20. 11/04 Acid-Base Chemistry [MT 6]
Transcription
20. 11/04 Acid-Base Chemistry [MT 6]
Chem 104A, UC, Berkeley Molecular Orbitals of Ethene Chem 104A, UC, Berkeley 1 Chem 104A, UC, Berkeley Molecular Orbital Analysis of Ethene Dimerisation the reaction is said to be a "symmetry forbidden" – interestingly, this reaction is rare and very slow ! Chem 104A, UC, Berkeley Molecular Orbitals of 1,3-Butadiene 2 Chem 104A, UC, Berkeley Chem 104A, UC, Berkeley Molecular Orbital Analysis of Diels-Alder reaction 3 Chem 104A, UC, Berkeley Acid-Base Chemistry Reading : MT 6 Chem 104A, UC, Berkeley The Acid Base Theory of Brønsted and Lowry In 1923, within several months of each other, Johannes Nicolaus Brønsted (Denmark) and Thomas Martin Lowry (England) published essentially the same theory about how acids and bases behave. •An acid is a "proton donor." •A base is a "proton acceptor." 4 Chem 104A, UC, Berkeley HCl + H2O <===> H3O+ + Cl¯ HCl - this is an acid, because it has a proton available to be transfered. H2O - this is a base, since it gets the proton that the acid lost. Now, here comes an interesting idea: H3O+ - this is an acid, because it can give a proton. Cl¯ - this is a base, since it has the capacity to receive a proton. Notice that each pair (HCl and Cl¯ as well as H2O and H3O+ differ by one proton (symbol = H+). These pairs are called conjugate pairs. Chem 104A, UC, Berkeley HCl + stronger acid NH4+ stronger acid NaOH ---> OHstronger base + Weaker conjugate acid stronger base + H2O ---> H2O weaker conjugate acid NaCl weaker conjugate base + NH3 weaker conjugate base 5 Chem 104A, UC, Berkeley H n A H 2O H n 1 A H 3O [ H n 1 A ][ H 3O ] pK a1 log [ H n A] pK a 0 strong pK a 0 weak Chem 104A, UC, Berkeley Amphoteric Compound H n A H 2O H n 1 A H 3O NH 3 H 2O NH 4 OH 6 Chem 104A, UC, Berkeley Oxyacids AOp(OH)q A=Si, N, P, As, S, Se, Te, Cl, Br, I p=# of nonhydrogenated oxygen atom + H A ----O As atom A is rendered more positive, it becomes easier to break the O-H bond Because of enhanced bond polarization. The greater the formal charge on A. the stronger the acid should be. Chem 104A, UC, Berkeley Oxyacids AOp(OH)q p=# of nonhydrogenated oxygen atom p=0: p=1: p=2: p=3: PKa PKa PKa PKa 8-9 very weak 1-2 weak -2 ~ -3 strong -7 very strong A=Si, N, P, As, S, Se, Te, Cl, Br, I 7 Chem 104A, UC, Berkeley O p=3 2 1 0 Empirical Rule (Pauling) PK a 8 5 p Chem 104A, UC, Berkeley 8 Chem 104A, UC, Berkeley Chem 104A, UC, Berkeley As successive protons are removed, the PKa increases by ~4 Or 5 each time. H 3 PO4 H 2 PO4 HPO4 ( 2.15) (7.20) (12.37) H 2 SO4 HSO4 ( 3.0) (2.0) 9 Chem 104A, UC, Berkeley Hn X 0.1 M HCl, H2S,H2O, H3PO4,H2PO4-,HPO42-,PO43- Chem 104A, UC, Berkeley Acidity H2Se > H2S > H2O Conjugated bases SeH-, SH-, OH- of larger molecules lower charge density weaker attraction for H+ 10 Chem 104A, UC, Berkeley Acidity NH3 < H2O < HF Conjugated bases NH2-, OH- , FNH2- -1/2 on each lone pair HO- -1/3 on each lone pair F- -1/4 on each lone pair Strongest attraction for proton Strongest conjugated base Weakest acid NH3 Chem 104A, UC, Berkeley Lewis Concept A base: an electron-pair donor Species with lone pair type orbitals An acid: an electron-pair acceptor Species with empty non-bonding type orbitals MO theory 11 Chem 104A, UC, Berkeley 2 u* 2 g* Lewis acid BeL2, MgL2 1 u 1 ub 1 gb x* Lewis acid BL3, AlL3 GaL3 InL3 * 104A, UC, Berkeley Chem y ' s* 2pz yb b x 2s sb 2e1 2a1' znb 2py 2px Ligand Group Orbitals LGOs 1a '' 2 LGO1 1e1' 1a1' B LGO3 LGO2 3H BH3 12 Chem 104A, UC, Berkeley Lewis base NL3, PL3, AsL3, SbL3, BiL3 NH3 (C3v: E, 2C3, 3v) z 3H N NH3 H(3) H(1) H(2) 2e -13.5 eV 4a1 y x - s2 + s3 e -15.5 eV The symmetry of 3H’s group orbitals: e (2px, 2py) a1 2s1 - s2 - s3 r = A1 + E a1 (2pz) C3v E 2C3 3v A1 1 1 1 A2 1 1 -1 E 2 -1 0 3a1 s1 + s2 + s3 -17.0 eV x2+y2, z2 z 1e a1 (2s) -25.6 eV (x,y) -31.0 eV 2a1 Chem 104A, UC, Berkeley x z O H H y 2pz 1s -15.9 eV 2py H H Other: OL-, SL-, SeLFClBrI- 2px LGO 2s Lewis Base OL2, SL2, SeL2, TeL2 -32.4 eV O O 13 Chem 104A, UC, Berkeley Type of non-protic acid-base reactions: 1. Adduct formation: acid-base react to form a bond and produce a single molecule. 