question: How do metals occur in nature?

Answer: Metals occur in nature in free State or combined state.

Free State: Metals which do not react with air, water, carbon dioxide and non-metals occur in free State or native state in nature e.g., Silver, Gold and Platinum.

Combined State: Reactive metals occur in combined state in the form of compounds with other elements i.e., in the form of oxides, sulphides, carbonates, sulphates, silicates etc., e.g., iron usually occurs as its oxide Fe2O3 in earth crust.

Inner-Transition Elements or f-Block Elements

The element which have partially filled (n-2)f sub-shell are called as inner transition elements. Inert transition elements are called as rare earth elements because these elements occur very rarely. This elements have outermost two-shells incompletely filled i.e. penultimate (n-1)d and pre-penultimate (n-2)f.

Inner transition elements consists of two series at the bottom of periodic table, i.e., Lanthanides and Actinides.

Lanthanides

The first series of 14 elements in f-block following Lanthanum (La) at the bottom of periodic table is called as lanthanide series. It starts with Cerium (Ce) with atomic number 58 and ends at Lutetium (Lu) with atomic number 71. It is also called as 4f series.

General electronic configuration of lanthanides is [Xe] 4f1-14 5d0-1 6s2.

Atomic NumberElementSymbolElectronic Configuration
57LanthanumLa[Xe] 4f0 5d1 6s2
58CeriumCe[Xe] 4f1 5d1 6s2
59PraseodymiumPr[Xe] 4f3 6s2
60NeodyniumNd[Xe] 4f4 6s2
61PromethiumPm[Xe] 4f5 6s2
62SamariumSm[Xe] 4f6 6s2
63EuropiumEu[Xe] 4f7 6s2
64GadoliniumGd[Xe] 4f7 5d1 6s2
65TerbiumTb[Xe] 4f9 6s2
66DysprosiumDy[Xe] 4f10 6s2
67HolmiumHo[Xe] 4f11 6s2
68ErbiumEr[Xe] 4f12 6s2
69ThuliumTm[Xe] 4f13 6s2
70YtterbiumYb[Xe] 4f14 6s2
71LutetiumLu[Xe] 4f14 5d1 6s2

Question: What is the position of lanthanides in periodic table?

Answer: Lanthanides belong to 3rd group and 6th period of periodic table. They are place in f-block at the bottom of the periodic table.

Lanthanide Contraction

The gradual decrease in atomic & ionic sizes of f-block elements with increase in atomic number is called as lanthanide contraction In lanthanides as we move from left to right i.e. from cerium to lutetium, atomic number increases but electrons are added to the same 4f –orbital. This results in increase in nuclear charge f-orbital is more defused in shape and hence it has poor shielding effect i.e. with increasing atomic number, effective nuclear charge increases, but electrons in 4f orbitals covers the nucleus poorly for outermost shell.

This cause increasing in attraction between nucleus and outermost electron and decreases in atomic and ionic size. The total decrease in atomic and ionic sizes from Ce to Lu is 10pm to 18pm respectively, and this decrease is very small as compared to decrease in other period. Due to lanthanide contraction, lanthanide have nearly same size they show same properties, therefore they are very difficult to separate form one another.

Effects of Lanthanoid contraction
Decrease in basicity of hydroxides
Ionic radii of past lanthanide ion

Question: What are chemical twins? Write two examples.

Answer: The Zr-Hf (group 4), Nb-Ta (group 5), Mo-W (group 6) and Tc-Re (group 7) etc. have almost identical sizes. These pair of elements are called as chemical twins. Examples are Zr and Hf have 145 pm and 144 pm sizes i.e. almost same. Hence they are chemical twins.

Question: Explain why Gd3+ is colourless.

Answer: The electronic configuration of Gd3+ is [Xe] 4f7. Extra stability of half filled orbital, does not follow f-f transition. Hence Gd3+ does not absorb radiation in visible region. Hence Gd3+ is colourless.

Oxidation States of Lanthanides

Lanthanides show common +3 oxidation state in solid state or in aqueous solution by loss of two 6s and one 5d electrons. Lanthanum shows +3 oxidation state only. Gadolinium and Lutetium also show +3 oxidation state only. Some lanthanides also show +2 and +4 oxidation state.

Elements having +2 oxidation state: Sm, Nd, Eu, Tm, Yb

Elements having +4 oxidation state: Ce, Pr, Nd, Tb, Dy

Applications of Lanthanides

Actinides

The second series of 14-element in f-block following Actinium (Ac) at the bottom of periodic table is called actinides series. It starts with Thorium (Th) with atomic number 90 and ends at Lawrencium (Lr) with atomic number 103. It is also called as 5f series.

General electronic configuration of actinides is [Rn] 5f1-14 6d0-1 7s2.

Question: What is the position of actinides in the periodic table?

Answer: Actinides belong to 3rd group and 7th period of periodic table. They are place in f-block at the bottom of the periodic table.

Atomic NumnerElementSymbolElectronic Configuration
89ActiniumAc[Rn] 5f0 6d1 7s2
90ThoriumTh[Rn] 5f0 6d2 7s2
91ProtactiumPa[Rn] 5f2 6d1 7s2
92UraniumU[Rn] 5f3 6d1 7s2
93NeptuniumNp[Rn] 5f4 6d1 7s2
94PlutoniumPu[Rn] 5f6 6d0 7s2
95AmericiumAm[Rn] 5f7 6d0 7s2
96CuriumCm[Rn] 5f7 6d1 7s2
97BerkeliumBk[Rn] 5f9 6d0 7s2
98CaliforniumCf[Rn] 5f10 6d0 7s2
99EinsteniumEs[Rn] 5f11 6d0 7s2
100FermiumFm[Rn] 5f12 6d0 7s2
101MendeleviumMd[Rn] 5f13 6d0 7s2
102NobeliumNo[Rn] 5f14 6d0 7s2
103LawrenciumLr[Rn] 5f14 6d1 7s2

Question: What are trans uranic element? Write their names.

Answer: The chemical elements with atomic number greater than 92 which is atomic number of uranium are called as trans uranic elements. These elements follow uranium (92) and they are prepared synthetically in the laboratory through nuclear reaction. The starting element for this purpose is always uranium. Therefore they are called trans uranic elements. Trans uranic elements are also called as synthetic elements, e.g., Neptunium, Plutonium, Americium, Curium, etc.

Distinguish between Lanthanides and Actinides

LanthanidesActinides
Their compounds are less basic in nature.Their compounds are more basic in nature.
They do not form oxocations.They form oxocations such as UO+, PuO+, NpO2+.
They are non radioactive (except promethium).They are radioactive.
They have lower melting point and boiling point.They have higher melting point and boiling point.
They have less tendency to form complexes.They have more tendency to form complexes.
They show +2 and +4 oxidation states in addition to +3 oxidation state.They show +4, +5, +6 and +7 oxidation states in addition to +3 oxidation state.

Similarities between Lanthanides and Actinides

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