Engineering 45 Atomic Structure and InterAtomic Bonding Bruce Mayer, PE Registered Electrical & Mechanical Engineer BMayer@ChabotCollege.edu Engineering-45: Materials of Engineering 1 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Learning Goals Understand the Sources/Causes of Atom-Level Bonding Understand The Number & Types of Bonding Determine Which properties May be inferred from bonding trends Engineering-45: Materials of Engineering 2 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt The Nuclear Atom Current Best Model of the Atomic Structure • A Small & Dense NUCLEUS surrounded by an Electronic Cloud Nucleus Composition → Two Constituents • PROTONS → POSITIVE Electronic Charge • NEUTRONS → UNcharged Electronic Cloud Composed of NEGATIVELY Charged ELECTRONS Engineering-45: Materials of Engineering 3 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Atomic Facts ELEMENTS are Defined by the Atomic Number, Z • Z Number of Protons – For NATURALLY Occurring Elements Z Ranges from 1 (H) to 92 (U) By the Electronic Neutrality Requirement • [No. Protons] = [No. Electrons] Electronic Charge = 1.6x10-19 Amp•sec • Note: 1 A•s = 1 Coulomb (C) Engineering-45: Materials of Engineering 4 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Since The No. of NEUTRONS Are not Constrained by Charge Neutrality, Then The SAME Element May Have Different No.s of Nuetrons, N • Elemental Forms with Different Neutron Counts are Called ISOTOPES – e.g,; Consider Oxygen with Z = 8 O Isotope Neutrons, N Abundance 16 O 17 O 18 O Engineering-45: Materials of Engineering 5 16-8 = 8 99.7620% 17-8 = 9 0.0383% 18-8 = 10 0.2001% Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt http://ie.lbl.gov/education/isotopes.htm Atomic Facts cont Recall the Periodic Table Engineering-45: Materials of Engineering 6 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Atomic Facts cont.2 Atomic Weight/Mass, A Weighted Average of Naturally Occurring Isotopes SubAtomic Particle Masses • Electron, e- = 9.11x10-31 kg • Proton, p+ , and Neutron, n = 16 700x10-31 kg Since Mp+ & Mn >> Me• Then A (Z+N)Mn Engineering-45: Materials of Engineering 7 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt amu & gMol By SI DEFINITION 12.00000... grams of 12C contains ONE gram-Mol of Carbon • 1 Mol of Any element Contains 6.023x1023 Protons and/or Electrons – 6.023x1023 Avagrado’s Number Atomic Mass Unit, amu • 1 amu/atom = 1 g/mol – e.g.; Atomic Wt of Niobium = 92.91 amu/atom = 92.91 g/mol Engineering-45: Materials of Engineering 8 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Atomic Reactions Nuclear Reaction • Change in the Number of Neutrons, N, or Protons, Z, in an Atom – Remember, Changing Z Changes the ELEMENT TYPE e.g., a Nuclear Reaction can Change LEAD to GOLD Chemical Reaction • Exchange or ReArrangement of ELECTRONS – VAST Majority of Matl Sci Done with Chem Rcns Engineering-45: Materials of Engineering 9 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Electron Behavior → Quanta Electronic Behavior Governed by Quantum (Energy) Mechanics (QE) • QE Studied in Advanced Physics/Chemistry, and Some Branches of Engineering Basic Principle of QE as Applied to Materials Science • Electrons can have ONLY DISCRETE Quantities (quanta) of Energy – i.e., e- Energy Levels are QUANTIZED Engineering-45: Materials of Engineering 10 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Bohr Atom 1st Quantum Model orbital electrons: n = principal quantum number 1 2 n=3 • Electrons Revolve Around Nucleus at Discrete Energy Levels Called Orbitals A Refined Model Based on Wave Mechanics • e- Treated as Both a WAVE and a PARTICLE – Position is Determined STATISTICALLY, not Physically Engineering-45: Materials of Engineering 11 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Atom: Shells & Valence VALENCE Electron Nucleus INNER Shell Electron Neutron VALENCE Shell/Orbit Engineering-45: Materials of Engineering 12 Proton Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Atom Structure - Valence Only the electrons (e-) in the OUTERmost electron shell can participate in CHEMICAL Reactions Adding or Removing an e- creates a CHARGED Atom Called an ION Engineering-45: Materials of Engineering 13 Valence e- Behavior Governs