BSCCH-201 Inorganic Chemistry II PDF 2021

BSCCH- 201 B. Sc. II YEAR INORGANIC CHEMISTRY-II SCHOOL OF SCIENCES DEPARTMENT OF CHEMISTRY UTTARAKHAND OPEN UNIVERSITY BSCCH-201 INORGANIC CHEMISTRY-II SCHOOL OF SCIENCES DEPARTMENT OF CHEMISTRY UTTARAKHAND OPEN UNIVERSITY Phone No. 05946-261122, 261123 Toll free No. 18001804025 Fax No. 05946-264232, E. mail [email protected] htpp://uou.ac.in Board of Studies Prof. Govind Singh Prof. B. S. Saraswat Director, School of Sciences Professor Chemistry Uttarakhand Open University Department of Chemistry School of Sciences, IGNOU, New Delhi Prof S. P. S. Mehta Prof. D. S. Rawat Professor Chemistry Professor Chemistry Department of Chemistry Department of Chemistry DSB Campus, Kumaun University Delhi University, Delhi Nainital Dr. Charu C. Pant Programme Coordinator Department of Chemistry School of Sciences, Uttarakhand Open University Haldwani, Nainital Programme Coordinators Dr. Shalini Singh (Assistant Professor) Department of Chemistry School of Sciences, Uttarakhand Open University Haldwani, Nainital Unit Written By Unit No. 1. Dr. K. S. Dhami (Ret. Proff.) 01, 02, 03, 04 & 05 Department of Chemistry D.S.B. Campus, Kumaun University Nainital 2. Dr. Geeta Tiwari 06, 07, 08 & 09 Department of Chemistry D.S.B. Campus, Kumaun University Nainital Course Editor Prof. B.S. Saraswat Professor of Chemistry (Retd.) School of Sciences, Indira Gandhi National Open University (IGNOU), Maidan Garhi, New Delhi - 110068 Title : Inorganic Chemistry II ISBN No. : 978-93-90845-04-0 Copyright : Uttarakhand Open University Edition : 2021 Published by : Uttarakhand Open University, Haldwani, Nainital- 263139 CONTENTS BLOCK- 1 d- BLOCK ELEMENTS Unit-1 Chemistry of elements of first transition series 1-24 Unit-2 Chemistry of element of second transition series 25-45 Unit-3 Chemistry of element of third transition series 46-66 BLOCK-2 f- BLOCK ELEMENTS Unit-4 Chemistry of Lanthanide elements 67-82 Unit-5 Chemistry of Actinides elements 83-95 BLOCK-3 CO-ORDINATION CHEMISTRY AND REDOX REACTIONS Unit-6 Co-ordination Compounds 97-124 Unit-7 Isomerism of Co-ordination Compounds 125-165 Unit-8 Oxidation and Reduction 166-192 BLOCK- 4 CONCEPTS OF ACIDS AND BASES Unit-9 Acids and Bases 193-218 INORGANIC CHEMISTRY-II BSCCH-201 UNIT 1: CHEMISTRY OF THE ELEMENTS OF FIRST TRANSITION (3-d) SERIES CONTENTS: 1.1 Objectives 1.2 Introduction 1.3 Characteristic Properties of d-Block Elements 1.4 Properties of the Elements of the First Transition series 1.5 Binary Compounds and Complexes 1.6 Relative Stability of their Oxidation States 1.7 Coordination number and Geometry 1.8 Summary 1.9 Terminal Questions 1.10 Answers 1.1 OBJECTIVES The objective of writing the text material of this unit is to acquaint the readers to the characteristic properties of the d-block elements, in general, such as their general electronic configuration and variable oxidation states, complex formation tendency, magnetic properties, formation of coloured ions/compounds, catalytic activity, etc. and periodic properties, viz., atomic radii, atomic volume, ionic radii, melting and boiling points, ionization energies and reactivity, standard electrode potentials and reducing properties, etc. along with their periodic variation along the series. It is also aimed at throwing light on the above properties of the first transition series, in particular, to illustrate the relative stability of the oxidation states of these elements along with to discuss the coordination number and geometry of their complexes and the binary compounds of these elements. 1.2 INTRODUCTION The d-block elements have been defined as “the elements whose atoms receive the last electron in the d-subshell belonging to the penultimate or (n-1)th shell”. The d-block elements are also called the transition elements or metals. This is because they exhibit gradual transitional behaviour between highly reactive s-block UTTARAKHAND OPEN UNIVERSITY Page 1 INORGANIC CHEMISTRY-II BSCCH-201 (electropositive) and p-block (electronegative) elements, i.e. their properties have been found to be intermediate between those of the s-block and p-block elements. Thus these elements are located in the middle of the periodic table and are the members of the Groups 3 to 12 (IIIB to VIII to II B) in the modern periodic table. According to IUPAC definiton, “a transition element is an element which has an incomplete d-subshell in either neutral atom or in ions in chemically significant (or common) oxidation state”. According to this definition zinc (Zn), cadmium (Cd) and mercury (Hg) are excluded from the list of transition elements as they neither have partly filled d-subshell in their atoms or ions nor they show the usual properties of transition elements to an appreciable extent. Still in order to rationalize the classification of elements, they are studied along with other d-block elements. There are four series of elements which constitute the d-block elements. Each series comprises ten elements as given below: 1. Elements of the First Transition series or 3d-Transition series: The elements from scandium (Sc, Z = 21) to Zinc (Zn, Z = 30) form the 3d-series. 2. Elements of the Second Transition series or 4d-Transition series: This series consists of the elements from yttrium (Y, Z = 39) to cadmium (Cd, Z = 48). 3. Elements of the Third Transition series or 5d-Transition series: The elements lanthanum (La, Z= 57) and hafnium (Hf, Z= 72) to mercury (Hg, Z = 80) constitute the 5d-Transition series. 4. Elements of the Fourth Transition series or 6d-Transition series: The elements actinium (Ac, Z = 89) and rutherfordium ( Rf, Z = 104) to copernicum ( Cn, Z = 112) are the members of this series. All these elements are radipoactive and do not occur in nature. These have been artificially made in the laboratory. 1.3 CHARACTERISTIC PROPERTIES OF D-BLOCK ELEMENTS Some of the important characteristics of the d-block elements are summarized as follows: 1.3.1 Electronic Configuration and Variable Oxidation States UTTARAKHAND OPEN UNIVERSITY Page 2 INORGANIC CHEMISTRY-II BSCCH-201 The d-block elements have a valence shell electronic configuration of (n-1)d1-10ns0-2 where (n-1) stands for inner shell whose d-orbitals may have one to ten electrons and the s-orbitals of the outermost shell (n) may have no electron or one or two electrons. The filling of d-orbitals takes place after the s-orbital of next higher shell has already filled as has been discussed in Aufbau principle in Unit 1 (BCH-101). This is because ns orbitals have lower energy than (n-1)d orbitals. But during ionization of the elements (oxidation), the electrons are first lost from ns level followed by the expulsion from (n-1)d subshell (deviation from the expected behaviour) because (n- 1)d subshell becomes of the lower energy than ns subshell once the filling of electrons commences in (n-1)d subshell. Most of the d-block elements show several oxidation states (variable) in their compounds due to the availability of d-electrons in the valence shell which comprises of the two subshells, viz., (n-1)d and ns whose orbitals are quite close together in energy and hence the electrons can be used from both the subshells for bonding and under different conditions different number of electrons can be used by them. The variability in the oxidation states increases towards the middle of the series from both ends, i.e. left → middle ← right. It has been observed that the d-block elements can form ionic bonds in their lower oxidation states and the ionic character of the bond decreases as well as the covalent character increases with increasing oxidation state. As a result, with decreasing ionic character the acidic character of the oxides and chlorides increases. 1.3.2 Complex Formation Tendency: The cations of d-block elements are unique in their tendency to form complexes with several molecules such as ammonia, water, etc. or different ions such as cyanide, NO- 2, halide ions, etc. These molecules or ions are called ligands. The complex forming tendency of these elements is attributed to the following factors: (a) Small size and high positive charge density, (b) Availability of vacant d-orbitals of right energy to accept the lone pairs of electrons from the approaching ligands, (c) Exhibition of variable oxidation states. UTTARAKHAND OPEN UNIVERSITY Page 3 INORGANIC CHEMISTRY-II BSCCH-201 The detailed account of this tendency will be given in the respective sections mentioned ahead. 1.3.3 Magnetic Properties: Many compounds of d-block elements exhibit magnetic properties. Qualitatively speaking, there are several kinds of magnetism. The substances which are weakly repelled by the strong magnetic field are termed as diamagnetic while those which are weakly attracted by the strong magnetic field are called paramagnetic. These substances lose their magnetism on removing the magnetic field. Diamagnetism is the property of the completely filled electronic subshells and is shown by all substances to more or less extent. Paramagnetism is produced by the presence of unpaired electrons and because most of the d-block metal atoms and ions have unpaired electrons, they are paramagnetic in behaviour. In some transition metals (e.g. Fe, Co, Ni) unpaired electron spins are more pronounced and show much more paramagnetism than the other d-block metals. Such metals are called ferromagnetic metals and magnetic property shown by them is known as ferromagnetism. Such metals can be permanently magnetized. The detailed account will be given in the section 1.4 of this unit and in subsequent units. 1.3.4 Formation of Coloured Ions/ Compounds: The majority of compounds of d-block elements, whether ionic or covalent, are coloured in solid or solution state. This property of d-block elements is in marked difference from those of s or p-block elements which are white or light coloured. The colour of a substance arises from the property of the substance to absorb light of certain wavelength in the region of visible light (white light) when the latter interacts with the substance. The coloure of the substance is the colour of the transmitted light component and is complementary to the colour of light component absorbed. The colour of d-block metal ions is associated with (a) an incomplete d-subshell in the metal ion, (b) the nature of surrounding groups around the metal ion. UTTARAKHAND OPEN UNIVERSITY Page 4 INORGANIC CHEMISTRY-II BSCCH-201 The whole act of exhibition of colour by d-block ions/compounds can be explained as follows. In a free gaseous or isolated ion the five d-orbitals are degenerate, i.e. of same energy. Since five d-orbitals are oriented differently in space, the surrounding groups affect the energy of some orbitals more than others in the compounds. This destroys their degeneracy. For example, in the simplest case of an octahedral complex, they form two groups of orbitals of different energy: Fig. 1.1 Bary centre Thus, in d-block metal ions with partially filled d-subshell, it is possible to promote electron(s) from one set of d-orbitals to another set (group) of higher energy by fairly small energy absorbed from the visible light. The colour of the compounds depends on the energy difference (gap) between the two groups (sets) of d-orbitals. This in turn depends on the nature of ligands and their arrangement around the metal ion in the compound / complex. 