Stefan Svensson 2004

ACID and BASES - a Summary
Brönsted-Lowry : Acids donate protons

Bases accept protons

Lewis -acid : Electron pair acceptor

Lewis-base: Electron pair donator.

Acetic acid

O

O

CH3 C OH

ättiksyra

Aniline

NH2

+ H2O

CH3 C O

+ H2O

NH3

+

H3O

+

OH

Keq = [H 3 O+] [CH3 COO-]
[CH3 COOH][H2 O]

Acidity constant Ka:
Ka = K eq [H2 O] = [H3 O+] [CH3 COO-]
[CH3 COOH]

Ju starkare syra

-

= 1,76 x 10-5

pKa = -log Ka =4,76

ju svagare korresponderande bas.

Basstyrkan kan relateras till pKa för dess korresponderande syra.
Ju större pKa värde för korresponderande syra- ju starkare är basen.
Relative strength for some acids and their conjugate bases,
Strongest acid

Weakest acid

ACID
HSbF6
HCl
CH3COOH
CH3NH3+
H2O
(CH3)3COH
NH3
CH3CH3

Ex Lewis acids:
HCl, HNO3, HClO4

BF3

pKa
> -12
-7
4.8
10

Conj. BASE
SbF6ClCH3COOCH3NH2
OH-

15,7
18
33
50
AlCl3

Weakest base

(CH3)3CONH2CH3CH2TiCl4

Strongest base

ZnCl2

are complete ionised in water and appears to have the same
strength (the leveling effect of water)

compared with H-A The nature of the solvent CH3 H pKa ≈ 43 CH3 O H pKa ≈ 16 OH pKa ≈ 10 RCOOH pKa ≈ 4-5 A.2 F- < H-Br -7 > H2O < OH . CH3 C C H pKa = 25 + NH 2 NH 3 CH3 C C + NH 3 pKa = 33 .Bonding strength to the proton H-F pKa: 3.> B- H-Cl < < -9 Cl - > H2S SH - Br - < > H-I -10 > I- H2Se SeH - Increased acidity ⇔ decreased bonding strength Increased Basicity Higher acidity Increased Basicity Acidity increase with electronegativity CH4 < NH3 < R-OH < HF Electronegativity affect both polarity and the stability of the anion. Acidity increase with increased s-character in the hybridisation CH3 -CH3 < H2 C=CH 2 < HC≡CH Increased acidity sp3 sp2 sp pKa: ≈ 50 44 25 Increased s-character binds the electrons closer to the carbon nucleus More s-contribution ⇒ lower energy and higher anion stability Ex.Factors that influence the acidity of an organic compound H-A A B C D • • • • Examples The strength of the H-A bond The electronegativity of A Factors stabilising A.

8 OH Phenol: OH O O pKa CH3 CH2 OH 15. and can thereby stabilise and solvate both cations and anions The solvent must act as a base otherwise can not acids dissociate. Polar solvent with high dielectric constant (ε) have better ability to solvate ions Water is extremely effective as ion solvating medium and is readily polarised.C Lower pK a for Carboxylic acids than Phenols due to: Resonance structures of the anion have identical energy The anion contain two electronegative oxygen atoms O H C pKa ≈ 3.8 C O O O O O Cl CH2 C OH 2. Ex.9 H O C H O O pKa ≈ 10 O CH3 C OH 4.9 O Cl CH2 C O The negative charge is spread by electronwithdrawing and thereby stabilising the anion D. HCl is a strong acid in methanol but not in toluene. .

88 sp Hybridisation HC C COOH Stronger acid Electrons are drawn closer to unsaturated carbon nucleus .07 .76 6.6 Kcal Formic acid 3. Minor steric effects may count for the differences (pKa ≈ 4.Τ∆So and ∆Go = -2. For other short aliphatic acid (C3 -C5 ) are the differences in pKa small.5.ACIDS Aliphatic acids Alkyl groups can inductively decrease the acid strength Compare: acetic acid and formic acid pKa 4.77 O O Me H C C O O But often depends differences in relative solvation possibilities of ionisation.5.25 sp2 1.larger s contribution This change the inductive effect from donating to withdrawing when sp3 → sp.05) CH3 CH2 COOH pKa 4.1 -0.303 RT log K eq pKa ∆Go ∆Ho Τ∆So Acetic acid 4.ethyne .6. Differential solvation of the acid anions makes the acid strength to differ. Formiat ion is stronger solvated. Entropy has a greater effect Through solvation of the ions by water molecules is the orderliness increased. ∆Go = ∆Ho .5 -0. Similar to acidities in the serie: ethane .ethene.77 5.76 versus 3.80 .88 sp3 CH2 CH COOH 4.13 .17 Kcal Low enthalpy The energy required for dissociation of the O-H bond is canceled by the energy evolved in solvating the resultant ions.

