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10/31/2016 CHAPTER 3 Atomic Structure: Explaining the Properties of Elements We are going to learn about the electronic structure of the atom, and will be able to explain many things, including atomic orbitals, oxidation numbers, and periodic trends. 1 10/31/2016 Chapter Outline 3.1 Waves of Light 3.2 Atomic Spectra 3.3 Particles of Light: Quantum Theory 3.4 The Hydrogen Spectrum and the Bohr Model 3.5 Electrons as Waves 3.6 Quantum Numbers 3.7 The Sizes and Shapes of Atomic Orbitals 3.8 The Periodic Table and Filling Orbitals 3.9 Electron Configurations of Ions 3.10 The Sizes of Atoms and Ions 3.11 Ionization Energies 3.12 Electron Affinities 3 The Electromagnetic Spectrum Continuous range of radiant energy, (also called electromagnetic radiation). 2 10/31/2016 Electromagnetic Radiation Mutually propagating electric and magnetic fields, at right angles to each other, traveling at the speed of light c a) Electric b) Magnetic Speed of light (c) in vacuum = 2.998 x 108 m/s Properties of Waves - in the examples below, both waves are traveling at the same velocity Long wavelength = low frequency Short wavelength = high frequency 3 10/31/2016 · u = wavelength, = frequency, u = velocity Units: wavelength = meters (m) frequency = cycles per second or Hertz (s-1) wavelength (m) x frequency (s-1) = velocity (m/s) Example: A FM radio station in Portland has a carrier wave frequency of 105.1 MHz. What is the wavelength? 4 10/31/2016 Chapter Outline 3.1 Waves of Light 3.2 Atomic Spectra 3.3 Particles of Light: Quantum Theory 3.4 The Hydrogen Spectrum and the Bohr Model 3.5 Electrons as Waves 3.6 Quantum Numbers 3.7 The Sizes and Shapes of Atomic Orbitals 3.8 The Periodic Table and Filling Orbitals 3.9 Electron Configurations of Ions 3.10 The Sizes of Atoms and Ions 3.11 Ionization Energies 3.12 Electron Affinities 9 Atomic Spectra a) Absorption: Fraunhofer lines (dark spectra) b) Emission: e.g Na (bright line spectra) 10 5 10/31/2016 Atomic Absorption Spectra: Dark Lines Spectrometer - a device that separates out the different wavelengths of light. A “white” light sources produces a “continuous” spectrum; atomic sources produces a "discrete" spectrum. a) Hydrogen b) Helium c) Neon 11 Atomic Emission (Line) Spectra 6 10/31/2016 Chemistry in Action: Element from the Sun In 1868, Pierre Janssen detected a new emission line in the solar emission spectrum that did not match known emission lines The mystery element was named -- Chapter Outline 3.1 Waves of Light 3.2 Atomic Spectra 3.3 Particles of Light: Quantum Theory 3.4 The Hydrogen Spectrum and the Bohr Model 3.5 Electrons as Waves 3.6 Quantum Numbers 3.7 The Sizes and Shapes of Atomic Orbitals 3.8 The Periodic Table and Filling Orbitals 3.9 Electron Configurations of Ions 3.10 The Sizes of Atoms and Ions 3.11 Ionization Energies 3.12 Electron Affinities 1 4 7 10/31/2016 Blackbody Radiation 15 Photoelectric Effect • phenomenon of light striking a metal surface and producing an electric current (flow of electrons). • If radiation below threshold energy, no electrons released. 16 8 10/31/2016 Blackbody Radiation and the Photoelectric Effect Explained by a new theory: Quantum Theory • Radiant energy is “quantized” – Having values restricted to whole-number multiples of a specific base value. • Quantum = smallest discrete quantity of energy. • Photon = a quantum of electromagnetic radiation 17 Quantized States Quantized states: discrete energy levels. Continuum states: smooth transition between levels. 