the Atom’s Ability to combine with other elements Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Valence e- Importance A CHEMICAL reaction is the restructuring of the VALENCE Electrons in two or more Elements Valence electron structure determines all of the following properties Composition Thermal Electrical Optical Engineering-45: Materials of Engineering 14 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Electron Configuration of Atoms 3 M d p s 2 L p s 6 2 1 n K s 2 1st Shell 2nd Sub-shell 10 6 2 Four QUANTUM NUMBERS Describe the Electronic Configuration of Atoms • 3rd Quantum No. Describes the Number of VALENCE Electrons 3rd # Electrons 4th Spin Per Sub-shell Engineering-45: Materials of Engineering 15 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Electron Energy States e- have DISCRETE energy states; tend to occupy LOWEST available energy state. 4d 4p N-shell n = 4 3d 4s Energy 3p 3s M-shell n = 3 2p 2s L-shell n = 2 1s K-shell n = 1 Engineering-45: Materials of Engineering 16 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Shell Filling Rules Following Quantum Mechanics 1. Electrons Fill Shells/Orbitals to MINIMIZE the Overall Atom Energy 2. Only TWO e- can Occupy a Single Orbital – Must Have OPPOSITE “SPINS”: ↑ and ↓ 3. Electrons Stay as Widely Separated in physical space as Possible – Favors EMPTY Orbitals as opposed to Half-Filled Orbitals of the SAME Energy Leads to apparently “NONsequential” Filling; e.g. Ca (20) and Sc (21) Engineering-45: Materials of Engineering 17 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Electronic Configuration The Normal Fill Sequence • 1s → 2s → 2p → 3s → 3p → 4s → 3d → 4p → 5s → 6s → 4f → 5d → 6p → 7s → 5f → 6d → 7p For a Given Shell Structure We can Write a ShortHand for an Element’s Electronic Structure; e.g., Sulfur S 1s 2s 2 p 3s 3 p 2 Principal Quantum No. SubShell Engineering-45: Materials of Engineering 18 2 6 2 4 Number of VALENCE Electrons Electrons Per SubShell Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Stable Electron Configurations Stable Electron Configurations • Have COMPLETE s & p SubShells – i.e., The VALENCE SubShell is FULL • Are VERY Unreactive Engineering-45: Materials of Engineering 19 “OCTET” RULE: Ns2Np6 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Periodic Table Structure Columns Engineering-45: Materials of Engineering 20 (valence shells) Rows (valence electron structure) n=1 n=2 n=3 n=4 (1s1) (2s1) (3s1) (4s1) Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Periodic Table Structure cont. Rows: Same OUTER Shell (Primary Quantum No.) Column: SAME Number Of Valence Electrons Similar Properties Trends: Atomic Radii, Electronegativity (tendency to acquire electrons) METALS NONMETALS Radii Less ElectroNeg Engineering-45: Materials of Engineering 21 More ElectroNeg Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Periodic Table Structure Organized by Quantum No., Valence (or Group), and SubShell Engineering-45: Materials of Engineering 22 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Metals, SemiMetals, NonMetals s p d Quantum No. Engineering-45: Materials of Engineering 23 f Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Metals, SemiMetals, NonMetals METALS • Solid at Room Temperature – Except Hg • Maleable & Ductile • Conduct Electricity SemiMetals • 6 or 7 (Astatine is the Wobbler) • Have Some MetalLike Properties NonMetals (17) – Solids at Rm Temp – Can Conduct Electricity • Poor Heat Conductors • Have Some NonMetal-Like Props • Brittle and Fracture Easily Engineering-45: Materials of Engineering 24 – Hard & Brittle Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt At Refined Shell Model for Nitrogen Valence SHELL (L or 2) Valence SUBShell (2p) Engineering-45: Materials of Engineering 25 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Molecular Bonding Molecules (2+ units of SAME atom) and Compounds (2+ DIFFERENT atoms) are Formed by CHEMICAL Bonding CHEMICAL Bonds Result from ELECTRON Configuration Rearrangement • STRONG Bonds → Ionic, Metallic, Covalent • WEAK Bonds → Van Der Waals – DiPole, Polar, H-Bond Engineering-45: Materials of Engineering 26 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Bond-Energy Curve Force Balance Between