Electronic Structure and the Periodic Table Learning Outcomes

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1 Electronic Structure and the Periodic Table Learning Outcomes (a) Electronic structure (i) Electromagnetic spectrum and associated calculations Electromagnetic radiation may be described in terms of waves. Electromagnetic radiation can be specified by its wavelength () and by its frequency (). The electromagnetic spectrum is the range of frequencies or wavelengths of electromagnetic radiation. The unit of measurement of wavelength is the metre or an appropriate submultiple. The unit of measurement of frequency is the reciprocal of time in seconds (s -1 ) and is called the Hertz (Hz). The velocity of electromagnetic radiation is constant and has a value of approximately 3 x 10 8 ms -1. Velocity, frequency and wavelength are related in the expression: c = Under certain circumstances electromagnetic radiation may be regarded as a stream of particles, rather than as waves. These particles are known as photons. The energy (E) of radiation, and the energy associated with photons, is related to frequency by Planck s constant (h) in the expressions: E = h for one photon E = Lh for one mole of photons where L represents Avogadro s Constant. (ii) Electronic configuration and the Periodic Table The emission spectrum of hydrogen provides evidence of energy levels. Quantum theory states that matter can only emit or absorb energy in small fixed amounts (called quanta). The energy of a bound electron in an atom is quantised. An atom can be considered as emitting a photon of light energy when an electron moves from a higher energy level to a lower energy level. Each line of the emission spectrum represents radiation of a specific wavelength or frequency from which the difference in energy between the levels can be calculated. Emission spectra of elements with more than one electron provide sublevels within each principal energy level above the first. The principal energy levels correspond to the principal shells. The second and subsequent principal shells contain sub-shells which correspond to the sublevels. Sub-shells can be labelled s, p, d and f. 1

2 The types of sub-shells within each principal shell are as follows: First shell s subshell Second shell s and p subshells Third shell s, p and d subshells Fourth and subsequent shells s, p, d and f subshells Heisenberg s uncertainty principle states that it is impossible to define with absolute precision, simultaneously, both the position and the momentum of an electron. Electrons, like photons, display the properties of particles and waves. Treating bound electrons in atoms as waves leads to regions of high probability of finding the electrons. These regions are called atomic orbitals. There are four types of orbitals, namely s, p, d and f, each with a characteristic shape or set of shapes. Diagrams of the shapes of s and p orbitals can be drawn and recognised. Diagrams of d orbitals can be recognised. An orbital holds a maximum of two electrons, as required by the Pauli exclusion principle. The number of orbitals in each subshell is as follows : s subshell one s orbital p subshell three p orbitals d subshell five d orbitals f subshell seven f orbitals In an isolated atom the orbitals within each subshell are degenerate. The aufbau principle states that orbitals are filled in order of increasing energy. The relative energies corresponding to each orbital can be represented diagrammatically for the first four shells of a multi-electron atom. Hund s Rule states that when degenerate orbitals are available, electrons fill each singly, keeping their spins parallel before spin pairing starts. Electronic configurations using spectroscopic notation and orbital box notation can be written for elements of atomic numbers 1 to 36. The Periodic Table can be subdivided into four blocks (s, p, d and f) corresponding to the outer electronic configurations of the elements within these blocks. The variation in first ionisation energy with increasing atomic number for the first 36 elements can be explained in terms of the relative stability of different electron configurations, and so provides evidence for these electronic configurations. The relative values of first, second and subsequent ionisation energies can be explained in terms of the stabilities of the electronic configurations from which the electrons are being removed. 2

3 (iii) Spectroscopy Atomic emission spectroscopy and atomic absorption spectroscopy involve transitions between electronic energy levels in atoms. Generally, the energy differences correspond to the visible region of the electromagnetic spectrum, ie, to the approximate wavelength range of nm. Some applications use the ultra-violet region (wavelength range approximately nm). In emission spectroscopy the sample is energised by heat or electricity causing electrons to be promoted to higher energy levels. The wavelength of the radiation emitted as electrons fall back to lower energy levels is measured. In absorption spectroscopy electromagnetic radiation is directed at the sample. Radiation is absorbed as electrons are promoted to higher energy levels. The wavelength of the absorbed radiation is measured. Each element provides a characteristic spectrum which can be used to identify an element. The amount of species can be determined quantitatively if the intensity of emitted or transmitted radiation is measured. (b) Chemical Bonding (i) Covalent Bonding Non-polar covalent bonding and ionic bonding can be considered as being at opposite ends of a bonding continuum with polar covalent bonding lying between these two extremes. Different electron models can be used to explain the experimental evidence associated with covalent bonding. Lewis electron dot diagrams represent bonding and non-bonding electron pairs in molecules and in polyatomic ions. A dative covalent bond is one in which one atom of the bond provides both electrons of the bonding pair. Species such as ozone, sulphur dioxide and the carbonate ion can be equivalent electron dot diagrams known as resonance structures. (ii) Shapes of molecules and polyatomic ions The shapes of molecules or polyatomic ions can be predicted from the number of bonding electron pairs and the number of non-bonding electron pairs. The arrangement of electron pairs is linear, trigonal, tetrahedral, trigonal bipyramidal and octahedral when the total number of electron pairs is 2, 3, 4, 5 and 6, respectively. Electron pair repulsions decrease in strength in the order: non-bonding pair/non-bonding pair > non-bonding pair/bonding pair > bonding pair/bonding pair. These different strengths of electron pair repulsion account for slight deviations from expected bond angles in molecules such as NH 3 and H 2 O. 3

