Chapter 11 Modern Atomic Theory Rutherford’s Atom • The concept of a nuclear atom (charged electrons moving around the nucleus) resulted from Ernest Rutherford’s experiments. • Question left unanswered: how are electrons arranged and how do they move? Copyright © Houghton Mifflin Company. All rights reserved. 11 | 2 Rutherford’s Atom (cont.) Copyright © Houghton Mifflin Company. All rights reserved. 11 | 3 Electromagnetic Radiation • Electromagnetic radiation is given off by atoms when they have been excited by any form of energy, as shown in flame tests. • Flame tests: Sample: Color: LiCl SrCl2 NaCl KCl CaCl2 Copyright © Houghton Mifflin Company. All rights reserved. 11 | 4 Electromagnetic Waves • Velocity = c = speed of light – 2.997925 x 108 m/s – All types of light energy travel at the same speed. • Amplitude = A = measure of the intensity of the wave, i.e.“brightness” Copyright © Houghton Mifflin Company. All rights reserved. 11 | 5 Electromagnetic Waves (cont.) • Wavelength = = distance between two consecutive peaks or troughs in a wave – Generally measured in nanometers (1 nm = 10-9 m) – Same distance for troughs • Frequency = = the number of waves that pass a point in space in one second – Generally measured in Hertz (Hz), – 1 Hz = 1 wave/sec = 1 sec-1 • c=x Copyright © Houghton Mifflin Company. All rights reserved. 11 | 6 Types of Electromagnetic Radiation Copyright © Houghton Mifflin Company. All rights reserved. 11 | 7 Planck’s Discovery • Showed that for certain applications light energy could be thought of as particles or photons Copyright © Houghton Mifflin Company. All rights reserved. 11 | 8 Emission of Energy by Atoms/Atomic Spectra • Atoms that have gained extra energy release that energy in the form of light. Copyright © Houghton Mifflin Company. All rights reserved. 11 | 9 Atomic Spectra • Line spectrum: very specific wavelengths of light that atoms give off or gain • Each element has its own line spectrum, which can be used to identify that element. • This is the basis of atomic absorption spectroscopy. Copyright © Houghton Mifflin Company. All rights reserved. 11 | 10 Atomic Spectra (cont.) • Hydrogen atoms have several excited state energy levels. • Different colors are produced when the excited atoms return to the ground state. • The line spectrum of hydrogen must be related to energy changes in the atom. Copyright © Houghton Mifflin Company. All rights reserved. 11 | 11 Atomic Spectra (cont.) • The atom is quantized, i.e. only certain energies are allowed. Continuous levels Copyright © Houghton Mifflin Company. All rights reserved. Quantized levels 11 | 12 Bohr’s Model (Niel’s Bohr 1885-1911) • Energy of the atom is quantized – An atom can only have certain specific energy states called quantum levels or energy levels. – When an atom gains energy, an electron “moves” to a higher quantum level. – When an atom loses energy, the electron “moves” to a lower quantum level. – Lines in a spectrum correspond to the difference in energy between the levels. Copyright © Houghton Mifflin Company. All rights reserved. 11 | 13 Bohr’s Model (cont.) • Ground state: minimum energy of an atom • The ground state of hydrogen corresponds to having its one electron in the n=1 level • Excited states: energy levels higher than the ground state Copyright © Houghton Mifflin Company. All rights reserved. 11 | 14 Bohr’s Model (cont.) • Distances between energy levels decrease as the energy increases – 1st energy level can hold 2 electrons, the 2nd level 8 electrons, the 3rd 18 electrons, etc. Copyright © Houghton Mifflin Company. All rights reserved. 11 | 15 Problems with the Bohr Model • Only explains hydrogen atom spectrum (and other 1-electron systems). • Neglects interactions between electrons. • Assumes circular or elliptical orbits for electrons (which is not true). Copyright © Houghton Mifflin Company. All rights reserved. 11 | 16 Wave Mechanical Model of the Atom • Experiments later showed that electrons could be treated as waves: Louis De Broglie • The quantum mechanical model treats electrons as waves and uses wave mathematics to calculate probability densities of finding the electron in a particular region in the atom. – Schrödinger Wave Equation Copyright © Houghton Mifflin Company. All rights reserved. 11 | 17 Orbitals and Energy Levels • Solutions to the wave equation give regions in space of high probability for finding the electron. These are called orbitals. • Each principal energy level contains one or more sublevels. Sublevels are made up of orbitals. Copyright © Houghton Mifflin Company. All rights reserved. 11 | 18 Orbitals and Energy Levels (cont.) Copyright © Houghton Mifflin Company. All rights reserved. 