Chemistry Unit 3: Atomic Structure Basics of the Atom Subatomic Charge Particle Location in the Atom Mass proton 1+ in nucleus ~ 1 a.m.u. neutron 0 in nucleus ~ 1 a.m.u. electron 1– around nucleus ~ 0 a.m.u. a.m.u.: unit used to measure mass of atoms “atomic mass unit” atomic number: # of p+ -- the whole number on Periodic Table -- determines identity of the atom 10 Ne 20.1797 mass number: (# of p+) + (# of n0) (It is NOT on “the Table.”) To find net charge on an atom, consider e– p+ and ____. ____ ion: a charged atom anion: a (–) ion cation: a (+) ion -- more e– than p+ -- more p+ than e– -- formed when atoms gain e– -- formed when atoms lose e– I think that an ions are negative ions. “When I see a cation, I see a positive ion; that is, I… C A + ion.” Other Mnemonic Devices Metals form positive ions Cations are “paws”itive Description Net Charge Atomic Number Mass Number 15 p+ 16 n0 18 e– 3– 15 31 P3– 38 p+ 50 n0 36 e– 2+ 38 88 Sr2+ 2– 52 128 Te2– 1+ 19 39 K+ 52 p+ 76 n0 54 e– 19 p+ 20 n0 18 e– Ion Symbol Isotopes: different varieties of an element’s atoms -- have diff. #’s of n0; thus, diff. mass #’s -- some are radioactive; others aren’t All atoms of an element react the same chemically. p+ n0 Common Name H–1 Mass 1 1 0 protium H–2 2 1 1 deuterium H–3 3 1 2 tritium Isotope C–12 atoms 6 p+ 6 n0 C–14 atoms 6 p+ 8 n0 stable radioactive Complete Atomic Designation …gives very precise info about an atomic particle mass # charge (if any) element symbol atomic # 125 53 Goiter due to lack of iodine I – iodine is now added to salt Protons Neutrons Electrons 92 146 92 11 12 10 34 45 36 27 32 24 17 20 18 25 30 18 Complete Atomic Designation 238 U 92 23 + Na 11 79 2– Se 34 59 3+ Co 27 37 – Cl 17 55 7+ Mn 25 Radioactive Isotopes: have too many or too few n0 Nucleus attempts to attain a lower energy state by releasing extra radiation energy as __________. e.g., a- or b-particles, g rays half-life: the time needed for ½ of a radioactive sample to decay into stable matter e.g., C–14: half-life is 5,730 years decays into stable N–14 Say that a 120 g sample of C-14 is found today… Years from now 0 5,730 11,460 17,190 22,920 = C–14 = N–14 g of C–14 g of N–14 present present 120 0 60 30 60 90 15 7.5 105 112.5 Half Life Graph (Sr-90 Activity) Average Atomic Mass (AAM) This is the weighted average mass of all atoms of an element, measured in a.m.u. Ti has five naturallyoccurring isotopes For an element with isotopes A, B, etc.: AAM = Mass A (% A) + Mass B (% B) + … % abundance (use the decimal form of the % e.g., use 0.253 for 25.3%) Lithium has two isotopes. Li-6 atoms have mass 6.015 amu; Li-7 atoms have mass 7.016 amu. Li-6 makes up 7.5% of all Li atoms. Find AAM of Li. Li batteries AAM = Mass A (% A) + Mass B (% B) AAM = 6.015 amu (0.075) + 7.016 amu (0.925) AAM = 0.451 amu + 6.490 amu AAM = 6.94 amu ** Decimal number on Table refers to… molar mass (in g) OR AAM (in amu). 6.02 x 1023 atoms 1 “average” atom Isotope Mass Si-28 Si-29 27.98 amu 28.98 amu ? Si-30 % abundance 92.23% 4.67% 3.10% AAM = MA (% A) + MB (% B) + MC (% C) 28.086 = 27.98 (0.9223) + 28.98 (0.0467) + X (0.031) 28.086 = 28.086 = 0.927 = 0.031 25.806 + 1.353 27.159 X = MSi-30 = 29.90 amu + 0.031X + 0.031X 0.031X 0.031 Historical Development of the Atomic Model Greeks (~400 B.C.E.) Democritus & Leucippus Matter is discontinuous (i.e., “grainy”). “atomos” = uncuttable or indivisible Greek model of atom Solid and INDESTRUCTABLE Hints at the Scientific Atom ** Antoine Lavoisier: law of conservation of mass mass R = mass P ** Joseph Proust (1799): law of definite proportions: every compound has a fixed proportion e.g., water…………………….. 