9 10/31/2016 The energy of the photon is given by Planck’s Equation. E = h h = 6.626 × 10−34 J∙s (Planck’s constant) Sample Exercise 7.2 What is the energy of a photon of red light that has a wavelength of 656 nm? The value of Planck’s constant (h) is 6.626 × 10-34 J . s, and the speed of light is 3.00 × 108 m/s. 10 10/31/2016 Chapter Outline 3.1 Waves of Light 3.2 Atomic Spectra 3.3 Particles of Light: Quantum Theory 3.4 The Hydrogen Spectrum and the Bohr Model 3.5 Electrons as Waves 3.6 Quantum Numbers 3.7 The Sizes and Shapes of Atomic Orbitals 3.8 The Periodic Table and Filling Orbitals 3.9 Electron Configurations of Ions 3.10 The Sizes of Atoms and Ions 3.11 Ionization Energies 3.12 Electron Affinities 2 1 11 10/31/2016 The Hydrogen Spectrum and the Rydberg Equation 1 1 1 = 1.097 10 2 nm 1 2 2 n λ i nf Exercise 7.4: using the Rydberg Equation What is the wavelength of the line in the emission spectrum of Hydrogen corresponding from ni = 7 to nf = 2? 1 1 1 = 1.097 102 nm1 2 2 n n λ f i 12 10/31/2016 Using the Rydberg Equation for Absorption What is the wavelength of the line in the absorption spectrum of Hydrogen corresponding from ni = 2 to nf = 4? 1 1 1 = 1.097 102 nm1 2 2 n n λ f i The Bohr Model of Hydrogen Neils Bohr used Planck and Einstein’s ideas of photons and quantization of energy to explain the atomic spectra of hydrogen photon of light (h) n=4 n=3 n=2 + h h n=1 n=2 n=3 n=1 absorption emission 13 10/31/2016 Electronic States • Energy Level: • An allowed state that an electron can occupy in an atom. • Ground State: • Lowest energy level available to an electron in an atom. • Excited State: • Any energy state above the ground state. “Solar system” model of the atom where each “orbit” has a fixed, QUANTIZED energy given by - E orbit 2.178 x 10-18 Joules n2 where n = “principle quantum number” = 1, 2, 3…. This energy is exothermic because it is potential energy lost by an unbound electron as it is attracted towards the positive charge of the nucleus. 14 10/31/2016 E = h E = h The Rydberg Equation can be derived from Bohr’s theory Ephoton = DE = Ef - Ei 15 10/31/2016 Example DE Calculation Calculate the energy of a photon absorbed when an electron is promoted from ni = 2 to nf = 5. Sample Exercise 3.5 How much energy is required to ionize a ground-state hydrogen atom? Put another way, what is the ionization energy of hydrogen? 16 10/31/2016 Strengths and Weaknesses of the Bohr Model • Strengths: • Accurately predicts energy needed to remove an electron from an atom (ionization). • Allowed scientists to begin using quantum theory to explain matter at atomic level. • Limitations: • Applies only to one-electron atoms/ions; does not account for spectra of multielectron atoms. • Movement of electrons in atoms is less clearly defined than Bohr allowed. Chapter Outline 3.1 Waves of Light 3.2 Atomic Spectra 3.3 Particles of Light: Quantum Theory 3.4 The Hydrogen Spectrum and the Bohr Model 3.5 Electrons as Waves 3.6 Quantum Numbers 3.7 The Sizes and Shapes of Atomic Orbitals 3.8 The Periodic Table and Filling Orbitals 3.9 Electron Configurations of Ions 3.10 The Sizes of Atoms and Ions 3.11 Ionization Energies 3.12 Electron Affinities 34 17 10/31/2016 Light behaves both as a wave and a particle Classical physics - light as a wave: c = = 2.998 x 108 m/s Quantum Physics Planck and Einstein: photons (particles) of light, E = h Several blind men were asked to describe an elephant. Each tried to determine what the elephant was like by touching it. The first blind man said the elephant was like a tree trunk; he had felt the elephant's massive leg. The second blind man disagreed, saying that the elephant was like a rope, having grasped the elephant's tail. The third blind man had felt the elephant's ear, and likened the elephant to a palm leaf, while the fourth, holding the beast's trunk, contended that the elephant was more like a snake. Of course each blind man was giving a good description of that one aspect of the elephant that he was observing, but none was entirely correct. In much the same way, we use the wave and particle analogies to describe different manifestations of the phenomenon that we call radiant energy, because as yet we have no single qualitative analogy that will explain all of our observations. http://www.wordinfo.info/words/images/blindmen-elephant.gif 18 10/31/2016 Standing Waves 37 Not only does light behave like a particle sometimes, but particles like the electron behave like waves! WAVE-PARTICLE DUALITY Combined these two equations: E = mc2 and E = h, therefore - 19 10/31/2016 The DeBroglie wavelength explains why only certain orbits are "allowed" - a) stable b) not stable Sample Exercise 3.6 (Modified): calculating the wavelength of a particle in motion. (a)Calculate the deBroglie wavelength of a 142 g baseball thrown at 44 m/s (98 mi/hr) (b)Compare to the wavelength of a hydrogen atom (9.11 x 10-31 kg) 20 10/31/2016 Using the wavelike properties of the electron. Close-up of a milkweed bug Atomic arrangement of a Bi-SrCa-Cu-O superconductor 21 10/31/2016 Chapter Outline 3.1 Waves of Light 3.2 Atomic Spectra 3.3 Particles of Light: Quantum Theory 3.4 The Hydrogen Spectrum and the Bohr Model 3.5 Electrons as Waves 3.6 Quantum Numbers NOTE: will do Section 3.7 first 3.7 The Sizes and Shapes of Atomic Orbitals 3.8 The Periodic Table and Filling Orbitals 3.9 Electron Configurations of Ions 3.10 The Sizes of Atoms and Ions 3.11 Ionization Energies 3.12 Electron Affinities 43 E. Schrödinger (1927) The electron as a Standing Wave mathematical treatment results in a “wave function”, = the complete description of electron position and energy electrons are found within 3-D “shells”, not 2-D Bohr orbits shells contain atomic “orbitals” (s, p, d, f) 22 10/31/2016 E. Schrödinger (1927) The electron as a Standing Wave Each orbital can hold up to 2 electrons The probability of finding the electron = 2 Probabilities are required because of “Heisenberg’s Uncertainty Principle” We can never SIMULTANEOUSLY know with absolute precision both the exact position (x), and momentum (p = mass·velocity or mv), of the electron. Dx·D(mv) h/4 Uncertainty in Uncertainty in position momentum If one uncertainty gets very small, then the other becomes corresponding larger. If we try to pinpoint the electron momentum, it's position becomes "fuzzy". So we assign a probability to where the electron is found = atomic orbital. 