1.3.5 Catalytic Activity: The catalytic activity of d-block elements and their compounds is associated with their variable oxidation states and their capability of forming interstitial compounds. A number of d-block metals and their compounds are known to catalyse various reactions of industrial importance, e.g., vanadium (V) oxide in the manufacture of sulphuric acid by contact process, etc. An important view of the mechanism of catalysis is that at solid surface of the catalyst, bonds would be formed between the molecules of the reactants and atoms of the catalysts thereby increasing the concentration of the reactants at the surface. This weakens the bonds of the reactant molecules due to lowering of the activation energy. UTTARAKHAND OPEN UNIVERSITY Page 5 INORGANIC CHEMISTRY-II BSCCH-201 1.3.6 Formation of Interstitial and Non-stoichiometric Compounds: The d-block elements form interstitial compounds with small non-metal atoms such as H, C, N, B, Si, etc. due to the ability of metal lattice to accommodate these non– metal atoms between the metal atoms without distortion of structure. One of the striking properties of these metals is the formation of non-stoichiometric compounds which often exhibit semiconductivity, fluorescence and behave as heterogeneous catalysts. This non-stoichiometry is due to the defects in the solid structures. 1.3.7 Metallic Character and Alloy Formation: All the d-block elements are metals, good conductors of heat and electricity, are malleable and ductile. All are solids except Hg (mercury) which exists as liquid at ordinary temperature. These metals form alloys with each other due to almost similar sizes of the atoms. Thus the atoms of one metal can easily take up positions in the crystal lattice of the other. The alloys are usually harder and have higher melting points than the parent metals, are more resistant to corrosion than their constituents. 1.3.8 Periodic Properties and Their Variation along the Series: The atomic radii, atomic volumes, ionic radii, melting and boiling points, ionization energies and reactivity, standard electrode potential and reducing properties, etc. are the important periodic properties of the d–block elements which vary and have a definite trend, in general, along each series. These will be discussed below: a) Atomic Radii, Atomic Volumes and Ionic Radii. The atomic radii generally decrease, with a few exceptions, on moving from left to right in each series of the transition elements due to increased nuclear charge at each step and constant value of the azimuthal quantum number (i.e. l) receiving the last electron. The d-block elements have low atomic volumes as compared to those of the neighbouring s- and p-block elements. This is due to the fact that in these elements UTTARAKHAND OPEN UNIVERSITY Page 6 INORGANIC CHEMISTRY-II BSCCH-201 (n-1) d-subshells are being filled and the increased nuclear charge pulls the electron cloud inwards. The ionic radii of the d-block elements follow the same trend as the atomic radii, i.e. the radii of the ions having the same charge decrease with increasing atomic number. These properties will be discussed in detail for every series. b) Melting and Boiling Points The melting and boiling points of these elements are generally very high showing that they are held by strong forces. The melting and boiling points have the highest values in the middle of the series because, perhaps these elements have the maximum number of unpaired d-electrons available for bonding, detailed account of which will be given ahead for every series. c) Ionization Energies and Reactivity The ionization energy values of the d-block elements are fairly high and lie in between those of s- and p-block elements, i.e. these elements are less electropositive than s-block elements and more so than p-block elements. Hence, these elements do not form ionic compounds as readily as s-block elements and form covalent compounds as well. Because of the existence of covalent bonding, they have high heats of sublimation, i.e. a large amount of energy is required to convert them from solid to vapour state. The metal ions also do not get hydrated easily. Due to these parameters, the metal ions have a small tendency to react. Examples will be given in each series. d) Standard Electrode Potentials and Reducing Properties The standard reduction potential values of transition elements are generally lower (negative) than that of the standard hydrogen electrode (taken as zero). Thus they evolve H2 gas from acids though most of them do that at low rate. These metals are poor reducing agents which are contrary to the expected behaviour because of the high heats of vaporisation, high ionization energies and low heats of hydration. Example, if available will be given in each series. UTTARAKHAND OPEN UNIVERSITY Page 7 INORGANIC CHEMISTRY-II BSCCH-201 1.4 PROPERTIES OF THE ELEMENTS OF FIRST TRANSITION SERIES As has already been mentioned in the beginning that the first transition series is also known as 3d-series because the last or the differentiating electron in the atoms of these elements enters the 3d-subshell. This series starts at scandium, the element of Group 3 and ends at zinc, the element of Group 12, containing a total of ten elements. Thus, this series of elements lies in between calcium (Ca, Z=20) and gallium (Ga, Z=31), the elements of Group 2 and Group 13. The ten elements of the first transition series are scandium (Sc, Z=21), titanium (Ti, Z=22), vanadium (V, Z=23), chromium (Cr, Z=24), manganese (Mn, Z=25), iron (Fe, Z= 26), cobalt (Co, Z= 27), nickel (Ni, Z=28), copper (Cu, Z= 29) and zinc (Zn, Z= 30). These elements are much more important than those of second transition series. All the characteristics properties of the d-block elements are shown by the elements of first transition series which are given below: 1.4.1 Electronic Configuration and Variable Oxidation States. The general valence shell electronic configuration of these elements is 3dx4sy where x=1 to 10 and y= 1 or 2, i.e. the 3-d subshell has one to ten electrons from Sc to Zn and 4s-subshell, in general, has two electrons (i.e. 4s2 ) except in Cr and Cu which have only one 4s electron (i.e. 4s1 ). The exceptional valence shell configuration of Cr and Cu is attributed to the exchange energy effect and the extra stability of the resulting half–filled and completely–filled subshells. “The shifting of an electron from one subshell to another of similar or slightly higher energy in order to achieve the half-filled or completely-filled subshell is known as exchange energy effect”. The state of affairs can be shown as follows: Cr (Z= 24): 3d44s2 (expected but unstable) 3d54s1 (actual, more stable). Cu (Z=29): 3d94s2 (expected but unstable) 3d104s1 (actual, more stable). As is evident, there is exchange of electrons from 4s to 3d subshell thereby increasing the stability of the valence shell configuration in Cr and Cu atoms. Thus, among 3d- series elements, only Cr and Cu exhibit irregular/anomalous electronic configurations. UTTARAKHAND OPEN UNIVERSITY Page 8 INORGANIC CHEMISTRY-II BSCCH-201 The first transition series elements generally show variable (many) oxidation states in their compounds / ionic forms. The cause of showing different oxidation states is that these elements have several 3d electrons which are quite close to 4s – electrons in energy. The minimum oxidation state shown by all the elements of this series is +2 except Cr and Cu which show +1 oxidation state as well. The number of oxidation states shown increases from Sc to Mn and then decreases till Zn which shows the +2 oxidation state only. As a result, among these elements, Cr and Mn show the maximum number of oxidation states from +1 to +6 and +2 to +7, respectively. From Sc to Mn, the highest oxidation state shown by any element is equal to the group number but the latter elements do not follow this trend. This is evident from the following table: Elements: Sc Ti V Cr Mn Fe Co Ni Cu Zn Group 3 4 5 6 7 8 9 10 11 12 number Lowest +2 +2 +2 +1 +2 +2 +2 +2 +1 +2 oxidation state Highest +3 +4 +5 +6 +7 +6 +4 +3 +2 +2 oxidation state It has been observed that the lower (+2, +3, etc.) oxidation states generally dominate the chemistry of the first transition series. For an element the relative stability of various oxidation states can be explained on the basis of the stability of d0 , d5 and d10 configurations, e.g. Ti4+ ion (3d04s0) is more stable than Ti3+ (3d14s0) because of the presence of 3d0 subshell. Similarly, Mn2+ (3d54d0) ion is more stable than Mn3+ (3d44s0) ion since Mn2+ ion has 3d5 subshell. It has also been observed that first transition series elements form ionic oxides and chlorides in the lower oxidation states which are basic in nature. As the oxidation state of the elements increases, covalent character and acidic nature of these compounds also increases, e.g., MnO (+2) is basic, Mn2O3 (+3) and MnO2 (+4) are amphoteric and Mn2O7 (+7) is acidic. Similarly, CrO (+2) is basic, Cr2O3 (+3) is amphoteric and CrO3 (+6) is acidic. Also VCl2 (+2) is basic and VOCl3 (+5) is acidic. UTTARAKHAND OPEN UNIVERSITY Page 9 INORGANIC CHEMISTRY-II BSCCH-201 1.4.2 Complex Formation Tendency: The elements of first transition series fulfill all conditions of complex formation and are, thus, most suitable for this purpose. As a result, the cations of these elements have a strong tendency to form complexes with certain molecules (e.g. CO, NO, NH3, etc.) or several ions (e.g. F-, Cl-, CN- etc.). These molecules and ions are called ligands (L) and have one or more lone pairs of electrons on their donor atom (usually central atom) which they donate to the metal ion/atom (M) during the process of complex formation via M←L coordinate covalent bonds. This happens because the metal ions are electron deficient in most of their oxidation states or even the atoms are electron acceptors. Small size and high charge density of the metal ions facilitate the formation of the complexes which also depends on the basicity of the ligands. The complex formation tendency increases as the positive oxidation state of the metal ion increases. The nature of the complexes depends on the orbitals available on the metal ion / atom for bonding. These orbitals are s, p and d type. The structures commonly found in the complexes of the elements of first transition series are linear, square planar, tetrahedral and octahedral. This shows that the metal orbitals are hybridized before bonding with the ligand orbitals, e.g. [Ni(CN)4]2- ion is square planar while [NiCl4]2- ion is tetrahedral (detail of the complexes have been given ahead in this section). 