Lecture+18_Polyatomic+nomenclature_Begin+VSEPR+and+Hybridization

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Announcements for October 11 th , 2023 The plan: • Polyatomic ions and nomenclature • VSEPR and Hybridization Theory Monday reading : Chapter 8, Sections 6 – 8; Chapter 2, Section 8 (polyatomic ions) Wednesday reading: Chapter 9, Sections 1, 2, 4, 5 ( VSEPR Simulator ) • Homework 6 due Monday, October 16 th by 11:59 PM • Fall Break is Thursday and Friday this week – no recitation, no Friday lecture
Some commonly occurring ions are polyatomic Ammonium: [NH 4 ] + Acetate: [CH 3 CO 2 ] - Hydroxide: [OH] - Carbonate: [CO 3 ] -2 Nitrate: [NO 3 ] - Phosphate: [PO 4 ] -3 Sulfate: [SO 4 ] -2 Cyanide: [CN] - • Molecular ions held together internally by covalent bonds • Have net negative charge (usually) due to octet (closed valence shell) electron configuration Perchlorate: [ClO 4 ] -
Periodic approach to remembering polyatomic anions Group 14 Group 15 Group 16 Group 17 Carbon ate : 𝐶? 3 −2 Nitr ate : ?? 3 − Nitr ite : ?? 2 − Phosph ate : ?? 4 −3 Phosph ite : ?? 3 −3 Sulf ate : 𝑆? 4 −2 Sulf ite : 𝑆? 3 −2 Per chlor ate : 𝐶𝑙? 4 − Chlor ate : 𝐶𝑙? 3 − Chlor ite : 𝐶𝑙? 2 − Hypo chlor ite : 𝐶𝑙? − Max of 3 O’s in Period 2 Max of 4 O’s in Period 3 Net charge becomes less negative (+1 proton to central atom!) Per-[ ]-ate [ ]-ate [ ]-ite Hypo-[ ]-ite -O Oxidation number (charge state) for a set of homologous oxoanions never changes Group 17 oxoanions (Cl, Br, I): Group 14 – 16 oxoanions: [ ]-ate [ ]-ite -O -O -O -O -O -O Cl = Chlor-, Br = Brom-, I = Iod-
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Ca CO 3 Nomenclature: Polyatomic ions form ionic bonds with metals Fe 2 (SO 4 ) 3 NH 4 ClO 4 Na 2 SO 3 • Main group metal: Named as Type I • Transition metal: Named as Type II • Polyatomic ion: No change to polyatomic cation or anion name
To neglect or not neglect resonance in hypervalent molecules Sulfate (SO 4 2- ): S — O Bond order = ___ Do bond lengths follow a trend that supports the need of resonance structures? Sulfuric acid (H 2 SO 4 ): S — O Bond order = ____ S — O length = 149 pm S — O length = 142 pm S — OH length = 157 pm S — O Bond order = ___ S — O Bond order = ____ S — OH Bond order = ____ Theory does not support double-bonding properties. What else could be the reason? Octet-abiding FC minimized Scientists still debate this topic! There is still much to be learned about bonding!
