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Strc Effcts, AcidBasesGstud

Strc Effcts, AcidBasesGstud

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Published by Karl Calilung

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Published by: Karl Calilung on Sep 19, 2012
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09/19/2012

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Structural Effects

 electron delocalization (Resonance)
CH2 .. CH Cl : ..
.. O C .. .. NH 2 .. NH 2

.. Cl : ..

:O: CH3 C .. O H ..

Structural Effects
 electron delocalization (Resonance)

Structural Effects
 electron delocalization (Resonance)

Structural Effects  electron delocalization (Resonance) :O: H :O: C H . NH2 .... :O N+ . :O: .

..Hyperconjugation Structural Effects H H C CH CH 2 H H H + H C CH CH2 .H C CH CH2 H + H ..+ H C CH CH2 H H .- .

Structural Effects Hyperconjugation Dienes CH2 CH CH CH2 cumulative conjugated isolated .

.Structural Effects Hyperconjugation H H C H - H C H . + H + H H C H .. - .

Structural Effects Hyperconjugation H H C C H O H H H + H C C O H - O O .

Structural Effects + CH 3 CH 3 + CH 2 + CH 2 H 3C CH3 C + CH 3 - H :CH 3 O2N C: H H 3 - . CH C. H .

Inductive Effect with excess positive charges R N R R + + Structural Effects Electron attracting inductive effect NH 3 + NO2 those with electronegative atoms NH 2 OH OCH 3 F Cl Br groups exhibiting orbital electronegativity C N N N those with easily polarizable valence electrons I - .

Inductive Effect   Structural Effects Electron attracting inductive effect H3C Cl  CH3  CH2  Cl CH3 H3C N CH3 -+ CH3  CH2  O H  .

Inductive Effect alkyl groups CH3 negative groups COO - Structural Effects Electron repelling inductive effect S - O - O H3C C O -- H3 C S - H 3C CH C N H 3C O R C O C O O R S O O O O .

Steric Effect Structural Effects .

Hydrogen Bonding F O N Structural Effects F O N H H H    H  H  H  H R H O H H O H OH OH O O H O O R F O H H R C O H O C R H C O O H .

Acids and Bases Brønsted–Lowry Acids and Bases • An acid is a proton donor • A base is a proton acceptor HBr + H2O Br + H3O acid base NH4 + OH NH3 + H2O base acid Note that water can act as an acid or a base .

Acids and Bases Brønsted–Lowry Acids and Bases HBr + H2O Br + H3O HBr + H O H Br + O H H H acid base conjugate base conjugate acid Every acid–base reaction involving proton transfer has two conjugate acid–base pairs. .

(think empty orbital) A Lewis base is an electron pair donor. .Acids and Bases Lewis Acids and Bases • A Lewis acid is an electron pair acceptor. (think filled orbital) The result of a Lewis acid–base reaction is often called an adduct.

Acids and Bases Lewis Acids and Bases H O O H + H H H H Lewis acid Electron deficient Lewis base Electron rich Adduct New covalent bond .

Acids and Bases Lewis Acids and Bases Examples of Lewis Acids: Fe3+ AlCl3 H3O+ Examples of Lewis Bases: NH3 H2O Cl  .

Acids and Bases .

Acids and Bases • pH = – log[H3O+] HA + H2O A A + H3O Ka = H3O HA pKa = – log (Ka) .

base (lower energy) AHA ionization easier . base (higher energy) STRONG ACID Has a weak conj.Acids and Bases Acid Strength HA + H2O H3O+ + AE N E R G Y A- WEAK ACID Has a strong conj.

Acids and Bases .

Acids and Bases Acid Strength • Factors that influence stability of the conjugate base include: – – – – – Resonance Electronegativity Atomic Size Hybridization Inductive Effects .

Acids and Bases Resonance Effects increasing quality of resonance pKa Values 18 R OH R CH3 CH3 45 R NH2 28 30 NH2 25 OH 10 O CH3O C CH3 25 O O R C OH 5 O R C CH3 O O 20 R C NH2 15 R C CH2 C R 9 .

• The Acetate Ion O CH3 C OH -H+ Base Acids and Bases O CH3 C O acetic acid O CH3 C O acetate ion Resonance Stabilized Equivalent structures (charges on oxygens) .

• The Phenolate Ion O O O Acids and Bases O O O More resonance structures. but not more stable than acetate Nonequivalent structures (note charges on carbon and oxygen) .

Acids and Bases increasing electronegativity Electronegativity pKa Values O CH4 >45 RCH3 45 R C CH3 20 O NH3 H2O HF 34 16 3.5 RNH2 35 ROH 18 R C NH2 15 O R C OH 5 .

81 Å H2O H2S H2Se H2Te 16 7 4 3 R C OH O R C SH S R C SH HBr Br– 1.36 Å 1.16 Å .Acids and Bases increasing size Electronegativity pKa Values O HF HCl 3.95 Å I– HI 2.5 –7 –9 –10 F– Cl– 1.

CH3. Si electronegative elements alkyl groups and elements less electronegative than carbon pull electron density push electron density toward carbon away from carbon . B. N R. O.Acids and Bases Inductive Effects Electron-withdrawing Groups Electron-donating Groups  Cl  C  CH3  C F. Cl. Br.

Acids and Bases Inductive Effects Chlorine helps to stabilize – CO2– by withdrawing electrons  Cl  O C O This effect diminishes with distance—it extends for about 3 bonds       Cl C C C O O .

13 increasing substitution I Br Cl CH2COOH CH3 Cl COOH 4.87 CH2COOH 2.81 1.65 .81 CH2 Cl COOH 2.29 Cl Cl CH Cl C Cl COOH COOH F CH2COOH 2.66 0.75 CH2COOH 2.Acids and Bases increasing electronegativity Inductive Effects pKa Values 3.

pair acceptor  electron poor Electrophiles R R C+ R : CH2 R. NO2+ R C+ O X2 in protic solvent X O R C O OH AlCl3  AlCl4 CO2 H2O SO3 SO3H +  CH3 H+ BF3 FeBr3 .  may possess formal positive charge  incomplete octets  greatly reduced e. e.density  those that can yield e.poor species + X.

pair donor  excess negative charges  fractional negative charges OHROX- CN-  may have a lone pair e- R R C: R R O C O- NH2N3- O- .Nucleophiles  e.

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