1.4.3 Magnetic Behaviour: As has been mentioned earlier, there are several kinds of magnetism observed in the ions /compounds or complexes of transition metals. Among the transition metal compounds paramagnetism is common though some metals in the elemental form also show ferromagnetism. Origin of Paramagnetism The electrons being charged particles act as tiny magnets (or micro magnets) by themselves and determine the magnetic properties of the substances in two ways: (a) Spin motion or spinning of the electron on its axis produces spin magnetic moment and UTTARAKHAND OPEN UNIVERSITY Page 10 INORGANIC CHEMISTRY-II BSCCH-201 (b) Orbital motion or the movement of the electron round the nucleus produces orbital magnetic moment. The resultant of the above two moments gives the total moment produced by an electron. The observed magnetic moment of the compounds is the sum of the moments of all the electrons present in them. If the two electrons with opposite spins are paired in the same orbital, the magnetic moment produced by one electron is cancelled by that caused by the other electron because both the electrons will have equal but opposite moment thereby giving zero resultant magnetic moment. Such substances which have paired electrons will not show paramagnetism, rather they are diamagnetic. But if there are unpaired electrons in the ions/atoms of the substance it has the moment produced by all the unpaired electrons. The resultant or total moment in them is sufficiently high to overcome the magnetic moment induced by an approaching magnetic field. Hence, such substances instead of experiencing repulsion, are attracted in a magnetic field and are called paramagnetic substances. The magnetic moments of atoms, ions and molecules are expressed in units called Bohr Magneton (B.M.) which is defined in terms of the fundamental constants as 1 B.M. = where h = Planck’s constant, e = electronic charge, c = velocity of light and m = mass of electron. The magnetic moment of a single electron is given by the expression (According to wave mechanics) Where S= resultant spin quantum number and g = gyromagnetic ratio (called g- factor). The quantity is the value of the spin angular momentum of the electron and thus g is the ratio of magnetic moment to the angular momentum. For a free electron, g value is nearly 2 (i.e. 2.00023). In transition metal compounds/complexes, the unpaired electrons are present in the outer shell of metal ions and in such cases the spin component is much more UTTARAKHAND OPEN UNIVERSITY Page 11 INORGANIC CHEMISTRY-II BSCCH-201 significant than the orbital contribution because the orbital motion of these electrons is said to be quenched or suppressed. Therefore, the latter can be neglected in comparison to the former. In such cases, the total magnetic moment is, therefore, considered entirely due to the spin of the unpaired electrons and µs is given by µs= 2 = BM (By putting the value of g = 2) Now S= n×s where n= number of unpaired electrons and s= spin quantum number (irrespective of its sign) S= n× = Putting this value of S in the above expression µs = = B.M. Or µs = B.M. µs is also expressed as µeff., i.e. effective magnetic moment which is dependent only on the number of unpaired electrons and their spins. Hence, this formula of magnetic moment is also called spin only formula. Thus, the permanent magnetic moment of 3d-transition elements gives important information about the number of unpaired electrons present in them and it varies with n. The calculated magnetic moments corresponding to 1, 2, 3, 4 and 5 unpaired electrons will be (using above formula) 1.73 B.M., 2.83 B.M., 3.87 B.M., 4.90 B.M. and 5.92 B.M. , respectively. The number of unpaired electrons evaluated from the magnetic moment value for a compound/complex gives the valuable information regarding the type of orbitals that are occupied as well as those available for hybridisation and also the structure of the molecules or complexes provided we have the idea of strength of the ligands (spectrochemical series). For example, here we discuss the structure of [MnBr4]2- complex ion in which Mn is in +2 oxidation state and its coordination number is 4. UTTARAKHAND OPEN UNIVERSITY Page 12 INORGANIC CHEMISTRY-II BSCCH-201 Mn atom (Z=25): [Ar] 3d54s2 4p0 Ground state of Mn Excited state of Mn Hybridization state of Mn+2 SP3 Hybridization 2+ - In the complex ion, Mn ion is linked with four Br ions as ligands which exert weak ligand field on the metal ion orbitals. As a result the five unpaired d-orbitals remain unaffected and one s and 3p empty orbitals of metal ion (only four hybrid orbitals are required) hybridise before bond formation producing sp3 hybrid orbitals thus giving tetrahedral structure to the complex ion. The calculated magnetic moment of this complex is nearly 5.92 B.M. which indicates the presence of five unpaired electrons. If that is the situation, the tetrahedral structure of the complex ion is confirmed involving only s and p orbitals. Similarly for the complexes with coordination number 6, i.e. six ligands are attached to the central metal ion, we can predict whether the complex is outer or inner orbital complex from the knowledge of weak and strong ligands, e.g. [Co(H2O)6]2+ is an outer orbital complex and [Co(NH3)6]2+ is an inner orbital complex having the central metal ion, Co2+ involving sp3d2 and d2sp3 hybridisation, respectively. 1.4.4 Formation of Coloured Ions/Compounds The cause of the exhibition of colour by the ions/compounds/complexes of the d- block elements has been discussed earlier. The elements of first transition series form coloured ions/compounds/complexes due to the presence of unpaired electrons in them. For example, [Co(H2O)6)2+ is pink, Cu+ (d10) ion and its salts are colourless but Cu2+ (d9) ion and its compounds are coloured, CuSO4.5H2O is blue which actually is represented as [Cu(H2O)4]SO4.H2O and [Cu(NH3)4]2+ is dark blue (almost violet). Similarly, [Ni(NO2)6]4- is red and [Ni(NH3)6]2+ is blue. Among the other compounds VO2+ is pale yellow, CrO42- is strongly yellow, MnO4- is purple in colour, and [Ti(H2O)6]3+ is green coloured. UTTARAKHAND OPEN UNIVERSITY Page 13 INORGANIC CHEMISTRY-II BSCCH-201 The colour of the complex ion depends on the nature of the ligands and type of complex formed. The metal ions with completely empty or completely filled d- subshell (as well as their compounds) are colourless, viz., Sc3+ (3d0), Ti4+(3d0), Cu+(3d10), Zn2+(3d10) etc. 1.4.5 Catalytic Activity Elements of the first transition (3d) series and their compounds have been used in many industrial processes. Their availability in a variety of oxidation states makes them capable of forming intermediate products with various reactants and their tendency to form interstitial compounds which can absorb and activate the reacting species facilitate their application as catalyst. For example, finely divided Ni is used as a catalyst in hydrogenation reactions; MnO2 catalyses the decomposition of H2O2; TiCl4 is used as a catalyst for polymerisation of ethene in the manufacture of polythene; V2O5 is employed in the catalytic oxidation of SO2 to SO3 in the contact process of manufacture of H2SO4; Fe is used in the manufacture of NH3 by Haber’s process; Cu acts as a catalyst in the manufacture of (CH3)2SiCl2 during the synthesis of silicones. Cu/V is used in the large scale production of Nylon-66. Fe(III) ions catalyse the reaction between iodide and peroxodisulphate ions. 1.4.6 Formation of Interstitial and Non-stoichiometric Compounds Elements of the 3d-transition series are capable of forming interstitial compounds, e.g., Ti2C, V2C, ScN, TiN, Fe4N etc. These compounds have the properties of alloys being hard and good conductors etc. These elements also form non-stoichiometric compounds. For example, titanium forms TiOx (x=0.65 - 1.25 and 1.998 - 2.000); vanadium forms VOx (x= 0.79 - 1.29); manganese forms MnxO (x= 0.848 - 1.00); iron form FexO (x = 0.833 - 0.957), etc. These compounds have variable composition and are formed due to the variability of oxidation states and solid defects. Sometimes the interstitial and non- stoichiometric compounds are the same. 1.4.7 Metallic Character and Alloy Formation The metals of first transition series are hard, malleable and ductile. These exhibit face centered cubic (fcc), body centered cubic (bcc) or hexagonal close packed (hcp) type UTTARAKHAND OPEN UNIVERSITY Page 14 INORGANIC CHEMISTRY-II BSCCH-201 of lattice structures. These metals are good conductors of heat and electricity. Copper and metals of the iron triad are softer than other metals. The common alloys of these metals are as follows: brass (Cu-Zn), nichrome (Ni-Cr), monel metal (Cu-Ni), german silver (Cu-Ni-Zn), stainless steel (Fe-Cr-Ni-Mn), alnico steel (Fe-Ni-Co-Al), etc. These alloys are harder and have higher melting points than the parent metals. They are also more resistant to corrosion than their constituents. 