Summary of Lewis structures (1) Octet-abiding Lewis structures – model for predicting molecular connectivity (2) Formal charges – electron counting mechanism used to predict molecular electronic distribution ( lower formal charges or (-) on more EN atom = better structure! ) (3) Resonance structures – delocalization of electron density between covalent bonds and/or lone pairs; consequence of multiple acceptable Lewis structure. (4) Hypervalent compounds – Lewis structures which “violate” the octet rule C H H H H I I I −1 0 0 1) Identify central atom and arrange bonding atoms around as far apart as possible 2) Count valence electrons 3) Connect central atom to surrounding atoms 4) Distribute remaining electrons as lone pairs; then multibonds CH 4 • Can occur for 3 rd period and below elements • Larger atomic radius permits this! • Last resort for accommodating bonding FC = 0 0 0 -1 0 +1 • Stabilizing effect for spreading e - density over multiple atoms
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Lewis structures fail to capture spatial geometry of molecular structure C H H H H Methane (CH 4 ): • 90 o bond angles? Best 2D structure! • H atoms could be further separated… • Experiment indicates methane’s geometry is 3D • 3D permits greater separation between C-H bonds (________ angle) • Bonding atoms point to vertices of ____________ Function of substances depends on their molecular- level structure! Diamond Graphite Mohs hardness 10 ~1 Electrical conductivity Insulator Weak metal Optical Transparent Absorbs visible light Density (g/cm 3 ) 3.52 2.27 Reality:
V alence S hell E lectron P air R epulsion theory uses electron- pair repulsions to predict molecular shapes • _________ pairs and atoms attached to the central atom through ____________ pairs (“ __________________________ ”) determine the central atom ___________ number (SN) • Electron pairs are oriented in 3D space to minimize _____________________ • Regular polyhedral geometries adopted to minimize repulsion between _________________ Lone pair Central atom Bonding pair Bonding atom _____________ geometry – 3D geometry of bonding and lone pairs attached to the central atom ______________ geometry – the geometry defined by the actual attached atoms; ignore lone pairs of electrons SN: Lone pairs are "fatter" than bonded electrons (affects ______)
Construct the Lewis structure for ammonia (NH 3 ), assign its steric number, electron domain geometry (EDG), and propose a name for the molecular geometry (MG). 1. Construct the Lewis structure! 2. Assign a steric number! 3. The adopted EDG sets electron lone pairs and bonding pairs as far apart as possible 4. MGs are based on atomic positions (lone pairs ignored) – use your 3D imagination!
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How do molecules form bonds? Overlap of valence orbitals (Valence Bond Theory) O H H _______________________: No more than two unique electrons may occupy ANY orbital (atomic and molecular!) O H H + + Half-filled orbitals overlap to permit ______________________________ Measured H 2 O bond angle is _____! O O O 2s 2p
C can accept _____ more electrons to fulfill octet (1) Where do the electrons go??? (2) What is the mechanism to bond formation? (3) How is molecular stability achieved? Atoms bond by sharing electrons, and electrons are shared by mixing orbitals together (orbital overlap) 2p 2s Energy 𝑪: ?𝒔 ? ?𝒔 ? ?𝒑 ? 1s ‘3D’ Lewis structure (Tetrahedral geometry) 2p-orbitals oriented at 90 o angles!!! C-atom H-atom _____
Quantum mechanically consistent bonding models Valence bond (hybridization) theory (now) • Pictures bonds as localized pairs of e - ’s shared between atoms • Qualitative prediction of bond strengths and MGs • Blend atomic orbitals → Hybrid orbitals • H 2 O σ -bond: sp 3 (O) – 1s (H) orbitals overlapping • Average O 2s and three 2 p’s → four identical sp 3 Hybridization H —O σ -bond Molecular orbital H — O —H delocalized σ -bond Two different ways of looking at the same thing! Molecular orbital (MO) theory (later) • (Approximately) solves the Schrödinger equation for molecules • Electron energy level diagrams (like atoms) • Pictures e - ’s as delocalized across bonding atoms • Atomic orbitals mix to make bonding and antibonding orbitals • H 2 O σ -bond: 1s (H) – 2s(O) – 1s (H) orbitals overlapping
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Use the atomic orbital picture to describe the bonding in BeH 2 according to Valence Bond Theory. Experiment shows both chemical bonds must be identical (Be – H bond length → 133.4 pm). 1. Construct the Lewis structure! 2. Assign a steric number and identify the number of valence e - ’s present! 3. VSEPR enables us to predict EDG and MG through minimizing e - -e - repulsion 4. What valence orbitals can Be use to bond? 5. Construct electron energy level diagrams of each atom to propose a possible bonding scheme. Bond 1: Bond 2: • Atoms taught us that there can be no more than 2 e - ’s /orbital! • Valence Bond Theory requires half-filled orbitals to overlap
Hybridization of atomic orbitals mechanism: Promotion 2s 2 Energy Be: 1s 2 2s 2 2p 0 1s 1 H: 1s 1 1s 1 H: 1s 1 Energy 1s 1 1s 1 Promotion Half-filled orbitals for overlap! Experimentally, both bonds have same length and strength Bond 1: Bond 2:
+ → + Hybridization of atomic orbitals mechanism: Hybridization 2s 1 Energy 2p 1 1s 1 1s 1 Energy 2p 0 1s 1 1s 1 sp hybrid orbitals make the H-Be-H bonds linear Hybridization or mixing of atomic orbitals gives new blended bonding orbitals: Hybridization # AOs in = # __________ out = # _____ and ___________ If we call the z-axis the bonding axis, then: • 2s and 2p z orbitals hybridize to make two new sp-orbitals • The 2p x and 2p y are unaffected
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Formation of 1 sp-hybrid orbital (2 total will be made) Mixing of 2s and 2p orbitals Why use a hybrid orbital? (1) Mixing enables optimal _________ (2) Bonding lobe volume increases – ________________________________ _____________________________!!!