8 g O : 1 g H chromium (II) oxide……. 13 g Cr : 4 g O Hints at the Scientific Atom (cont.) ** John Dalton (1803): law of multiple proportions: When two different compounds have same two elements, equal mass of one element results in integer multiple of mass of other 2 e.g., water…………………….. 8 g O : 1 g H hydrogen peroxide..…….16 g O : 1 g H 3 chromium (II) oxide……. 13 g Cr : 4 g O chromium (VI) oxide……13 g Cr : 12 g O John Dalton’s Atomic Theory (1808) 1. Elements are made of indivisible particles called atoms. 2. Atoms of the same element are exactly alike; in particular, they have the same mass. 3. Compounds are formed by the joining of atoms of two or more elements in fixed, whole number ratios. e.g., 1:1, 2:1, 1:3, 2:3, 1:2:1 NaCl, H2O, NH3, Fe2O3, C6H12O6 Dalton’s model of atom ** William Crookes (1870s): Rays causing shadow were emitted from cathode. Maltese cross CRT radar screen television computer monitor J.J Thomson (~1900) J.J. Thomson discovered that “cathode rays” are… …deflected by electric and magnetic fields electric field lines “cathode rays” Crooke’s tube … (–) particles J.J. Thomson ++++++ – – – – – – electrons phosphorescent screen William Thomson (a.k.a., Lord Kelvin): Since atom was known to be electrically neutral, he proposed the plum pudding model. -- Equal quantities of (+) and (–) charge distributed uniformly in atom. Lord Kelvin ++ ++ + ++ + + ++ – – – – – -- (+) is ~2000X more massive than (–) plum pudding – – – – – – Thomson’s plum pudding model Ernest Rutherford (1909) Gold Leaf Experiment Beam of a-particles (+) directed at gold leaf surrounded by phosphorescent (ZnS) screen. a-source lead block particle beam ZnS screen gold leaf Most a-particles passed through, some angled slightly, and a tiny fraction bounced back. Conclusions: 1. Atoms are mostly empty space 2. (+) particles are concentrated at center nucleus = “little nut” 3. (–) particles orbit nucleus Rutherford’s ModelModel Dalton’s (also thePudding Greek) Thomson’s Plum Model – + – + + – – + – – + + + N – + – – – – – – +– + + – – – ** James Chadwick discovered neutrons in 1932 n0 have no charge and are hard to detect purpose of n0 = stability of nucleus photo from liquid H2 bubble chamber Chadwick And now we know of many other subatomic particles: quarks, muons, positrons, neutrinos, pions, etc. Discovery of the Neutron 9 4 Be + 4 2 He 12 6 C + 1 0 n James Chadwick bombarded beryllium-9 with alpha particles, carbon-12 atoms were formed, and neutrons were emitted. Dorin, Demmin, Gabel, Chemistry The Study of Matter 3rd Edition, page 764 *Walter Boethe Recent Atomic Models Max Planck (1900): Proposed that amounts of energy are quantized only certain values are allowed Niels Bohr (1913): e– can possess only certain amounts of energy, and can therefore be only certain distances from nucleus. planetary (Bohr) model e– found here N e– never found here Bohr Atom The Planetary Model of the Atom Bohr’s Model Nucleus Electron Orbit Energy Levels quantum mechanical model electron cloud model charge cloud model Schroedinger, Pauli, Heisenberg, Dirac (up to 1940): According to the QMM, we never know for certain where the e– are in an atom, but the equations of the