1.4.8 Periodic Properties and Their Variation along the Series The melting and boiling points, atomic and ionic radii, atomic volumes, ionization energies and standard electrode potentials along with reducing properties are the main periodic properties of these metals along the series from Sc to Zn, which are discussed below: a) Atomic Radii, Atomic Volumes and Ionic Radii As has been discussed earlier for d-block elements, the atomic radii of the elements of first transition series follow the same trend as is applied for other d-block elements. The values generally decrease along the series up to Ni then increase slightly for Cu but pronouncely for Zn. Thus Zn has exceptional value only lower than those for the first two elements and higher than those of others. This is evident from the following table: Metal Sc Ti V Cr Mn Fe Co Ni Cu Zn atoms Atomic 144 132 122 118 117 117 116 115 117 125 radii: (pm) This happens due to the increased attraction between the outer electrons and increasing nuclear charge along the period. The close values of the atomic radii from Cr to Cu are due to the existence of increased screening effect of 3d-electrons which are added in each step and which shield the 4s-electrons from the inward pull though the nuclear charge increases continuously in the series from one element to the other. The screening effect in Zn (3d10) is maximum and hence has exceptional value. UTTARAKHAND OPEN UNIVERSITY Page 15 INORGANIC CHEMISTRY-II BSCCH-201 The atomic volumes of these elements as given below are comparatively low because of the filling of 3d-orbitals instead of 4s which is the subshell of the last shell. This causes increased nuclear pull acting on the outer electrons. The densities of these elements are very high. Atomic volumes decrease up to Cu and increase thereafter for Zn. Metal atoms Sc Ti V Cr Mn Fe Co Ni Cu Zn Atomic 15.0 11.0 8.3 7.2 7.3 7.1 6.7 6.6 7.1 9.2 3 volume:(cm ) The ionic radii of these elements follow the same trend as the atomic radii, i.e. the radii of the ions with the same charge generally go on decreasing as we move across the series except only for the last element. Radii of the bivalent and trivalent ions of the elements of this series are listed below: Bivalent Sc2+ Ti2+ V2+ Cr2+ Mn2+ Fe2+ Co2+ Ni2+ Cu2+ Zn2+ ions Ionic radii 95 90 88 84 80 76 74 72 72 74 (pm) Trivalent Sc3+ Ti3+ V3+ Cr3+ Mn3+ Fe3+ Co3+ Ni3+ -- -- ions Ionic radii 81 76 74 69 66 64 63 62 -- -- (pm) b) Melting and Boiling Points The melting and boiling points of these elements are generally high and have irregular trend in the values as given below: Elements Sc Ti V Cr Mn Fe Co Ni Cu Zn Melting 1540 1670 1900 1875 1245 1535 1495 1453 1083 420 point0C As is evident from this table, the highest melting point is for V (1900 0C) and Zn, the last element has exceptionally low melting point (420 0C). Among other elements UTTARAKHAND OPEN UNIVERSITY Page 16 INORGANIC CHEMISTRY-II BSCCH-201 Mn and Cu have lower melting points as compared to other members. The boiling points are very high, >22000C except for Zn (9060C) as expected. c) Ionization Energies and Reactivity The first ionization energy values of 3d-series elements show irregular trend as shown below: Elements: Sc Ti V Cr Mn Fe Co Ni Cu Zn I.E. (KJ): 631 658 650 653 717 759 758 737 746 906 But the second and third I.E. values generally show the increasing trend from Sc to Zn. The appreciably higher value of first I.E. for Zn is attributed to the additional stability associated with completely filled 3d-subshell (3d104s2). The variation or irregularity occurring in the values of I.E. across the series are mainly due to the changes in atomic radii because of the screening effect of extra electrons added to 3d- subshell which is exerted on the nuclear charge. On account of the factors given above, the elements of first transition series show less reactivity. d) Standard Electrode Potentials and Reducing Properties The standard reduction potentials of the elements of 3d-series except copper are lower than that of standard hydrogen electrode. Element Sc Ti V Cr Mn Fe Co Ni Cu Zn EoR -2.10 -1.60 -1.20 -0.74 -1.18 -0.41 -0.28 -0.25 +0.34 -0.76 (volts) These elements evolve H2 from acids though at very low rate. M + 2H+ →M2+ + H2 (g). Cu does not react with acids. It has the tendency to get reduced. Sometimes the metals are protected from the attack of acids by a thin impervious layer of an inert oxide, e.g. Cr. These metals are oxidized easily to their ions and hence are reducing agent though poor due to the obvious reasons given above. UTTARAKHAND OPEN UNIVERSITY Page 17 INORGANIC CHEMISTRY-II BSCCH-201 1.5 THE BINARY COMPOUNDS OF FIRST TRANSITION SERIES ELEMENTS Those compounds which are formed by the combination of two different elements / ions are called binary compounds. For example, oxides, sulphides, halides, phosphides, carbides, nitrides, etc. 1.5.1 Oxides The elements of the 3d-transition series react with oxygen at high temperature to give oxides. These oxides are less basic and less soluble in water. Oxides in lower oxidation states are ionic and basic, in the intermediate oxidation states their nature is amphoteric and in higher oxidation states, ionic nature decreases and covalent nature increases thereby increasing the acidic character of the oxides. It means the acidity of a salt depends on its covalent nature which in turn is based on the oxidation state of the element. Thus, oxidation state ∝ covalent nature ∝ acidic nature. Accordingly, the oxides may be classified as (a) basic oxides, (b) amphoteric oxides and (c) acidic oxides. (a) Basic oxides are those which are formed by the metals in the lower oxidation states. These are ionic in nature, soluble in non-oxidising acids, e.g. HCl. For example, TiO, CrO, MnO, FeO, Cu2O, CoO, NiO, etc. (b) Amphoteric oxides are the oxides containing the metals in the intermediate oxidation states. These oxides are also soluble in non-oxidising acids, e.g., HCl. Examples TiO2, VO2, Cr2O3, Mn3O4, MnO2, CuO, ZnO, etc. (c) Acidic oxides are of weak acidic nature and are formed by the elements in higher oxidation states. These are soluble in bases. For example, V2O5, CrO3, MnO3, Mn2O7 etc. Reducing and oxidising nature of oxides. The electron exchange property determines the redox nature of oxides. The oxide containing the metal is lower oxidation state acts as electron donor and hence is a reductant (reducing agent). As atomic number increases, the reducing property in the lower oxidation state also increases, e.g., TiO < VO < CrO. If the metal in the oxide is in higher oxidation state, the oxide is electron acceptor or oxidising agent, e.g., CrO3, Mn2O7 etc. UTTARAKHAND OPEN UNIVERSITY Page 18 INORGANIC CHEMISTRY-II BSCCH-201 1.5.2 Halides The elements of 3d-transition series react with halogens at high temperature to give halides. The reactivity of halogens goes on decreasing from F2 to I2. Fluorides are ionic, others have ionic as well as covalent nature. Halides are formed by many of these elements in different oxidation states, e.g. TiCl3 ,TiCl4,VCl3,VCl5 etc. 1.5.3 Sulphides Metal sulphides may either be prepared by direct heating the mixture of metal and sulphur or by treating metal salt solution with H2S or Na2S: heat Metal + S metal sulphide Or metal salt solution + H2S/Na2S metal sulphide Metals in low oxidation state form sulphides which are insoluble in water. 1.5.4 Carbides Metal carbides are generally prepared by the following two methods: heat Metal + carbon metal carbide heat Or metal oxide + carbon metal carbide The carbides of these metals are classified as follows: (a) Metallic or Interstitial carbides These carbides are prepared as is given below. V+C VC TiO2 + 2C TiC + CO2 3Fe + C Fe3C These are hard solids, have metallic properties like lustre, are stable at high temperature, chemically inert and are conductors. Ni does not form carbide. In solid state, these have tetrahedral or octahedral voids which are occupied by carbon atoms. (b) Salt-like carbides These carbides are limited to Sc, Cu and Zn only and are ionic in nature: UTTARAKHAND OPEN UNIVERSITY Page 19 INORGANIC CHEMISTRY-II BSCCH-201 Sc2O3 + 7C 2ScC2 + 3CO ScC2 + 2H2O C2H2 + Sc(OH)2 Zn + C2H2 ZnC2 + H2 ZnC2 + 2H2O C2H2 + Zn(OH)2 1.6 RELATIVE STABILITY OF OXIDATION STATES OF THE ELEMENTS OF FIRST TRANSITION SERIES The stability of an element is determined by its electronic configuration. The elements of the 3d-transition series, generally exhibit variable oxidation states and are more stable in a particular oxidation state, e.g., Ti4+ > Ti3+ and Fe3+ > Fe2+ etc. Generally, lower oxidation states are less stable than the higher oxidation states. This relative stability depends on many factors: (a) Filled, half-filled and vacant d-orbitals present in the compound, i.e. d10, d5 and d0 configurations are more stable than other configurations, e.g. Ti4+(d0) > Ti3+(d1); Mn2+(d5) > Mn3+(d4). However, it is not always true, e.g. Cu+(3d10) is less stable than Cu2+(3d9) due to high lattice energy and solvation energies of Cu2+ in solid state and in solution. (b) Higher oxidation states become less stable as atomic number increases. For example, Sc3+ > Ti3+ > V3+ > ------- > Ni3+ > Cu3+. (c) In the binary compounds of elements of 3d-transition series, it has been observed that halogens and oxygen also illustrate the trend in stability. Generally, the group oxidation state for many elements is brought out more readily by oxygen than fluorine, the strongest halogen. This may be because fewer oxygen atoms are required than fluorine atoms to achieve the same oxidation state. For example, the group oxidation state (+7) of Mn is achieved in MnO4– , but MnF7 has never been prepared. In the d-block elements, the oxidation states can be stabilised by complex formation. Low oxidation states are less stable and ligands like CN-, N2, NO, CO, C6H6, C2H4 etc. called π-acceptors form complexes in these low oxidation states to stabilise them. These complexes are known as π-complexes, e.g. [Ni(CO)4], [Cr(C6H6)2], [Fe(C5H5)2] etc. Higher oxidation states are stabilized by complex formation with highly electronegative ligands. UTTARAKHAND OPEN UNIVERSITY Page 20 INORGANIC CHEMISTRY-II BSCCH-201 (d) The compounds in any oxidation state of the metal are regarded as stable if they have free existence, are not oxidised by air, are not hydrolysed by water vapour, do not disproportionate or decompose at normal temperature. 1.7 THE COMPLEXES OF THE FIRST TRANSITION SERIES ELEMENTS, THEIR COORDINATION NUMBER AND GEOMETRY The elements of first transition (3d) series fulfill all conditions of complex formation and thus are most suitable for this purpose. The general representation for the complexes is as follows: [M Ln]x± where n represents the number of lone pairs accepted by the central metal atom/ion from the ligands (L) and x is the charge on the metal complex which may be positive or negative or even zero in neutral complexes. All the elements of this series form complexes with a variety of ligands, e.g. [CrCl2(H2O)4]+, [Fe(CN)6]3-, [Ni(NH3)6]2+, [Co(H2O)6]2+, [Co(NH3)3(SCN)3], [Cu(NH3)4]2+, [Ag(NH3)2]+ etc. The elements of this series form stable complexes with N, O, and halogen donor ligands. Coordination Number (CN) The number of ligands (monodentate only) directly attached to the central metal atom / ion or more appropriately the number of lone pairs of electrons accepted by the central metal atom / ion from the ligands (mono as well as polydentate) in the process of the formation of the complexes (molecules or ions), is known as the coordination number (C.N.) of the metal. In the above examples, the C.N. of Ag+ ion is 2, that of Cu2+ ion is 4, for Cr3+, Ni2+, Co3+, Co2+ and Fe3+ ions it is 6. The central metal atom / ion and attached ligands are kept within the square brackets called coordination sphere. With the polydentate ligands the metal atom / ions form ring type complexes known as chelates (meaning claw). Geometry of the Complexes The coordination number of the central metal atom/ion of the complex is intimately related with its geometry. The relationship may be shown as follows: C.N. Geometry of the complex UTTARAKHAND OPEN UNIVERSITY Page 21 INORGANIC CHEMISTRY-II BSCCH-201 2 Linear: Cu+ and Ag+ complexes, e.g. [Ag(NH3)2]+ 4 Tetrahedral: Mn2+, Co2+, Fe2+, Ni2+, Cu2+ complexes with weak ligands viz. H2O, Cl-, Br-, I- etc., e.g. [MnCl4]2-, [MnBr4]2-, [NiCl4]2-, [CuCl4]2-, [FeCl4]2- etc. Square planar: Ni2+, Cu2+ complexes with strong ligands viz. CN-, NH3, en, dmg etc., e.g. [Ni(dmg)2], [Cu(en)2]2+, [Cu(NH3)4]2+, [Ni(CN)4]2- etc. 6 Octahedral: Cr2+, Cr3+, Mn2+, Fe2+, Fe3+,Co2+, Co3+, Ni2+ complexes with weak and strong field ligands, e.g. 3+ 2+ [Cr(H2O)6] , [Mn(H2O)6] , [Ni(NH3)6]2+, [Co(NH3)6]3+, [Co(en)3]3+ etc. It may be recalled that octahedral complexes of the metal ions with weak field ligands are outer orbital (also called high spin) complexes involving sp3d2 hybridisation and those with strong field ligands are inner orbital (also known as low spin) complexes, the central ion undergoing d2sp3 hybridisation. 