2. Displacement: one base (or acid) displace another 3. Double displacement (Metathesis): interchange of acids and bases Chem 104A, UC, Berkeley 14 x* * 104A, UC, Berkeley Chem y ' 2e1 * s 2a1' znb LUMO 2py 2px 2pz yb b x 1a LGO3 LGO2 '' 2 LGO1 1e1' 2s sb 1a1' B 3H BH3 Chem 104A, UC, Berkeley NH3 (C3v: E, 2C3, 3v) z 3H N NH3 H(3) H(1) H(2) 2e -13.5 eV 4a1 y x e - s2 + s3 -15.5 eV The symmetry of 3H’s group orbitals: e (2px, 2py) HOMO a1 2s1 - s2 - s3 r = A1 + E a1 (2pz) C3v E 2C3 3v A1 1 1 1 A2 1 1 -1 E 2 -1 0 3a1 s1 + s2 + s3 -17.0 eV z x2+y2, z2 1e a1 (2s) -25.6 eV (x,y) -31.0 eV 2a1 15 Chem 104A, UC, Berkeley Adduct formation AlCl3 Cl AlCl4 BH 3 CO H 3 B C O SO 3 Et 2O O3 S OEt2 Chem 104A, UC, Berkeley Displacement: one base (or acid) displace another A B B' A B' B F3 B SEt2 Et 2O F3 B OEt 2 SEt 2 Double displacement (Metathesis): interchange of acids and bases A B A' B' A B' A' B Me3 Si Cl F3 B F Me3 Si F F3 B Cl 16 Chem 104A, UC, Berkeley Relative strength of acid/base Reference acid H+,Mg2+, Sc3+ Hg2+ Base strength F Cl Br I F Cl Br I Chem 104A, UC, Berkeley Hard and Soft Acids and Bases (HSAB) Hard (class a): having contracted (tightly held) frontier orbitals Not readily polarized Soft (Class b): Having diffuse frontier orbitals Readily polarized 17 Chem 104A, UC, Berkeley Have vacant orbitals held in tight Have vacant orbitals, but larger radius Chem 104A, UC, Berkeley Have lone pairs in tightly held orbitals Have lone pairs in larger orbitals 18 Chem 104A, UC, Berkeley Table 1 Hard and Soft Acids and Bases Hard Bases H2O OH- FAcO- SO42- Cl- Soft Bases R2S RSH RSIR3P (RO)3P Borderline Bases ArNH2 C5H5N N3- Br- CO32- NO3 ROH CN- NO2- RO- R2O RNH2 NH3 RCN CO C2H4 C6H6 H- R- Hard Acids Soft Acids H+ Cu+ Li+ Na+ Borderline Acids Pd2+ Fe2+ Co2+ Cu2+ K+ Mg2+ Ca2+ Pt2+ Hg2+ BH3 Zn2+ Sn2+ Sb3+ Al3+ GaCl3 I2 Br2 CH2 carbenes Bi3+ BMe3 SO2 R3C+ NO+ GaH3 C6H5+ Cr2+ Fe3+ BF3 B(OR)3 AlMe3 AlCl3 AlH3 SO3 RCO+ CO2 HX (hydrogen-bonding molecules) Ag+ Chem 104A, UC, Berkeley Hard Bases (nucleophiles) Donor atoms have high electronegativity (low HOMO) and low polarizability and are hard to oxidize. They hold their valence electrons tightly. Soft Bases (nucleophiles) Donor atoms have low electronegativity (high HOMO) and high polarizability and are easy to oxidize. They hold their valence electrons loosely. Hard Acids (electrophiles) Possess small acceptor atoms, have high positive charge and do not contain unshared electron pairs in their valence shells. They have low polarizability and high electronegativity (high LUMO). Soft Acids (electrophiles) Possess large acceptor atoms, have low positive charge and contain unshared pairs of electrons (p or d) in their valence shells. They have high polarizability and low electronegativity (low LUMO) n.b “The HSAB principle is not a theory but a statement of experimental facts.” Pearson, R.G, Songstad, J.Amer.Chem.Soc., 1967, 89, 1827 19 Chem 104A, UC, Berkeley Pearson’s Principle: Hard acids prefer to bind to hard bases And soft acids prefer to bind to soft bases. Chem 104A, UC, Berkeley Keq CH3Hg CH3HgB BH H The simplest hard acid is the proton and methyl mercury cation is the simplest soft acid. Keq small B hard base Keq large B soft base I Br Cl S 2O3 2 S 2 PPh3 CN SCN SO3 NH 3 F OH 20 Chem 104A, UC, Berkeley Li-I +Ag-F H-F +Ag-I H=-17kcal/mol HgF2 +BeI2 HgI2 +BeF2 H=-95kcal/mol Chem 104A, UC, Berkeley Absolute Hardness IE EA ( ELUMO EHOMO ) 2 Hard: large HOMO-LUMO gap Soft: small HOMO-LUMO gap, ease of mixing ground/excited states, electron Density redistributed (polarized). 21 Chem 104A, UC, Berkeley Strong polar bond! Strong covalent bond! Chem 104A, UC, Berkeley Empirical approach to determine enthalpy of adduct formation A + B AB H E A EB C AC B E: susceptibility to undergo electrostatic interaction C: tendency to form covalent bonds 22 Chem 104A, UC, Berkeley Chem 104A, UC, Berkeley 23 Chem 104A, UC, Berkeley SO2 Me32 N Me3 N SO2 H (0.56 1.21 1.52 5.61) 9.2kcal / mol Experimental value: -9.6 kcal/mol 24