Atoms’ REPULSIVE and ATTRACTIVE Forces • ZERO Net Force • LOWEST System Energy r0 - equilibrium bond distance “just right”: Energy too close → Repulsion Bond Distance Equilibrium InterAtomic Distance, or LATTICE Constant Bond STRENGTH ↑ • Melting Temperature ↑ • Stiffness ↑ too far → Attaction Engineering-45: Materials of Engineering 27 Min U Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Ionic Bonding Ion An Atom That Has Gained/Lost e-(s) • Resulting Ion has +/- CHARGE Ionic Bonding Ocurrs Between + & - Ions • Requires Electron TRANSFER; e.g. NaCl X Na (metal) Unstable 1s22s22p63s1 Na (cation) Stable 1s22s22p6 electron + Coulombic Attraction Engineering-45: Materials of Engineering 28 Cl (nonmetal) Unstable 1s22s22p63s23p5 - Cl (anion) Stable 1s22s22p63s23p6 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Ionic Bonding Examples Dominant Bonding Type for CERAMICS H 2.1 Li 1.0 Na 0.9 K 0.8 Rb 0.8 Cs 0.7 Fr 0.7 NaCl MgO CaF 2 CsCl Be 1.5 Mg 1.2 Ca 1.0 Sr 1.0 Ti 1.5 Cr 1.6 Ba 0.9 Fe 1.8 Ni 1.8 Zn 1.8 As 2.0 F 4.0 Cl 3.0 Br 2.8 I 2.5 At 2.2 Ra 0.9 Give up electrons Engineering-45: Materials of Engineering 29 O 3.5 Acquire electrons Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt He Ne Ar Kr Xe Rn - CoValent Bonding Requires SHARED Electrons (Co-Valent) Example is CH4 (methane) • C: has 4 valence e-’s, needs 4 more • H: has 1 valence e-, needs 1 more Characteristics • If A compound, Then Electronegativities are comparable • ≥4 valence e-’s Cl2 Engineering-45: Materials of Engineering 30 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt CoValent Bonding Examples NonMetallic Elemental Molecules; e.g. F2 Elemental Solids; e.g., C, Si, Ge col IVA Hydrogen Compounds; Near Group-IVA Solid e.g., HF, HNO3 Compounds; e.g. GaAs H2O H2 F2 C(diamond) He H 2.1 Cl2 SiC Li O F Ne Be C 1.0 Na 0.9 K 0.8 1.5 Mg 1.2 Rb 0.8 Cs 0.7 Sr 1.0 Ba 0.9 Ca 1.0 Ti 1.5 Cr 1.6 Fr Ra Engineering-45: Materials of Engineering 0.7 0.9 31 2.0 2.5 Si 1.8 Fe 1.8 Ni 1.8 Zn 1.8 Ga 1.6 Ge 1.8 As 2.0 Sn 1.8 Pb 1.8 GaAs 4.0 Cl 3.0 - Ar - Br 2.8 I 2.5 Kr Xe - At 2.2 Rn - Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Mixed Ionic+Covalent Bonding Many Compounds Exhibit Ionic-Covalent Mixed Bonding % - Ionic 1 e X A X B 2 4 100% 1 • where XA & XB are Pauling ElectroNegativities Example MgO: XMg = 1.3, XO = 3.5 % - Ionic 1 e Engineering-45: Materials of Engineering 32 1.33.5 2 4 100% 70.2% 1 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Metallic Bonds Electrons Shared By All Atoms • “sea of electrons” around “ion cores” Ion Cores Ne config • Atoms Give Up Valence-eto the “sea”, leaving remaining Atoms with a Positive Ionic Charge – The Ion contains the Large & Heavy Nucleus and is thus FIXED in Space Generally Applies to Electro-Positive Elements • e.g.; Transition Metals such as Ti, Ni, Zn, Cu Engineering-45: Materials of Engineering 33 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Secondary Bonding Arises from Atomic or Molecular DIPOLES What’s a DiPole? • Separation of the + & Charge-Centers Fluctuating DiPoles • Charge Centers Due to SHORT-LIVED Charge Asymmentry – Generates an ELECTRIC Field within the Entity E-Field Engineering-45: Materials of Engineering 34 Liquifying Force for Electrically Neutral and Symetrical Molecules such as H2, N2 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Secondary Bonding cont. Ionic Bonding in some Molecules results in a PERMANENT Dipole The +/- End of These Polar Molecules can Then Attract the -/+ Ends of Other Polar Molecules General Case e.g.; HCl Liquid e.g.; Polymer Solid Engineering-45: Materials of Engineering 35 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Secondary Bonding, H Bond Recall that H has in Only a Single Proton and Electron • NO Neutrons When H forms an Ionic Bond, it Gives Up (for the most part) the e- This Proton-Induced Dipole is quite Strong and Can Lead to relatively powerful Dipole Bonding • Classic Example = H2O to Form Liquid or Solid • This Leaves the Hydrogen’s p+ Ionic Core Unscreened by any e-’s • This Forms a Molecule with a POSITIVE (and Negative) end Engineering-45: Materials of Engineering 36 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Summary: Chemical Bonding Bond Type Ionic Bond Energy Metallic