1.8 SUMMARY In contrast to main group elements, the last electron in the atoms of d-block elements enters the (n-1)d-subshell which influences the characteristics and periodicity in properties of transition elements. Hence, the text material of this unit is related with characteristic properties in general of d-block elements such as their electronic configuration, variable oxidation states, complex formation tendency, magnetic properties, formation of coloured ions / compounds, catalytic activity, formation of interstial and non-stoichiometric compounds, alloy formation, metallic character, melting and boiling points, atomic and ionic radii, ionization energies, reactivity, standard electrode (reduction) potential and reducing properties. The above properties have also been discussed for the elements of the first transition (3d) series in brief giving examples where ever possible. A brief but concrete account of binary compounds of elements of 3d-series along with relative stability of their oxidation states, their complexes, coordination number and geometry of the complexes has also been given. UTTARAKHAND OPEN UNIVERSITY Page 22 INORGANIC CHEMISTRY-II BSCCH-201 1.9 TERMINAL QUESTIONS 1. Give a brief note on the factor responsible for anomalous electronic configuration of Cr and Cu. 2. What accounts for the complex formation tendency of d-block elements? 3. Write a short note on the paramagnetism shown by d-block elements. 4. Why do 3d-series elements form coloured ions and compounds? 5. What are the non-stoichiometric compounds? 6. What are alloys? Give any two examples. 7. “Mn and Cr have highest number of oxidation states among first transition (3d) series elements”. Comment. 8. Which one is more stable: Ti4+ or Ti3+? 9. µeff for a metal ion with 3 unpaired electrons is a) 1.73 B.M. b) 2.83 B.M. c) 3.87 B.M. d) 4.90 B.M. 10. Finely divided Ni is used in a) The manufacture of H2SO4 b) The manufacture of HNO3 c) The manufacture of NH3 d) The hydrogenation reactions 11. Brass is an alloy of a) Cu-Zn b) Cu-Fe c) Cr-Ni d) Mn-Fe 12. MnO2 is a) An acidic oxide b) An amphoteric oxide c) A basic oxide d) None of the above 1.10 ANSWERS 1 to 7: please refer to the text UTTARAKHAND OPEN UNIVERSITY Page 23 INORGANIC CHEMISTRY-II BSCCH-201 8. Ti 4+ (3d0) is more stable than Ti3+ (3d1) 9. c 10. d 11. a, 12. b UTTARAKHAND OPEN UNIVERSITY Page 24 INORGANIC CHEMISTRY-II BSCCH-201 UNIT 2- CHEMISTRY OF THE ELEMENTS OF SECOND TRANSITION (4d) SERIES CONTENTS: 2.1 Objectives 2.2 Introduction 2.3 General characteristics 2.4 Comparative study with their 3d analogues in respect to Ionic radii, oxidation state, magnetic behavior 2.5 Spectrial properties and stereochemistry 2.6 Summary 2.7 Terminal Questions 2.8 Answers 2.1 OBJECTIVES The course material of this unit is being written with the objective of making it easy for the learners to understand the general characteristics of the elements of second transition (or 4d) series such as their electronic configuration, variable oxidation states, complex formation tendency, magnetic properties, formation of coloured ions / compounds, catalytic activity, formation of interstitial and non-stoichiometric compounds, metallic character and alloy formation as well as other periodic properties such as atomic and ionic radii, melting and boiling points, ionization energies and reactivity, standard electrode potential and reducing properties, etc. with their variation along the series. The comparative study of some of the above periodic properties, viz., ionic radii, oxidation states and the magnetic behaviour of these elements with those of their 3d analogues is also aimed at. The spectral properties ad stereochemistry of these elements and their compounds or complexes is also to be discussed to make the readers familiar with these fascinating aspects. UTTARAKHAND OPEN UNIVERSITY Page 25 INORGANIC CHEMISTRY-II BSCCH-201 2.2 INTRODUCTION The series of ten elements starting from yttrium, the element of Group 3 and ending at cadmium, the element of Group 12, constitutes the second transition series. These elements with their symbols and atomic numbers are given here: Yttrium (Y, Z = 39), zirconium (Zr, Z = 40), niobium (Nb, Z = 41), molybdenum (Mo, Z = 42), technetium (Tc, Z = 43), ruthenium (Ru, Z = 44), rhodium (Rh, Z = 45), palladium (Pd, Z = 46), silver (Ag, Z = 47) and cadmium (Cd, Z = 48). These elements are also known as the elements of 4d transition series because the differentiating or the last electron in the atoms of these elements enters the 4d subshell progressively giving 4d1 to 4d10 configurations, respectively. All the characteristic properties of d-block elements are exhibited by the members of this series also. These elements are the next higher analogues of first transition series elements and are less important. This series lies between strontium (Sr, Z =38) of s- Block (Group 2) and indium (In, Z = 49) of p-Block (Group 13) so that the gradual transition of properties may occur from s- to p- Block elements in the period. 2.3 GENERAL CHARACTERISTICS OF SECOND TRANSITION (4D) SERIES ELEMENTS All the general characteristics of the d-Block elements are applicable to the elements of second transition series though to the lesser extent. These are discussed below: 2.3.1 Electronic Configuration and Variable Oxidation States In yttrium 4d-subshell begins filling, its valence shell configuration being 4d15s2. The filling of 4d-subshell continues as we move along the series towards the last element, Cd which has 4d105s2 valence shell configuration. There are observed pronounced irregularities in the valence shell configurations of these elements which have the general valence shell configuration 4d1-105s1,2. Except for the last three elements, viz., Pd, Ag and Cd which have completely filled 4d-subshell (4d10), all have incomplete d-subshells. Y, Zr, Tc and Cd have 2 electrons in 5s-subshell (5s2) but Nb, Mo, Ru, Rh and Ag have only one electron, i.e., 5s1, in the last shell and Pd does not have any 5s- electron (5s0). The anomalous valence shell configuration of Pd (i.e. 4d105s0) is due to the shifting of both 5s-electrons to 4d-subshell so that it has UTTARAKHAND OPEN UNIVERSITY Page 26 INORGANIC CHEMISTRY-II BSCCH-201 completely filled state (i.e., 4d10) and becomes stable, though no satisfactory explanation is available for this shifting. For the elements which have partly filled 4d- subshell but still have only one electron in 5s subshell (5s1), the anomalous behaviour has not been explained with effective reasoning, only it is said for these elements that the nuclear-electron and electron-electron interactions play significant role for this behaviour. In Mo (4d5) and Ag (4d10), one electron is said to have shifted from 5s to 4d subshell to make the atoms of these elements extra stable due to exchange energy effect as has been given earlier for Cr and Cu elements of 3d- transition series. Like the elements of first transition (3d) series, the elements of this series also exist in various oxidation states in their compounds. This is because of the availability of several electrons in 4d and 5s subshells whose energies are fairly close to each other. Hence, under different experimental conditions different number of electrons can be used from both the subshells for bonding. It has been found for second transition series elements that the higher oxidation states become more stable. This can be illustrated by taking Fe and its next higher analogue, Ru. Fe shows +2 and +3 stable oxidation states and +4 and +6 unstable states but Ru has +2, +3, +4 and +6 as stable oxidation states while +5, +7 and +8 are unstable states for this element. The first element Y (+3) and the last element Cd (+2) exhibit only one oxidation state ( though Sc in 3d transition series has also been assigned a very uncommon oxidation state of +2) because of the stable valence shell configuration of the ions, viz., Y3+ [Kr]4d05s0 and Cd2+ [Kr]4d105s0. All other elements show a variety of oxidation states, both stable and unstable, the variability being the maximum towards the middle of the series as happens in case of elements of 3d-transitin series. Ruthenium, lying almost in the middle of the series, exhibits maximum number of oxidation states (i.e. 7) among all the elements of the series, including the unstable ones, ranging from +2 to +8 (i.e.+2, +3, +4, +5, +6, +7,+8). Up to Ru, the next higher member of Fe group, the highest oxidation state is equal to the group number, e.g., Sc: + 3 (Group 3); Zr: +4 (Group 4); Nb: +5 (Group 5), Mo: +6 (Group 6), Tc: +7 (Group 7) and Ru: +8 (Group 8) but the latter members of the series do not follow this trend. The lowest oxidation state is +1 only for Ag, the next congener of Cu. For Ru, Pd and Cd, the lowest oxidation state is +2, and +3 is the UTTARAKHAND OPEN UNIVERSITY Page 27 INORGANIC CHEMISTRY-II BSCCH-201 lowest oxidation state for other members of the series. This has been shown in the table below. Element Y Zr Nb Mo Tc Ru Rh Pd Ag Cd Group number 3 4 5 6 7 8 9 10 11 12 Lowest oxidation +3 +3 +3 +3 +4 +2 +3 +2 +1 +2 state Highest +3 +4 +5 +6 +7 +8 +6 +6 +3 +2 oxidation state Thus, it is concluded that the electronic structure of the atoms of the second transition series elements does not follow the pattern of the elements of the first transition series and also among the 4d series elements, the higher oxidation states become more pronounced and stable. 