QMM tell us the probability that we will find an electron within a certain distance from the nucleus. Electron Cloud Model • Orbital (“electron cloud”) instead of “orbits” – Region in space where there is 90% probability of finding an electron 90% probability of finding the electron Electron Probability vs. Distance Electron Probability (%) 40 30 20 10 0 0 50 100 150 Distance from the Nucleus (pm) Orbital Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem 200 250 Models of the Atom Review "In science, a wrong theory can be valuable and better than no theory at all." - Sir William L. Bragg e e + e + e + + e +e + e e + e + e Dalton’s Greek model model (400 (1803) B.C.) Thomson’s plum-pudding model (1897) Bohr’s model (1913) Dorin, Demmin, Gabel, Chemistry The Study of Matter , 3rd Edition, 1990, page 125 - - + Rutherford’s model (1909) Charge-cloud model (present) Models of the Atom Timeline e e + e - + e + + e +e +e e + e + e Dalton’s model Greek model (1803) (400 B.C.) 1803 John Dalton pictures atoms as tiny, indestructible particles, with no internal structure. 1800 - Thomson’s plum-pudding model (1897) - + Rutherford’s model (1909) 1897 J.J. Thomson, a British 1911 New Zealander scientist, discovers the electron, leading to his "plum-pudding" model. He pictures electrons embedded in a sphere of positive electric charge. Ernest Rutherford states that an atom has a dense, positively charged nucleus. Electrons move randomly in the space around the nucleus. 1805 ..................... 1895 1900 1905 1910 1904 Hantaro Nagaoka, a Japanese physicist, suggests that an atom has a central nucleus. Electrons move in orbits like the rings around Saturn. Dorin, Demmin, Gabel, Chemistry The Study of Matter , 3rd Edition, 1990, page 125 1915 Bohr’s model (1913) 1926 Erwin Schrödinger 1913 In Niels Bohr's model, the electrons move in spherical orbits at fixed distances from the nucleus. 1920 1925 Charge-cloud model (present) 1930 develops mathematical equations to describe the motion of electrons in atoms. His work leads to the electron cloud model. 1935 1940 1945 1924 Frenchman Louis 1932 James de Broglie proposes that moving particles like electrons have some properties of waves. Within a few years evidence is collected to support his idea. Chadwick, a British physicist, confirms the existence of neutrons, which have no charge. Atomic nuclei contain neutrons and positively charged protons. Light When all e– are in lowest possible energy state, ground state an atom is in the ____________. e.g., He: 2 e-, both in 1st energy level ENERGY (HEAT, LIGHT, ELEC., ETC.) If “right” amount of energy is absorbed by an e–, it can “jump” to a higher energy level. This is an unstable, excited state momentary condition called the ____________. e.g., He: 1 e- in 1st E level, 1 e- in 2nd E level When e– falls back to a lower-energy, more stable orbital (it might be the orbital it started out in, but it might not), atom releases the “right” amount of energy as light. EMITTED LIGHT Any-old-value of energy to be absorbed or released is NOT OK. This explains the lines of color in an emission spectrum. Emission Spectrum for a Hydrogen Atom Lyman series: e– falls to 1st energy level Balmer series: e– falls to 2nd energy level Paschen series: e– falls to 3rd energy level H discharge tube, with power supply and spectroscope typical emission spectrum Lyman (UV) Balmer (visible) Paschen (IR) 6TH E.L. 