Large Variable • Large =>Diamond • Small => Bismuth Variable • Large => Tungsten • Small => Mercury Secondary Smallest Covalent Engineering-45: Materials of Engineering 37 Notes NonDirectional e.g.; Ceramics Directional e.g.: SemiConductors, Ceramics, Polymer-Chains NonDirectional e.g.; Metals Directional Interchain (PolyMer) InterMolecular (Liq Water) Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Properties From Bonding: TMelt Bond Length Melting Temperature, TM Energy (r) r Bond Energy, E0 ro r Energy (r) smaller TM unstretched length ro r Eo = “bond energy” Engineering-45: Materials of Engineering 38 larger TM General Relationship: |E0|↑ TM ↑ Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Properties From Bonding: E Modulus of Elasticity Defined cross sectional area Ao length, Lo undeformed unstretched length ro L deformed F Mathematically, E Elastic modulus F L =E Ao Lo Engineering-45: Materials of Engineering 39 Modulus of Elasticity Curvature of E vs r curve Energy r Smaller E larger E General Relationship: |E0|↑ E ↑ Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Properties From Bonding: Coefficient of Thermal Expansion, , Defined Energy length, L o unheated, T1 ~symmetry at r0 L heated, T 2 Mathematically, ro r Smaller Larger coeff. thermal expansion L = (T2 -T1) Lo Engineering-45: Materials of Engineering 40 General Relationship: |E0|↑ ↑ Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Summary: Primary Bonds Ceramics (Ionic & covalent bonding): Metals (Metallic bonding): Polymers (Covalent & Secondary): Engineering-45: Materials of Engineering 41 Large bond energy large Tm large E small Variable bond energy moderate Tm moderate E moderate Directional Properties Secondary bonding dominates small Tm small E large Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt All Done for Today α Superimposed On Periodic Table GALLUIUM is the Tall Yellow one SODIUM is th Tall Blue one Engineering-45: Materials of Engineering 42 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt WhiteBoard Work – P2.13 K+ & O2- dipotassium oxide = K2O r0 = 1.5 nm Engineering-45: Materials of Engineering 43 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt Problem Tutorial Let’s Work Text Problem 2.14 Calcuim Oxide → Engineering-45: Materials of Engineering 44 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt P2.13 Engineering-45: Materials of Engineering 45 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt P2.13 Engineering-45: Materials of Engineering 46 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt P2.13 Engineering-45: Materials of Engineering 47 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt P2.14 Engineering-45: Materials of Engineering 48 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt P2.14 Engineering-45: Materials of Engineering 49 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt P2.15 % Program E45_Prob_2_15_1101.m: % Plot EA and ER vs r * Verify r0 numerically % Bruce Mayer, PE • ENGR45 • 24Jan11 % % Calc r0 numerically using anonymous fcn for En %* the eqn in text book is for r in nm % A = 1.436; B = 5.86e-6; En = @(r) B/r^9 - A/r % % find En,min at r = r0 us fminbnd command [r0, Emin] = fminbnd(En, 0, 1); disp('InterAtomic spacing for Min E, r0 in nm =') disp (r0) % % Calc En,min = En(r0) En_min = En(r0); disp('Min E, En_min in eV =') disp (En_min)% % Set Plotting Vector as 300 points r_plt = linspace (0.1, .4, 300); % in nm % % The Energy Functions EA = -A./r_plt; ER = B./r_plt.^8; Etot = EA + ER; % % Plot on Same Graph plot(r_plt,EA, r_plt,ER, r_plt, Etot), xlabel('r (InterAtom Spacing)'),... ylabel('Energy'), title('ENGR45 Problem 2.14'), grid,... legend('EA', 'ER', 'Etot'), axis([.1 .4 -8 8]) % % Compare to eqn 2.11 solution n = 9; disp('by eqn 2.11') r0eqn = (A/(n*B))^(1/(1-n)) E0eqn = -A/(A/(n*B))^(1/(1-n)) + B/(A/(n*B))^(n/(1-n)) BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt 50 Bruce Mayer, PE Engineering-45: Materials of Engineering NaCl electron Exchange Engineering-45: Materials of Engineering 51 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt WhiteBoard Work – P2.13 Ca2+ & O2- Engineering-45: Materials of Engineering 52 Bruce Mayer, PE BMayer@ChabotCollege.edu • ENGR-45_Lec-02_AtomicBonding.ppt