2.3.2 Complex Formation Tendency The availability of various oxidation states facilitates the complex formation tendency. The complex formation tendency is found in the elements of second transition series also though it is less pronounced. These metals are weakly electropositive and do not form stable complexes with wide range of ligands as is found in case of first transition series elements. These elements from stable complexes with P, S and heavier halogens as donor atoms in the ligands in contrary to the elements of 3d sereis. They also form π complexes with CO as ligand. The 4d series elements show the common as well as unusual coordination numbers in their complexes which may be 4, 6 and even more than six. The examples are available for most of the second transition series elements in various oxidation states. Yttrium forms complexes readily with NCS-, acac, EDTA etc., viz., [Y(NCS)6]3-, [Y(acac)3.H2O], [Y(EDTA)]- , respectively. Its complexes with C.N. 8 are also known. Zirconium usually gives halo complexes of the type [ZrX6]2- and [ZrX7]3- (X = halide ions), [Zr(acac)4], [Zr(C2O4)4]4- , [Zr(bipy)3] and also [Zr2F13]5- and [ZrCl4]3(POCl3)2 type. UTTARAKHAND OPEN UNIVERSITY Page 28 INORGANIC CHEMISTRY-II BSCCH-201 Niobium forms clusters only, e.g. [Nb6X12]n+, where n = 2, 3 or 4; [Nb6X14], [Nb6X15] and [Nb6X16], etc. Molybdenum forms a variety of complexes having Mo in different oxidation states and coordination numbers. For example, [Mo2Cl8]4-, [Mo2Cl9]3-, [MoCl6]2-, [Mo(CO)5]2, [Mo2(CO)10]2-, [Mo(CO)6], [Mo(CNR)7]2+, [Mo(CN)8]4-, [Mo(S2CNMe2)4], etc. Technitium also forms many complexes though not as many as are formed by manganese and rhenium. For example, [Tc(CO)4]3-, [Tc(CO)5]-, [Tc2(CO)10], [Tc(CN)7]4-, [Tc(CN)6]-, [Tc(NCS)6]-, [TcH9]2- etc. Ruthenium forms a variety of complexes both with normal and π-ligands, such as N2, CO etc. For example, [Ru(NH3)5N2]3+, [Ru(NH3)6]3+, [Ru(CO)5], [Ru3(CO)12] etc. The first complex further gives ploynuclear complex (N2 is weak π- ligand): [Ru (NH3)5 N2]3+ + [Ru (NH3)5. H2O]3+→ [(H3N)5 Ru-N2-Ru (NH3)5]4+ + H2O The complexes of Rh, Pd and Cd are as follows: [Rh(CO)4]-, [Rh4(CO)12], [Rh6(CO)16], [Pd(NH3)2Cl2], [Pd(NH3)4]2+, [Cd(CN)4]2-, [Cd (NH3)4]2+ and [[Pd(NH3)6]2+ etc. 2.3.3 Magnetic Properties The elements of second transition series exhibit paramagnetism due, obviously, to the presence of unpaired d-electrons in elemental or ionic forms. It has been observed that the magnetic moment, a measure of magnetism in the substances, increases with the number of unpaired electrons (the relationship of magnetic moment, µeff and number of unpaired electrons has been given in Unit 1 under magnetic properties of 3d-series elements). The relationship is called spin only formula because only spin contribution towards the total magnetic moment is considered and orbital contribution is regarded as quenched. However, if the orbital contribution is also considered in its full capacity to the total magnetic moment then the magnetic moment of the substance can be calculated by the formula: µeff = UTTARAKHAND OPEN UNIVERSITY Page 29 INORGANIC CHEMISTRY-II BSCCH-201 Where S is resultant spin angular momentum and L is the resultant orbital angular momentum. In the ions/compounds/complexes of second transition series elements, the spin only formula is used to calculate the number of unpaired electrons from µeff values. 2.3.4 Formation of Coloured Ions / Compounds. The elements of the second transition series also form coloured ions / compounds / complexes whether in solid or in solution state, due to usual reasons as have been given for those of first transition series as well as for general d-block elements. The cations having vacant or completely filled d-orbitals (d0 or d10) are colourless in the case of this series also. But, those with partly filled d-orbitals (d1, d2, d3……..d9) are coloured. It means the cations having all the electrons paired in d-orbitals or no electrons in this subshell are colourless but those cations / compounds having unpaired (some or all) in d-orbitals are coloured. If n is the number of unpaired electrons in d-subshell, then the ions having n = 0 are colourless while those having n = 1, 2,….,5 are coloured. In addition to the presence of unpaired electrons in d- subshell or incomplete d-subshell, the nature of atoms (in the compounds) or ligands (in the complexes) attached to central metal ion determines the colour of the compounds as a whole. As has been explained earlier, the colour in the substances is developed due to the movement of electrons from one d-orbital to another under the influence of visible light falling on the substance. The colour is intense if the transition is allowed but becomes dull if it is forbidden. If in place of inter orbital transition, inter atomic transitions take place, intense colours are produced because such transitions are not affected by the selection rules (viz. spin, Laporte and symmetry selection rules) thereby allowing free transition of electrons. 2.3.5 Catalytic Activity Like the elements of first transition series, those of second transition series also show catalytic activity, some of them being very important and useful as catalysts in a variety of reactions of industrial importance. This is because these are capable of forming inter mediate products with the reactants or have active centres on their UTTARAKHAND OPEN UNIVERSITY Page 30 INORGANIC CHEMISTRY-II BSCCH-201 surface in the activated state which can activate the reactants for the desired reactions. For example, (a) Pd is used in the hydrogenation of phenol to cyclohexanol. (b) Pd/Pt catalyses the hydrogenation of unsaturated hydrocarbons. (c) Mo is used as a promoter in the manufacture of ammonia by Haber process. (d) Pt/Rh is used as catalyst in the oxidation of NH3 to NO (manufacture of HNO3). 2.3.6 Formation of Interstitial and Non-stoichiometric compounds. The metals of second transition series, in general, form interstitial compounds with small non-metallic elements such as H, N, C etc. The lattice of these metals is capable of accommodating these small atoms between the metal atoms with no change in the lattice structure. Examples are: PdH0.6, ZrH1.98, ZrC, NbC, MoC, Mo2C, ZrN, NbN, Mo2N etc. These compounds have conductivity properties and are hard, thus behaving as alloys. These elements also form non-stoichiometric compounds which often exhibit semi conductivity, fluorescence and have centres of colours. Above examples of PdH and ZrH2 also furnish the examples of non-stoichiomestry. Apparently the molecular formula of these compounds does not correspond to M: H ratio of 1:1 and 1:2. Actually, the M: H ratio in these compounds is 1: 0.6 and 1:1.98, respectively. 2.3.7 Metallic character and Alloy Formation. All the elements of second transition series are metals which are hard, some of them malleable and ductile (e.g., Ag), fairly good conductors of heat and electricity. They crystallize in one of the following lattice structures: body centred cubic (bcc), face centredcubic (fcc) or hexa gonal close packed (hcp). The elements of this series also form alloys though to the lesser extent than the elements of first transition series due to the obvious reasons as given earlier. These alloys are also usually harder and have higher melting points than parent metals. They are also corrosion proof/resistant. These metals are less important than those of the first and third transition series. UTTARAKHAND OPEN UNIVERSITY Page 31 INORGANIC CHEMISTRY-II BSCCH-201 2.3.8 Periodic Properties and Their Variation along the Series The periodic properties of second transition series elements such as the atomic radii, ionic radii, atomic volumes, ionization energies, melting and boiling points, standard electrode potentials, reactivity and reducing properties also vary along the series from the first element Y to the last element Cd. These have been discussed below along with their variation in the series. (a) Atomic Radii, Atomic Volumes and Ionic Radii It has been observed that the atomic radii of the elements of second transition series, though not known with certainty, decrease from the first element, Y to Rh, the next congener of Co and increase thereafter up to the last element, Cd. The values are very close from Mo to Pd because of the increased screening effect of the 4d electrons which more or less counter balance the nuclear pull exerted on the 5s electrons. Then the screening effect becomes more and more pronounced thereby decreasing the attractive force between the nucleus and the outer electrons. As a result, atomic radii of Ag and Cd are increased. Cd has next highest atomic radius which is only lower than that for Y. These values have been given below: Elements Y Zr Nb Mo Tc Ru Rh Pd Ag Cd Atomic radii 162 145 134 130 127 125 125 128 13 148 (pm) 4 The atomic volumes of these elements which are dependent on the atomic radii show the same trend in their variation. The atomic volumes are being listed below: Elements Y Zr Nb Mo Tc Ru Rh Pd Ag Cd Atomic 19.8 14.0 10.8 9.4 - 8.3 8.3 8.9 10.3 13.0 volume (Cm3) For Tc its value has artibrarily been calculated but is not known with certainty. The values decrease from the first element, Y, upto Rh and then increase due to the obvious reason, i.e. increasing atomic radii values. UTTARAKHAND OPEN UNIVERSITY Page 32 INORGANIC CHEMISTRY-II BSCCH-201 The ionic radii follow almost the same trend as the atomic radii at least for the few elements. These elements form ions of variety of oxidation states but only those ions may be considered which bear the same charge. This analogy does not apply to the ions of these elements. For various ions, the ionic radii are listed here: Ions Y3+ Zr4+ Nb5+ Mo4+ Tc4+ Ru3+ Rh3+ Pd2+ Ag+ Cd2+ Ionic radii 104 86 70 79 - 81 80 80 123 97 (pm) As is evident from this table, ionic radii values are showing an irregular trend particularly for the later elements. (b) Melting and Boiling Points The melting and boiling points of these elements are generally very high, almost similar to those of the elements of first transition series except for a few elements which have very high values, e.g., Nb to Ru (see the table given below). The last element Cd, has exceptionally low value of melting point even lower than that of Zn. This may be attributed to its high atomic volume, almost one and half times to that of Zn. This results in weaker metallic bonding in the metal lattice of Cd. Melting point values of these elements are as follows: Element Y Zr Nb Mo Tc Ru Rh Pd Ag Cd Melting point 1490 1860 2415 2620 2200 2450 1970 1550 960 321 0 ( C) The highest melting point is for Mo followed by Ru and other elements have comparable values of melting point. Cd has the lowest value. These elements have very high boiling points, greater than 22000C except for Cd (7650C). (c) Ionization Energies and Reactivity The first ionization energies of these elements generally increase from the first element to the last one with a marked drop in the value for Ag. The values are listed below: Element Y Zr Nb Mo Tc Ru Ph Pd Ag Cd First ionization 636 669 664 694 698 724 745 803 732 866 energy (kJ/mol) UTTARAKHAND OPEN UNIVERSITY Page 33 INORGANIC CHEMISTRY-II BSCCH-201 These high values of first ionization energies can be correlated with the values of atomic radii which generally decrease along the series and the screening effect