23 10/31/2016 If an electron is moving at 1.0 X 108 m/s with an uncertainty in velocity of 0.10 %, then what is the uncertainty in position? Dx•D(mv) h/4 and rearranging Dx h/[4D(mv)] or since the mass is constant Dx h/[4mDv] Dx (6.63 x 10-34 Js) 4(9.11 x 10-31 kg)(.001 x 1 x 108 m/s) Dx 6 x 10-10 m or 600 pm Probability Electron Density for 1s Orbital 48 24 10/31/2016 Electron “Cloud” Representation Electron “Orbital” Representation 90% probablity surface 25 10/31/2016 Comparison of “s” Orbitals One “s” orbital in each shell. nodes 26 10/31/2016 The Three 2p Orbitals 53 The Five 3d Orbitals 54 27 10/31/2016 The Seven “f” Orbitals 3s + 2s n=1 n=2 n=3 1s Orbitals are found in 3-D shells instead of 2-D Bohr orbits. The Bohr radius for n=1, 2, 3 etc was correct, however. 28 10/31/2016 Do not appear until the 2nd shell and higher 3px 3py 3pz + n=1 n=2 n=3 2px 2py 2pz Do not appear until the 3rd shell and higher + n=1 n=2 n=3 29 10/31/2016 “The Shell Game” (n = 1) + n=1 n=2 n=3 In the first shell there is only an s "subshell" “The Shell Game” n=2 + In the second shell there is an s "subshell" and a p "subshell" n=1 n=2 n=3 30 10/31/2016 “The Shell Game” n=3 + n=1 n=2 n=3 In the third shell there are s, p, and d "subshells" “The Shell Game” n=4 “f” Orbitals don’t appear until the 4th shell 31 10/31/2016 Chapter Outline 3.1 Waves of Light 3.2 Atomic Spectra 3.3 Particles of Light: Quantum Theory 3.4 The Hydrogen Spectrum and the Bohr Model 3.5 Electrons as Waves 3.6 Quantum Numbers 3.7 The Sizes and Shapes of Atomic Orbitals 3.8 The Periodic Table and Filling Orbitals 3.9 Electron Configurations of Ions 3.10 The Sizes of Atoms and Ions 3.11 Ionization Energies 3.12 Electron Affinities 63 Completely describe the position and energy of the electron (part of the wave function ) 1. Principle quantum number (n): n = 1, 2, 3…… gives principle energy level or "shell" En constants n2 (just like Bohr's theory) http://www.calstatela.edu/faculty/acolvil/mineral/atom_structure2.jpg 32 10/31/2016 2. angular momentum quantum number (l) : l = 0, 1, 2, 3……n-1 describes the type of orbital or shape l=0 l=1 l=2 l=3 s-orbital p-orbital d-orbital f-orbital Equal to the number of "angular nodes" 3. magnetic quantum number (ml): ml = - l to + l in steps of 1 (including 0) indicates spatial orientation If l = 0, then ml = 0 (only one kind of s-orbital) ifl= 1, then ml = -1, 0, +1 (three kinds of p-orbitals) if l = 2, then ml = -2, -1, 0, +1, +2 (five kinds of d-orbitals) if l = 3, then ml = -3, -2, -1, 0, +1, +2, +3 (seven kinds of f-orbitals) 33 10/31/2016 Electron Spin • Not all spectra features explained by wave equations: – Appearance of “doublets” in atoms with a single electron in outermost shell. • Electron Spin – Up / down. 67 4. spin quantum number (ms): ms = 1/2 or -1/2 Electrons “spin” on their axis, producing a magnetic field ms = +1/2 spin “up” ms = -1/2 spin “down” 34 10/31/2016 orbital = s p d f l=0 1 2 3 ml = 0 n=1 2 3 4 5 6 -1 0 +1 -2 -1 0 +1 +2 -3 -2 -1 0 +1 +2 +3 max electrons/subshell = 2(2l + 1) max electrons/shell = 2n2 35 10/31/2016 Sample Exercise 3.9: Identifying Valid Sets of Quantum Numbers Which of these five combinations of quantum numbers are valid? n l ml ms (a) 1 0 -1 +1/2 (b) 3 2 -2 +1/2 (c) 2 2 0 0 (d) 2 0 0 -1/2 (e) -3 -2 -1 -1/2 Chapter Outline 3.1 Waves of Light 3.2 Atomic Spectra 3.3 Particles of Light: Quantum Theory 3.4 The Hydrogen Spectrum and the Bohr Model 3.5 Electrons as Waves 3.6 Quantum Numbers 3.7 The Sizes and Shapes of Atomic Orbitals 3.8 The Periodic Table and Filling Orbitals 3.9 Electron Configurations of Ions 3.10 The Sizes of Atoms and Ions 3.11 Ionization Energies 3.12 Electron Affinities 72 36 10/31/2016 Electron Configurations: In what order do electrons occupy available orbitals? Orbital Energy Levels for Hydrogen Atoms E 3s 3p 2s 2p 3d 1s Energy of orbitals in multi-electron atoms Energy depends on n + l 3+2=5 4+0=4 3+1=4 3+0=3 2+1=3 2+0=2 1+0=1 37 10/31/2016 Probability of finding the electron → 1s "Penetration" s>p>d>f 2s 3s 4s 2p 3p 4p 3d 4f for the same shell (e.g. n=4) the s-electron penetrates closer to the nucleus and feels a stronger nuclear pull or charge. 