5TH E.L. 4TH E.L. ~ ~ ~ ~ ~ ~ 3RD E.L. 2ND E.L. 1ST E.L. electromagnetic radiation (i.e., light) -- waves of oscillating electric (E) and magnetic (B) fields -- source is… vibrating electric charges E B Characteristics of a Wave crest amplitude A trough wavelength l frequency: the number of cycles per unit time (usually sec) -- unit is Hz, or s–1 or 1/s electromagnetic spectrum: contains all of the “types” of light that vary according to frequency and wavelength cosmic rays gamma rays X-rays UV visible IR microwaves radio waves ROYGBV 750 nm 400 nm large l small l -- visible spectrum ranges from low f high f only ~400 to 750 nm (a very low energy narrow band of spectrum) high energy Albert Michelson (1879) -- first to get an accurate value for speed of light Albert Michelson (1852–1931) The speed of light in a vacuum (and in air) is constant: c = 3.00 x 108 m/s -- Equation: c=fl In 1900, Max Planck assumed that energy can be absorbed or released only in certain discrete amounts, which he called quanta. Later, Albert Einstein dubbed a light “particle” that carried a quantum of energy a photon. -- Equation: Max Planck (1858–1947) E=hf E = energy, in J h = Planck’s constant = 6.63 x 10–34 J∙s (i.e., J/Hz) Albert Einstein (1879–1955) A radio station transmits at 95.5 MHz (FM 95.5). Calculate the wavelength of this light and the energy of one of its photons. 8 m/s 3.00 x 10 c=fl l = = 3.14 m 6 95.5 x 10 Hz f c E = h f = 6.63 x 10–34 J/Hz (95.5 x 106 Hz) = 6.33 x 10–26 J Electron Cloud Model • Orbital (“electron cloud”) instead of “orbits” – Region in space where there is 90% probability of finding an electron 90% probability of finding the electron Orbital Shape Orbital Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem Shapes of s, p, and d orbitals p-Orbitals px Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 335 pz py s, p, and d-orbitals s orbitals: Each holds 2 electrons (outer orbitals of Groups 1 and 2) Kelter, Carr, Scott, , Chemistry: A World of Choices 1999, page 82 p orbitals: Each of 3 sets holds 2 electrons = 6 electrons (outer orbitals of Groups 3 to 8) d orbitals: Each of 5 sets holds 2 electrons = 10 electrons (found in elements in third period and higher) f orbitals Relative Sizes 1s and 2s 1s Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 334 2s Copyright © 2006 Pearson Benjamin Cummings. All rights reserved. Periodic Patterns p block n s block 1 2 3 4 5 6 7 1s 1s 2s 2p d block (n-1) 3s 3p 4s 3d 4p 5s 4d 5p 6s 5d 6p 7s 6d 7p f (n-2) block 6 7 4f 5f Sections of Periodic Table to Know s-block p-block d-block f-block Energy Level Diagram of a Many-Electron Atom 6s 6p 5d 4f 32 5s 5p 4d 18 4s 4p 3d 18 Arbitrary Energy Scale 3s 3p 8 2s 2p Each orbital can only hold 2 e- 8 Start from the bottom and add e- 1s 2 NUCLEUS O’Connor, Davis, MacNab, McClellan, CHEMISTRY Experiments and Principles 1982, page 177 You don’t have to memorize the order…just start at the beginning and fill in e-… Periodic Patterns • Example - Hydrogen 1 2 3 4 5 6 7 1 1s 1st Period (row) 1 e- in “1s” orbital s-block Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem Writing Electron Configurations: Where are the e–? (probably) H 1s1 He 1s2 Li 1s2 2s1 N 1s2 2s2 2p3 Al 1s2 2s2 2p6 3s2 3p1 Ti 1s2 2s2 2p6 3s2 3p6 4s2 3d2 As 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p3 Xe 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 Filling Order 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6… Shorthand Electron Configuration (S.E.C.) To write S.E.C. for an element: 1. Put symbol of noble gas that precedes element in brackets. 