increases; therefore, the elements accordingly have higher values. For Ag low value is attributed to slightly higher atomic radius and availability of a single 5s electron. Appreciably higher value of ionization energy for Cd is due to the stability associated with filled 4d and 5s subshells (4d105s2). As discussed in section 1.3 above, various factors are responsible for low reactivity of the elements of second transition series. They are even less reactive than those of the first transition series. (d) Standard Electrode Potentials and Reducing Properties As is well known that the standard electrode potential (reduction) is related with the reducing properties of the elements, in general. Metals with negative values of standard electrode potential as compared to standard hydrogen electrode for which E0 value is taken as zero, act as reducing agents. Such metals can displace hydrogen gas from dilute acids. For the metals with negative E0 values but not reacting with acids, some other factors also play an import role such as formation of protective coating on the metal surface and making it unreactive. Strong reducing properties of metals make them displace other metal ions from their solutions. Though standard electrode potential values are available only for a few elements of this series, these are given below: Cd2+ + 2e → Cd, E0 = - 0.40 V (can displace H2 from dilute acids) Ag+ + e → Ag, E0 = + 0.80 V (does not react with dilute acids) From the above, it can be concluded that Cd2+ ions can give up the electrons and act as reducing agents while Ag+ ions do not give the electrons, rather take up the electrons easily. Hence, act as oxidizing agents when react with reducing ions, e.g., Zn + 2Ag+ → Zn2+ + 2Ag. 2.4 COMPARATIVE STUDY OF THE ELEMENTS OF THE SECOND TRANSITION SERIES AND THOSE OF FIRST TRANSITION SERIES (a) Oxidation States UTTARAKHAND OPEN UNIVERSITY Page 34 INORGANIC CHEMISTRY-II BSCCH-201 The elements of both the transition series exhibit variable oxidation states. Some of them are common and the others are uncommon or unfamiliar oxidation states. It may be recalled that for the elements of first transition (or 3d) series, generally lower oxidation states (viz. +2, +3, etc.) are most stable while the higher oxidation states are less stable. That is why their compounds in the higher oxidation states are less stable and more reactive. For example, Cr2O72- (Cr in +6 oxidation state) and MnO4- (Mn in +7 oxidation state) are strong oxidising agents and in their reactions get reduced to Cr3+ and Mn2+ states, which are stable, respectively. We can say that lower (+2 and +3) oxidation states generally dominate the chemistry of the first transition series elements, e.g., Co2+ ion is quite stable in aqueous medium as well as Co3+ in [Co(NH3)6]3+ ion is highly stable. On the other hand, Rh2+ ion, next congener of Co is hardly known. Similarly no such complex of Rh3+ is known as is formed by Co3+ ion with NH3. For the elements of second transition series, lower (+2 and +3) oxidation states are of relatively little importance but the higher oxidation states (e.g., +5, +6, +7, etc) are stable and important. For example, in manganese group (Group 7), Mn2+ ion is stable while Tc2+ ion is unstable; Tc3+ occurs in some π-complexes and clusters only. In Group 6, Cr (III) forms a large number of compounds and complexes, while Mo (III) forms only a few. Cr (VI) ions are less stable (as discussed above), but Mo (VI) ions are highly stable: [MoO4]2- ion is not easily reduced. In Group 7, again [MnO4]- is unstable but [TcO4]- is stable and very weak oxidising agent. Similarly, FeO4, CrCl6 and NiF6 are not known, while RuO4, MoCl6 etc. are quite stable. The highest oxidation state for 3d-series elements is +7 (in MnO-4), but for 4d-series members it is +8 (in RuO4). (b) Ionic Radii In terms of the ionic radii, it has been observed that the radii of 3d-series elements are smaller than those of 4d-series elements, i.e. r3d ions < r4d ions. The comparative table of ionic radii of the elements of the two series is being given here: Ions: Sc3 Ti4+ Cr4+ Zn2+ Radii (pm): 81 75 68 74 UTTARAKHAND OPEN UNIVERSITY Page 35 INORGANIC CHEMISTRY-II BSCCH-201 Ions: Y3+ Zr4+ Mo4+ Cd2+ Radii (pm) 104 86 79 97 This is due to the change in the value of n from 3 to 4 for the two series of elements. (c) Magnetic Behaviour It has been observed that the magnetic properties of the first transition series elements could be easily interpreted and the magnetic moment of their ions/atoms or compounds can be represented by the spin only formula which gives the idea of the number of unpaired electrons in them. From this, the geometry of the complexes of these elements could be explained. But the magnetic behaviour of the second transition elements is more complex and difficult to use the spin-only formula to get the number of unpaired electrons or the magnetic moment because the orbital contribution could not be ignored outrightly for the compounds / complexes of these elements. This is because 4d-orbitals are too much spread out in space and as a result the inter electronic repulsions in these are much less as compared to first transition series orbitals. A given set of ligands produces very large crystal field splitting energy in 4d-orbitals than in 3d-orbitals. Therefore, heavier elements of this series will tend to give low-spin or inner orbital complexes as compared to those of first transition series which form mainly high-spin (or outer orbital) complexes. 2.5 SPECTRAL PROPERTIES AND STEREOCHEMISTRY OF THE ELEMENTS OF THE SECOND TRANSITION SERIES We know that the electromagnetic radiations of white light such as sunlight consist of a continuous spectrum of wavelengths corresponding to different colours. If such a light falls on a compound, the light-matter interaction results in the absorption of either all the radiations giving black colour to the compound, or that of one radiation of a particular colour. In the latter case, the light of different colour is transmitted or reflected which is the complementary colour of the absorbed colour UTTARAKHAND OPEN UNIVERSITY Page 36 INORGANIC CHEMISTRY-II BSCCH-201 and is the colour of the compound. If the compound does not absorb in the visible region, it appears white. The transition metal ions / compounds / complexes show a variety of colours depending on the nature of metals and ligands. The colour of a compound arises due to the transition of electron(s) from ground state (lowest energy) to the excited state (higher energy). When a photon having energy equal to the difference between the two states, i.e., ground and excited state, strikes the compound or the ion, electronic transition (here promotion) takes place. In the complexes of the transition metals, this transition occurs from t2g to eg level in octahedral field and from e to t2 level in tetrahedral ligand environment. The energy difference between the two states involved in electronic transition is given by (as given in the figure 2.1) the following: ∆E = E2 - E1 = = hv (∴ v = ) Where ∆E = energy, h = Planck’s constant, c = velocity of light, λ = wavelength of light absorbed, v = frequency of light absorbed and v = wave number. /////// Fig. 2.1 The colour of the compound / complex exhibited due to the above transition is called the colour due to d-d transition. The examples of compounds / complexes which are coloured due to d-d transitions are provided by first transition (3d) series elements and a few heavier elements. Greater is ∆, more energy is required to cause the d-d transition. For 4d-series elements, increasing ∆ value in octahedral field is: Mo3+ < Rh3+ < Ru3+ < Pd4+ etc. UTTARAKHAND OPEN UNIVERSITY Page 37 INORGANIC CHEMISTRY-II BSCCH-201 The other types of electronic transitions which are responsible for the colours of the ions / compounds / complexes, particularly, of second transition (4d) series elements are the charge transfer processes (C.T.) from metal to ligand or ligand to metal. The electronic spectra of the complexes / compounds of second and third transition series elements are less important than those of the complexes of first transition series elments because in the former case the d-d and C.T. bands can not be separated but this is possible in the latter case. In the compounds / complexes of heavier elements of 4d series because of the larger magnitude of ∆ (Crystal field splitting energy), the d-d bands are found at lower wave lengths and hence overlap with the C.T. bands. The charge transfer process is similar to the internal redox process because electron transfer takes place during this process from metal to ligand or ligand to metal within a complex/compound. In heavier transition metal complexes the latter is generally observed. Thus, it is possible to classify and rank the metal ions according to their oxidising power Rh4+ > Ru4+ > Ru3+ > Pd2+ > Rh3+, etc. Greater the oxidising power of the metal ion and also greater the reducing power of the ligands, lower the energy at which the C.T. bands appear. Charge transfer transitions are Laporte and spin allowed, unlike d-d transitions, i.e., ∆l = ±1 and ∆ s = 0 because in these transitions, there occurs a transition of electron(s) between the orbitals of different atoms, viz., metal and ligand. These give rise to more intense or strong absorptions. When these transitions occur in visible region, the compound / complex shows intense colour. These transitions are of four types: (a) Ligand to metal transitions (b) Metal to ligand transitions (c) Intervalence or metal to metal transitions (d) Intra ligand charge transfer Among the oxo ions of 4d series elements, the decreasing order of energy of ligand to metal charge transfer is as follows: NbO43- > MoO42- > TcO4- UTTARAKHAND OPEN UNIVERSITY Page 38 INORGANIC CHEMISTRY-II BSCCH-201 But, the energy of charge transfer increases for the similar ions of 5d-series elements. For the above ions. The energy difference between 2p-orbitals of oxide ion and 4d-orbitals of the metal ions is very large lying in UV region and hence these ions are colourless. An example of metal-metal (or inter valence) charge transfer is the Ru-complex given below: (Fig. 2.2) or [(NH3)5RuII – Pyz – RuIII(NH3)5]5+ where bridging ligand is pyrazine group. In this complex electronic transition occurs from Ru(II) to Ru(III) through Pyz-bridging ligand and gives intense colour. The compounds with M-M bonds also give intense colour, e.g., [Mo2Cl8]4- is red in colour. Also, the metal carbonyls with M-M bonds are often intensely coloured (e.g., polynuclear carbonyls). Stereochemistry of the compounds and complexes The stereochemistry of the compounds and complexes of the elements of this series may be summarized groupwise. The elements exhibit different stereochemistry depending on the oxidation state, coordination number and ligand in the particular compound / complex. For example, the stereochemistry of zirconium (Group 4) is tabulated below in Table 2.1. Table 2.1: Oxidation states and stereochemistries of zirconiium compounds Oxidation Coordination Geometry Examples state number Zr0 6 Octahedral [Zr(bipy)3] UTTARAKHAND OPEN UNIVERSITY Page 39 INORGANIC CHEMISTRY-II BSCCH-201 Zr3+ 6 Octahedral ZrX3 (X = Cl, Br,I) Zr4+ 4 Tetrahedral [ZrCl4], [Zr(CH2C6H5)4] 6 Octahedral [ZrF6]2-, [ZrCl6]2-, [Zr(acac)2Cl2] 7 Pentagonal [ZrF7]3- bipyramidal 8 [Zr(acac)4] Sqnare antiprism [Zr(C2O4)4]4-, [ZrX4.