4 (iii) Ionic lattices, superconductors and semiconductors Ionic lattice structures: The geometry of the crystalline structure adopted by an ionic compound depends on the relative sizes of the ions. This affects the number of ions which can pack round an ion of opposite charge. Examples of crystal lattice structures are: sodium chloride caesium chloride Superconductors: Superconductors are a special class of materials that have zero electrical resistance at temperatures near absolute zero. Achieving temperatures near absolute zero is difficult and superconduction at these temperatures is impractical. Recently superconductors have been discovered which have zero resistance up to temperatures above the boiling point of liquid nitrogen - temperatures which are less costly to attain. Superconductors may have future applications in power transmission and electrically powered forms of transport. Semiconductors: A covalent element such as silicon or germanium which has a higher conductivity than that of a typical non-metal but a much lower conductivity than that of a metal is described as a semiconductor. Semiconductors are also referred to as metalloids and occur at the division between metals and non-metals in the Periodic Table. The electrical conductivity of semiconductors increases with increasing temperature. The electrical conductivity of semiconductors increases on exposure to light. This is known as the photovoltaic effect. Elements such as silicon and germanium have similar structures to diamond but the covalent bonds are weaker. Thermal agitation of the lattice can result in some of the bonding electrons breaking free, leaving positive sites called holes. When a voltage is applied to these elements, electrons and holes can migrate through the lattice. Doping pure crystals of silicon or germanium with certain other elements produces ntype and p-type semiconductors. The type of semiconduction depends on the specific dopant used. In n-type and p-type semiconductors the main current carriers are surplus electrons and positive holes respectively. Crystals of silicon or germanium can be prepared with bands of n-type or p- type semiconductors. The p-n junction which occurs between a layer of n-type 4

5 and a layer of p-type semiconductor has specific electrical properties which form the basis of the electronics industry. Solar cells use the photovoltaic effect to convert sunlight into electricity. (c) Some Chemistry of the Periodic Table (i) The second and third short periods: oxides, chlorides and hydrides Melting points, boiling points and electrical conductivities of the oxides, chlorides and hydrides of the elements of the second and third periods can be explained in terms of their structure and type of bonding. Metal oxides tend to be basic and non-metal oxides tend to be acidic but amphoteric oxides exhibit both acidic and basic properties. Most ionic chlorides dissolve in water without reaction but some covalent chlorides are hydrolysed, producing fumes of hydrogen chloride. Ionic hydrides possess the hydride ion which acts as a reducing agent. On reaction with water ionic hydrides produce hydrogen gas and the hydroxide ion. Electrolysis of molten ionic hydrides produces hydrogen gas at the positive electrode. (ii) Electronic configuration and oxidising states of transition metals Electronic configuration: The d block transition metals are metals with an incomplete d subshell in at least one of their ions. The filling of the d orbitals follows the aufbau principle, with the exception of chromium and copper atoms. These exceptions are due to a special stability associated with all the d orbitals being half filled or completely filled. When transition metals form ions it is the s electrons which are lost first rather than the d electrons. Oxidation states: An element is said to be in a particular oxidation state when it has a specific oxidation number. The oxidation number is determined by following certain rules. Transition metals exhibit variable oxidation states of differing stability. Compounds of the same transition metal but in different oxidation states may have different colours. Oxidation can be considered as an increase in oxidation number and reduction can be considered as a decrease in oxidation number. Compounds containing metals in high oxidation states tend to be oxidising agents whereas compounds with metals in low oxidation states are often reducing agents. 5

6 (iii) Transition metal complexes A complex consists of a central metal ion surrounded by ligands. Ligands are electron donors and may be negative ions or molecules with nonbonding pairs of electrons. Ligands can be classified as monodentate, bidentate, etc. The number of bonds from the ligand to the central metal ion is known as the coordination number of the central ion. Complexes are written and named according to IUPAC rules. In a complex of a transition metal the d orbitals are no longer degenerate. The energy difference between subsets of d orbitals depends on the position of the ligand in the spectrochemical series. Colours of many transition metal complexes can be explained in terms of d-d transitions. UV and visible spectroscopy: Catalysis: The effects of d-d transitions can be studied using ultra-violet and visible absorption spectroscopy. Ultra-violet and visible absorption spectroscopy involve transitions between electronic energy levels in atoms and molecules where the energy difference corresponds to the ultra-violet and visible regions of the electromagnetic spectrum. The wavelength ranges are approximately nm for ultra-violet and nm for visible. An ultra-violet/visible spectrometer measures the intensity of radiation transmitted through the sample and compares this with the intensity of incident radiation. Transition metals or their compounds act as catalysts in many chemical reactions. It is believed that the presence of unpaired d electrons or unfilled d orbitals allows intermediate complexes to form, providing reaction pathways of lower energy compared to the uncatalysed reaction. The variability of oxidation states of transition metals is also an important factor. 6

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