2. Continue writing e– config. from that point S [ Ne ] 3s2 3p4 Co [ Ar ] 4s2 3d7 In [ Kr ] 5s2 4d10 5p1 32 Ge 72.61 Cl [ Ne ] 3s2 3p5 Rb [ Kr ] 5s1 Shorthand Configuration A neon's electron configuration (1s22s22p6) B 3rd energy level (or 3rd period) C 1 electron in the s orbital D orbital shape (s,p,d,f…etc.) [Ne] 3s1 22s22p6] 3s1 [ 1s Na = electron configuration Shorthand Configuration Review Element symbol Electron configuration Ca [Ar] 4s2 V [Ar] 4s2 3d3 F [He] 2s2 2p5 Ag [Kr] 5s2 4d9 I [Kr] 5s2 4d10 5p5 Xe [Kr] 5s2 4d10 5p6 or [Xe] Fe 22p64s [He] 2s[Ar] 3s223d 3p664s23d6 Sg [Rn] 7s2 5f14 6d4 Three Principles about Electrons 3d10… 4s2 3p6 3s2 Aufbau Principle: e– will fill the lowest-energy orbital available Hund’s Rule: 2p6 2s2 1s2 for equal-energy orbitals (p, d) each must have one e– before any take a second Friedrich Hund Pauli Exclusion Principle: two e– in same orbital have different spins Wolfgang Pauli Orbital Diagrams …show spins of e– and orbital location O 1s22s22p4 1s P 2s 2p 3s 3p 3s 3p 1s22s22p63s23p3 1s 2s 2p The Importance of Electrons orbitals: regions of space where an e– may be found In a generic e– config (e.g., 1s2 2s2 2p6 3s2 3p6…): coefficient # of energy level superscript # of e– in those orbitals In general, as energy level # increases, e–… HAVE MORE ENERGY AND ARE FURTHER FROM NUCLEUS 16 Electron Configuration S 32.066 • Longhand Configuration S 16e- 1s2 2s2 2p6 3s2 3p4 Kernel (Core) Electrons Valence Electrons (Highest energy level) • Shorthand Configuration S 16e 2 4 [Ne] 3s 3p Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem kernel (core) electrons: in inner energy level(s); close to nucleus valence electrons: in outer energy level INVOLVED IN CHEMICAL BONDING He: 1s2 Ne: [ He ] 2s2 2p6 (2 valence e–) Ar: [ Ne ] 3s2 3p6 (8 valence e–) Kr: [ Ar ] 4s2 3d10 4p6 (8 valence e–) (8 valence e–) Noble gas atoms have FULL valence orbitals. They are stable, low-energy, and unreactive. Other atoms “want” to be like noble gas atoms… ** So, they lose or gain e–... octet rule: the tendency for atoms to fill valence orbitals completely with 8 e– (outer E level) doesn’t apply to He, Li, Be, B (which require 2) or to H (which requires either 0 or 2)…“duet rule” chlorine atom, Cl fluorine atom, F How to be like 9 p+, 9 e– 17 p+, 17 e– [He] 2s22p5 a noble gas…? [Ne] 3s23p5 gain 1 e– or lose 7 e-? 9 p+, 10 e– F– F is more stable as an F– ion gain 1 e– or lose 7 e-? 17 p+, 18 e– Cl– Cl is more stable as a Cl– ion sodium atom, Na lithium atom, Li 3 p+, 3 e– [He] 2s1 How to be like a noble gas…? lose 1 e– or gain 7 e-? 3 p+, 2 e– Li+ Li is more stable as the Li+ ion. 11 p+, 11 e– [Ne] 3s1 lose 1 e– or gain 7 e-? 11 p+, 10 e– Na+ Na is more stable as Na+ ion Know charges on these columns of Table: 1+ 2+ Group 1: Group 2: Group 3: Group 5: Group 6: Group 7: Group 8: 1+ 2+ 3+ 3– 2– 1– 0 0 3+ 3– 2– 1– Periodic Patterns and Charge Trends n p s +1 +2 d 1 2 3 4 5 6 7 Variable Charge f (n-2) 6 7 +3 -3 -2 -1 1s Naming Ions Cations e.g., use element name and then say “ion” Ca2+ calcium ion Cs1+ cesium ion Al3+ aluminum ion Anions e.g., change ending of element name to “ide” and then say “ion” S2– sulfide ion P3– phosphide ion N3– nitride ion O2– oxide ion Cl1– chloride ion Extra Slides