(diars)2] Dodecahedral The stereochemistry of niobium (Group 5 element) is being summarized below in Table 2.2. Table 2.2: Oxidation states and stereochemistries of niobium compounds Oxidation Coordination Geometry Examples state number -3 5 Trigonal [Nb(CO)5]3- bipyramidal -1 6 Octahedral [Nb(CO)6]- +3 6 Trigonal prism [NbO2]- Octahedral [Nb2Cl9]3- 8 Dodecahedral [Nb(CN)8]5- +4 6 Octahedral [NbCl6]2- Distoted K3[NbF7] pentagonal 7 bipyramidal 8 Square antiprism [Nb(SCN)4(dipy)2] Dodecahedral K4[Nb(CN)8] +5 4 Tetrahedral [NbO4]- UTTARAKHAND OPEN UNIVERSITY Page 40 INORGANIC CHEMISTRY-II BSCCH-201 5 Trigonal [NbCl5], [Nb(NR2)5] bipyramidal 6 [NbCl5.OPCl3], [NbCl6]- Octahedral The stereochemistry of molybdenum (Group 6 element) is given below in Table 2.3. Table 2.3: Oxidation states and stereochemistries of molybdenum compounds Oxidation Coordination Geometry Examples state number -2 5 Trigonal bipyramidal [Mo(CO)5]2- -1 6 Octahedral [M2(CO)10]2- 0 6 Octahedral [Mo(CO)6s], [Mo(CO)5I]- +2 6 Octahedral [Mo(diars)2 X2] 7 Capped trigonal prismatic [Mo(CNR)7]2+ 9 Cluster compound Mo6Cl12 +3 6 Octahedral [Mo(NCS)6]3-, [MoCl6]3- 8 Dodecahedral [Mo(CN)7(H2O)]4- +4 6 Octahedral [Mo(NCS)6]2- 8 Dodecahedral [Mo(CN)8]4- +5 5 Trigonal bipyramidal MoCl5 6 Octahedral [Mo2Cl10], [MoOCl5]2- 8 Dodecahedral [Mo(CN)8]3- +6 4 Tetrahedral [MoO4]2-, [MoO2Cl2] UTTARAKHAND OPEN UNIVERSITY Page 41 INORGANIC CHEMISTRY-II BSCCH-201 6 Octahedral [MoO6], [MoF6] The stereochemistry of technetium (Group7 element) is not much explored. Only very few examples of this element are known. Still some of them are given in Table 2.4. Table 2.4: Oxidation states and stereochemistries of technitium compounds Oxidation Coordination Geometry Examples state number 0 6 Octahedral [Tc2(CO)10] +2 6 Octahedral [Tc(diars)2Cl2] +3 6 Octahedral [Tc(diars)2Cl2]+ +4 6 Octahedral [TcX6]2- +5 5 Square pyramidal [TcOX4]- 8 Dodecahedral [M(diars)2Cl4]+ +6 6 Octahedral [TcF6] +7 4 Tetrahedral [TcO4]-, [TcO3Cl] The stereochemistry of ruthenium (Group 8 element) is being given in Table 2.5. Table 2.5: Oxidation states and stereochemistries of ruthenium compounds Oxidation Coordination Geometry Examples state number -2 4 Tetrahedral [Ru(CO)4]2- 0 5 Trigonal [Ru(CO)5], [Ru(CO)3(PPh3)2] bipyramidal +2 6 Octahedral [RuNOCl5]2-, [Ru(dipy)3]2+ +3 6 Octahedral [Ru(NH3)5Cl]2+, [Ru(H2O)Cl5]2- UTTARAKHAND OPEN UNIVERSITY Page 42 INORGANIC CHEMISTRY-II BSCCH-201 +4 6 Octahedral K2[RuCl6] +5 6 Octahedral K[RuF6], [RuF5]4 +6 4 Tetrahedral [RuO4]2- 5 Trigonal [RuO3(OH)2]2- bipyramidal 6 [RuF6] Octahedral +7 4 Tetrahedral [RuO4]- +8 4 Tetrahedral [RuO4] The stereochemistry of rhodium (Group 9 element) has been given in Table. 2.6. Table 2.6: Oxidation states and stereochemistries of rhodium compounds Oxidation Coordination Geometry Examples state number -1 4 Tetrahedral [Rh(CO)4]- +1 3 Planar [Rh(PPh3)3]ClO4 4 Tetrahedral [Rh(PMe3)4]+ 5 Trigonal bipyramidal [HRh(PF3)4] +3 5 Square pyramidal [RhI2(CH3)(PPh3)2] Octahedral 6 [Rh(H2O)6]3+, [RhCl6]3- +4 6 Octahedral K2[RhF6] +6 6 Octahedral [RhF6] The stereochemistry of less explored element palladium (group 10) has been given in Table. 2.7. UTTARAKHAND OPEN UNIVERSITY Page 43 INORGANIC CHEMISTRY-II BSCCH-201 Table 2.7: Oxidation states and stereochemistries of palladium compounds Oxidation Coordination Geometry Examples state number 0 3 Planar [Pd(PPh3)3] 4 Tetrahedral [Pd(PF3)4] +2 4 Planar [Pd(NH3)4]Cl2 +4 6 Octahedral [PdCl6]2- The stereochemistry of silver (Group 11element) is being given below: Table. 2.8. Table 2.9: Oxidation states and stereochemistries of silver compounds Oxidation Coordination Geometry Examples state number +1 2 Linear Ag(CN)2-, Ag(NH3)2+ 4 Tetrahedral [Ag(SCN)4]3-, [Ag(py)4]ClO4 6 Octahedral AgCl, AgF, Ag Br, (NaCl structure) +2 4 Planar [Ag(py)4]2+ +3 4 Planar [AgF4]- Octahedral 6 [Ag(IO6)2]7-, [AgF6] 2.6 SUMMARY In this unit, an effort has been made to discuss the general characteristics of the elements of the second transition series such as their electronic configuration and variation in the oxidation states, magnetic behaviour, complex formation tendency, colour of the compounds/complexes, catalytic activity, formation of interstitial and non-stoichiometric compounds, metallic character and alloy formation along with the UTTARAKHAND OPEN UNIVERSITY Page 44 INORGANIC CHEMISTRY-II BSCCH-201 periodic properties and their variation across the period. A comparative account of these elements with their 3d analogues in respect to their ionic radii, oxidation states and magnatic behaviour has also been given. A brief discussion of spectral properties and a tabular account of the stereochemistry of the compounds of the elements of this series have also been recorded. It is hoped that this will enable the learners to understand the subject matter in a better and easier way. 2.7 TERMINAL QUESTIONS 1. What are the transition elements? Why are they called so? 2. Mention three main factors that enable transition elements to form complexes. 3. Write down the names and symbols of 4d and 5d congeners of element manganese. 4. Which ion is more stable Ag+ or Ag2+ and why? 5. Write down the valence shell electronic configuration of Pd (Z = 46). 6. Write down two applications of Pd as catalyst. 2.8 ANSWERS 3. Technetium (Tc) and rhenium (Re) 4. Ag+ ion due to 4d10 configuration 5. 4d10 5s0 For Ans. 1, 2 & 6 please refer to the text. UTTARAKHAND OPEN UNIVERSITY Page 45 INORGANIC CHEMISTRY-II BSCCH-201 UNIT-3 CHEMISTRY OF THE ELEMENTS OF THIRD TRANSITION (5d) SERIES CONTENTS: 3.1 Objectives 3.2 Introduction 3.3 General characteristics 3.4 Comparative study with their 3d analogues 3.5 Ionic radii, oxidation states, magnetic behavior 3.6 Spectral properties and stereochemistry 3.7 Summary 3.8 Terminal Questions 3.9 Answers 3.1 OBJECTIVES Objectives this unit are to make the learners understand the general characteristics of the elements of the third transition (5d) series such as their electronic configuration, variable oxidation states, complex formation tendency, magnetic properties, formation of coloured ions / compounds, catalytic activity, formation of interstitial and non-stochiometric compounds, metallic character and alloy formation, their periodic properties such as atomic and ionic radii, melting and boding points, ionisation energies and reactivity, standard electrode potential and reducing property along with their variation in the series. The comparative study of ionic radii, oxidation states and magnetic behaviour of these elements with those of the 3d and 4d analogues will also to be given so that the learners may understand the similarities and differences between the elements of the three series. The learners will also be acquainted to the spectral properties and stereochemistries of the compounds of these elements to make them familiar with these aspects. 3.2 INTRODUCTION The third transition series also contains ten elements and starts at lanthanum (La, Z = 57), the element of Group 3, with 5d16s2 valence shell configuration. The UTTARAKHAND OPEN UNIVERSITY Page 46 INORGANIC CHEMISTRY-II BSCCH-201 next element of this series is hafnium (Hf, Z = 72), the element of Group 4, with 5d26s2 configuration in the valence shell. In between these two d-block elements, there occurs a series of 14 elements (from Z = 58 to 71) which are called lanthanides because they succeed La and are closely related with it. These fourteen elements are also known as elements of 4f series. Thus 5d series element La precedes and Hf succeeds the lanthanides. After Hf the filling of 5d subshell continues in tantalum (Ta, Z = 73), tungsten (W, Z = 74), rhenium (Re, Z = 75), osmium (Os, Z = 76), iridium (Ir, Z = 77), platinum (Pt, Z = 78), gold (Au, Z =79) and mercury (Hg, Z=80), the element of Group 12, with 5d106s2 valence shell configuration. All the elements of this series have 2 electrons in 6s subshell and 5d subshell is being progressively filled with 1 to 10 electrons, except Au which has one electron (6s1) due to the shifting of one s-electron to (n-1)d subshell to completely fill it (exchange energy effect). Because the last or the differentiating electron in the atoms of these elements enters the 5d subshell, the third transition series of elements is also known as 5d transition series. These elements are much more important than those of the second transition series. This series of elements lies between barium (Ba, Z = 56), the elements of Group 2, and thallium (Tl, Z = 81), the element of Group 13 so the gradual transition of the properties occurs in the period. These elements also exhibit all the characteristic properties of the d-block elements as happens for those of first transition and second transition series. 3.3 GENERAL CHARACTERISTICS OF THIRD TRANSITION (5-d) SERIES ELEMENTS The general characteristics of these elements are as follows: 3.3.1 Electronic Configuration and Variable Oxidation States The elements of this series show a regular trend in the electronic configuration of the valence shell like those of first transition series. The general valence shell electronic configuration of these elements is 5d1-106s1,2. The last two elements, viz, gold and mercury have completely filled 5d-subshell (i.e.5d10) whereas all other elements have 1 to 8 electrons, i.e., 5d1-8 in the d-subshell of penultimate shell. As has been given in the introduction, only Au has 6s1 configuration and all UTTARAKHAND OPEN UNIVERSITY Page 47 INORGANIC CHEMISTRY-II BSCCH-201 other elements have 6s2 configuration in the last shell, In Au exchange energy effect plays an important role to cause the sifting of one 6s-electron to 5d-subshell so that it has stable 5d10 configuration (i.e. 5d10 6s1 valence shell configuration) as was the case with copper (3d series) and silver (4d series). Like the elements of first and second transition series, the elements of this series also exist in various oxidation states in their compounds, i.e., the variation of the oxidation states is equally pronounced in the elements of all the three series (i.e., 3d, 4d- and 5d-). This is due to the availability of several electrons in 5d a

BSCCH-201 Inorganic Chemistry II PDF 2021

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