Hybridization of atomic orbitals mechanism: Overlap Energy 2p 0 Be(sp) — H(1s) H(1s) — Be(sp) Overlap (Bonding) Net energy of the system ______________ upon chemical bond formation – lowering _____________ drives chemical bonding! Energy 2p 0 1s 1 1s 1 (sp) 2
Summary of the hybridization mechanism • 2s and 2p z orbitals hybridize to make two new orbitals • The 2p x and 2p y are unaffected • # AOs in = # Hybrids out = # bonds and LPE 2s 2 Energy Be: 1s 2 2s 2 2p 0 1s 2 1s 2 2p 0 (sp) 2 Energy Be: 1s 2 (sp) 2 1s 1 H: 1s 1 1s 1 H: 1s 1 Energy Net energy of the system decreases upon chemical bond formation – lowering energy drives chemical bonding! 2p 0 (sp) 2
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Hybridization mechanism for SN 3 atomic centers: AX 3 EDG – _____________________ Molecular geometry – _____________________________________ Unhybridized 2p ______ hybrid orbitals 3 covalent bonds! AX 3 Energy Hybridization 2p 2s 3 atomic orbitals on B needed to make 3 hybrid orbitals!
Formation of 1 sp 2 -hybrid orbital (3 total will be made) Mixing of 2s and two 2p orbitals
Molecular Shapes: Steric Number 3 ; EDG = Trigonal planar AX 3 AX 2 E Trigonal Planar BH 3 ___________________ O 3 Central atom hybridization: sp 2 2 ________ domains 1 _________ domain 3 total _______ domains sp 2 sp 2 • Hybridization is dependent on number of electron domains • 1 AO/ domain needed for hybridization EDG: MG: Hybridization: _____________ ______________ ______
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Introduction of an e - lone pair reduces bond angles: ~2 o decrease for every lone pair Bonding domain __________ e - density between 2 nuclei Lone pairs spread to __________ electrostatic interaction with _________ AX 3 AX 2 E 120 o Trigonal Planar V-shaped <120 o All localized bonding domains Bond angle is an ideal 120 o LPE pushes bonding pairs _______ O 3 bond angle: ______ SO 2 bond angle: ______
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AX 4 AX 3 E AX 2 E 2 109.5 o <109.5 o <109.5 o Tetrahedral _______________ _______________ Central atom hybridization: _______ Molecular Shapes: Steric Number 4; EDG = Tetrahedral NH 3 CH 4 H 2 O • 4 e - domains per structure • 1 atomic orbital/ domain for hybridization
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Formation of 1 sp 3 -hybrid orbital (4 total will be made) Mixing of 2s and three 2p orbitals
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Hybridization theory and VSEPR Trivia: Hyb MG EDG Bond Angles Assign orbital hybridization, MG, EDG, and predicted bond angles to the following molecules: Lewis CH 2 Cl 2 [BF 2 ] - AlCl 3 [PO 3 ] -3 [ClF 2 ] +
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