4d distance from nucleus → http://www.pha.jhu.edu/~rt19/hydro/img73.gif Aufbau Principle - the lowest energy orbitals fill up first Filling order of orbitals in multi-electron atoms 1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s 38 10/31/2016 Shorthand description of orbital occupancy 1. No more than 2 electrons maximum per orbital 2. Electrons occupy orbitals in such a way to minimize the total energy of the atom = “Aufbau Principle” (use filling order diagram) 3. No 2 electrons can have the same 4 quantum numbers = “Pauli Exclusion Principle” (pair electron spins) ms = -1/2 spin “down” ms = +1/2 spin “up” •No two electrons in an atom can have the same set of four quantum numbers (n, l, ml, ms) •electrons must "pair up" before entering the same orbital 39 10/31/2016 4. When filling a subshell, electrons occupy empty orbitals first before pairing up = “Hund’s Rule” Px Py Pz NOT Px Py Pz “orbital box diagram” Electron Shells and Orbitals • Orbitals that have the exact same energy level are called degenerate. • Core electrons are those in the filled, inner shells in an atom and are not involved in chemical reactions. Px Py Pz + • Valence electrons are those in the outermost shell of an atom and have the most influence on the atom’s chemical behavior. 40 10/31/2016 H: He: Li: Be: B: C: N: O: F: Ne: 41 10/31/2016 Transition metals are characterized by having incompletely filled d-subshells (or form cations as such). Electron Configurations from the Periodic Table n-1 n-2 42 10/31/2016 Chapter Outline 3.1 Waves of Light 3.2 Atomic Spectra 3.3 Particles of Light: Quantum Theory 3.4 The Hydrogen Spectrum and the Bohr Model 3.5 Electrons as Waves 3.6 Quantum Numbers 3.7 The Sizes and Shapes of Atomic Orbitals 3.8 The Periodic Table and Filling Orbitals 3.9 Electron Configurations of Ions 3.10 The Sizes of Atoms and Ions 3.11 Ionization Energies 3.12 Electron Affinities 85 Electron Configurations: Ions • Formation of Ions: – Gain/loss of valence electrons to achieve stable electron configuration (filled shell = “octet rule”). – Cations: – Anions: – Isoelectronic: 43 10/31/2016 Cations of Transition Metals Fe Cu Sn Pb Sample Exercise 3.11: Determining Isoelectronic Species in Main Group Ions a) Determine the electron configuration of each of the following ions: Mg2+, Cl-, Ca2+, and O2b) Which ions are isoelectronic with Ne? 44 10/31/2016 Chapter Outline 3.1 Waves of Light 3.2 Atomic Spectra 3.3 Particles of Light: Quantum Theory 3.4 The Hydrogen Spectrum and the Bohr Model 3.5 Electrons as Waves 3.6 Quantum Numbers 3.7 The Sizes and Shapes of Atomic Orbitals 3.8 The Periodic Table and Filling Orbitals 3.9 Electron Configurations of Ions 3.10 The Sizes of Atoms and Ions 3.11 Ionization Energies 3.12 Electron Affinities 89 Periodic Trends – trends in atomic and ionic radii, ionization energies, and electron affinities 45 10/31/2016 Effective nuclear charge (Zeff) – Inner shell electrons “SHIELD” the outer shell electrons from the nucleus Zeff = Z - s (s = shielding constant) Zeff Z – number of inner or core electrons Across a period - Z Core Zeff Radius (nm) Na 11 10 1 186 Mg 12 10 2 160 Al 13 10 3 143 Si 14 10 4 132 Effective nuclear charge (Zeff) – Inner shell electrons “SHIELD” the outer shell electrons from the nucleus Down a family - Z Core Zeff Radius (nm) Na 11 10 1 186 K 19 18 1 227 Rb 37 36 1 247 Cs 55 54 1 265 46 10/31/2016 Trends in Effective Nuclear Charge (Zeff) and the Shielding Effect increasing Shielding increasing Zeff Atomic, Metallic, Ionic Radii For diatomic molecules, equal to covalent radius (one-half the distance between nuclei). For metals, equal to metallic radius (onehalf the distance between nuclei in metal lattice). For ions, ionic radius equals one-half the distance between ions in ionic crystal lattice. 47 10/31/2016 Trends in Atomic Size for the “Representative (Main Group) Elements” Increasing Atomic Size Decreasing Atomic Size Radius of Ions Cation is always smaller than atom from which it is formed. Anion is always larger than atom from which it is formed. 48 10/31/2016 Radii of Atoms and Ions must compare cations to cations and anions to anions Increasing Ionic Radius Decreasing Ionic Radius Sample Exercise 3.13: Ordering Atoms and Ions by Size Arrange each by size from largest to smallest: (a) O, P, S (b) Na+, Na, K 49 10/31/2016 Chapter Outline 3.1 Waves of Light 3.2 Atomic Spectra 3.3 Particles of Light: Quantum Theory 3.4 The Hydrogen Spectrum and the Bohr Model 3.5 Electrons as Waves 3.6 Quantum Numbers 3.7 The Sizes and Shapes of Atomic Orbitals 3.8 The Periodic Table and Filling Orbitals 3.9 Electron Configurations of Ions 3.10 The Sizes of Atoms and Ions 3.11 Ionization Energies 3.12 Electron Affinities 99 Ionization energy is the minimum energy (kJ/mol) required to remove an electron from a gaseous atom in its ground state. I1 + X (g) X+(g) + e- I1 first ionization energy I2 + X (g) X2+(g) + e- I2 second ionization energy I3 + X (g) X3+g) + e- I3 third ionization energy I1 < I2 < I3 < ….. 50 10/31/2016 General Trend in First Ionization Energies Decreasing First Ionization Energy Increasing First Ionization Energy Ionization Energies 51 10/31/2016 http://2012books.lardbucket.org/books/principles-of-general-chemistry-v1.0/s11-03-energetics-of-ion-formation.html Successive Ionization Energies (kJ/mol) 52 10/31/2016 Trends in the 1st Ionization Energy for the 2nd Row Li 520 kJ/mol 1s22s1 1s2 Be 899 1s22s2 1s22s1 B 801 1s22s22p1 1s22s2 C 1086 1s22s22p2 1s22s22p1 N 1402 1s22s22p3 1s22s22p2 O 1314 1s22s22p4 1s22s22p3 F 1681 1s22s22p5 1s22s22p4 Ne 2081 1s22s22p6 1s22s22p5 Sample Exercise 3.14: Recognizing Trends in Ionization Energies Arrange Ar, Mg, and P in order of increasing IE 53 10/31/2016 Chapter Outline 3.1 Waves of Light 3.2 Atomic Spectra 3.3 Particles of Light: Quantum Theory 3.4 The Hydrogen Spectrum and the Bohr Model 3.5 Electrons as Waves 3.6 Quantum Numbers 3.7 The Sizes and Shapes of Atomic Orbitals 3.8 The Periodic Table and Filling Orbitals 3.9 Electron Configurations of Ions 3.10 The Sizes of Atoms and Ions 3.11 Ionization Energies 3.12 Electron Affinities 10 7 Electron affinity is the energy release that occurs when an electron is accepted by an atom in the gaseous state to form an anion. X (g) + e- → X-(g) Energy released = E.A. (kJ/mol) F (g) + e- → F-(g) EA = -328 kJ/mol O (g) + e- → O-(g) EA = -141 kJ/mol 54 10/31/2016 Periodic Trends in Electron Affinity http://2012books.lardbucket.org/books/principles-of-general-chemistry-v1.0/s11-03-energetics-of-ion-formation.html 55 10/31/2016 56