11 | 19 Atomic Sublevels & Orbitals • Each type of sublevel has a different shape each and energy. s orbital shape: p orbital shapes: • Each sublevel contains one or more orbitals. Copyright © Houghton Mifflin Company. All rights reserved. 11 | 20 Atomic Sublevels & Orbitals (cont.) Copyright © Houghton Mifflin Company. All rights reserved. 11 | 21 Pauli Exclusion Principle • No orbital may have more than 2 electrons. • Electrons in the same orbital must have opposite spins. • s sublevel holds 2 electrons (1 orbital) • p sublevel holds 6 electrons (3 orbitals) • d sublevel holds 10 electrons (5 orbitals) • f sublevel holds 14 electrons (7 orbitals) Copyright © Houghton Mifflin Company. All rights reserved. 11 | 22 Sublevels and Orbitals n 1 2 3 4 Sublevels : Types of Orbitals (and numbers) 1s(1) 2s(1) 3s(1) 4s(1) 2p(3) 3p(3) 4p(3) 3d(5) 4d(5) 4f(7) For a multiple-electron atom, build-up the energy levels, filling each orbital in succession from lowest to highest. Degenerate orbitals: orbitals with the same energy e.g. Each p sublevel has 3 degenerate p orbitals Copyright © Houghton Mifflin Company. All rights reserved. 11 | 23 Orbital Filling 1s 2s 3s 4s 5s 6s 7s 2p 3p 4p 5p 6p 7p 3d 4d 5d 6d 4f 5f Therefore, the order of filling is: Copyright © Houghton Mifflin Company. All rights reserved. 11 | 24 Electron Configurations • For a set of degenerate orbitals, fill each orbital half-way first before pairing the electrons. • Electron configurations show how many electrons are in each sublevel of an atom – describes where the electrons are. - The electron configuration for a ground state Li atom is: - The electron configuration for a ground state N atom is: Copyright © Houghton Mifflin Company. All rights reserved. 11 | 25 Electron Configurations (cont) What is the electron configuation of: A. potassium B. cobalt Copyright © Houghton Mifflin Company. All rights reserved. 11 | 26 Electron Configurations (cont.) • Valence shell: highest energy level – Electrons in the valence shell are called valence electrons. – Core electrons: electrons not in the valence shell – Often use symbol of previous noble gas in brackets to represent core electrons: phosphorus: 1s22s22p6 3s23p3 = core valence Copyright © Houghton Mifflin Company. All rights reserved. 11 | 27 Electron Configuration and the Periodic Table • Elements in the same column on the periodic table have: – Similar chemical and physical properties – Similar valence shell electron configurations • same numbers of valence electrons • same orbital types, but different energy levels Be: Mg: Copyright © Houghton Mifflin Company. All rights reserved. 11 | 28 s1 1 2 3 4 5 6 7 p1 p2 p3 p4 p5 s2 p6 d1 d2 d3 d4 d5 d6 d7 d8 d9 d10 f1 f2 f3 f4 f5 f6 f7 f8 f9 f10 f11 f12 f13 f14 Copyright © Houghton Mifflin Company. All rights reserved. 11 | 29 Copyright © Houghton Mifflin Company. All rights reserved. 11 | 30 Orbital diagrams Orbital diagrams (or box diagrams) show orbitals as boxes grouped by sublevels with arrows representing the electrons. Sulfur has an electron configuration of : The orbital diagram for sulfur is: Copyright © Houghton Mifflin Company. All rights reserved. 11 | 31 Atomic Properties and the Periodic Table Copyright © Houghton Mifflin Company. All rights reserved. 11 | 32 Metallic Character: Metals • Metals – Malleable & ductile – Shiny, lustrous – Conduct heat and electricity – Form cations in solution – Lose electrons in reactions - oxidized Copyright © Houghton Mifflin Company. All rights reserved. 11 | 33 Metallic Character: Metalloids • Metalloids -Also known as semi-metals -Show some metal and some nonmetal properties Copyright © Houghton Mifflin Company. All rights reserved. 11 | 34 Metallic Character: Nonmetals • Nonmetals -Brittle in solid state -Form anions and polyatomic anions -Gain electrons in reactions - reduced Copyright © Houghton Mifflin Company. All rights reserved. 11 | 35 Metallic Character (cont.) • The ease of losing an electron varies as follows: Cs > Rb > K > Na > Li • The same trend is seen in the Group 2 metals: Copyright © Houghton Mifflin Company. All rights reserved. 11 | 36 Trend in Ionization Energy • Minimum energy needed to remove a valence electron from an atom in the gas phase: M(g) → M+(g) + 1e• The lower the ionization energy, the easier it is to remove the electron. – Metals in general have low ionization energies and nonmetals relatively high ones. • Ionization energy decreases down the group. – Valence electron is farther from the nucleus • Ionization energy increases left to right across the period. Copyright © Houghton Mifflin Company. All rights reserved. 11 | 37 Trend in Atomic Size Copyright © Houghton Mifflin Company. All rights reserved. 11 | 38