86 O C OH O C OH 3.95 10.6-(O2 N)3 C6 H4 OH pKa 9.4-(O2 N)2 C6 H4 OH 2.Substituted aliphatic acids CH3 O C OH 4.95 7.08 10. The anionic charge gets more concentrated as the EW-substituent is situated further apart ⇒ increased ∆S Phenols The Inductive effect falls off with distance from orto > meta > para. The changes in pKa and then free energy is largely due to entropy factor also here.16 O Cl Cl C C OH Cl 0.65 Inductive effects ( electron withdrawing.19 O .90 O CH C OH 2. but is also combined with mesomeric effect which affect primary at orto.25 I CH2 2.and para-positions. Alkyl groups have only marginal effects.86 O C OH Cl Cl 1.02 O O N O N O O With more powerful EW groups the negative charge gets delocalised ⇒ decreased ∆S (solvation can be less ordered) ⇒ lower pKa. Entalphy differ only little with different substituent.14 4.76 O C OH F CH2 Cl CH2 2.35 7. The water can be less ordered to solvate the ions. Methyl pKa C6 H5 OH o-MeC6 H4 OH m-MeC6 H4 OH p-MeC6 H4 OH 9.57 Cl CH2 O C OH Br CH2 2.01 1. C6 H5 OH o-O2 NC6 H4 OH m-O2 NC6 H4 OH p-O2 NC6 H4 OH 2.28 10.4.23 8. EW) delocalise the negative charge over the whole of the anion.

58 O O C O O C C X X N O O EW-groups increases the acid strength. or as few cases with intra-molecular hydrogen bonding C O H O O .17 3.09 4.34 2.08 4.85 3.94 3.23 O COOH C H O H H O C HOOC H Fumaric acid pKa1= 3. Phenyl as double bond is less electron donating than saturated acids.99 O O Br OMe OH 2.02 pKa2= 4. mesomeric effect may also decrease strength.groups may have both inductive (EW) and mesomer effect (ED) depending on position.09 2. As the entropy has a major effect on pKa:s also temperature influences the value of pKa.38 For malic and succinic acid is pKa2 higher as the first COO. Donating.81 4.87).43 2.23 2.98 4.effect of the second COOH falls off sharply as the COOH-groups are separated more than one saturated carbon. O Orto groups may also besides short inductive distance act through space.45 3. .20 4.Aromatic carboxylic acid Benzoic acid pKa 4. The effect can give a weaker acid also.83 4. Maleic acid has a low pK a1 compared with fumaric acid due to intra molecular Hbonding. pKa of X-C6 H4 COOH H Me NO2 Cl 4. O H C C O O H C H C O -H - H C C C H Maleic acid C O pKa1= 1.20 4.20 is stronger than the saturated acid ( 4.47 4.group is Elect.H+ H C H O O Again is the ∆S term most important for the pKa value.00 4. HO and MeO.92 pKa2= 6.24 4. which on the other hand also makes pKa2 higher due to stabilisation. Dicarboxylic acids pKa 1.83 3.20 4.19 HOOC-COOH HOOC-CH2 -COOH HOOC-CH2 -CH2 -COOH The inductive EW.

H2O H R N H2O H H O2H > H2O H R N H2O H R > H2O H R N R R Decreasing stabilisation by solvation Increasing electron-donating inductive effect on basicity In solvent where ions are not solvated by H-bonding is the order of base strength the same as the inductive effect of the alkyl groups.80 Et NH 2 Et NH Et 10. The more hydrogen atoms attached on nitrogen the more powerful solvation via Hbonding between these and water. Aliphatic bases pKa: NH3 Me NH 2 Me NH Me 9.93 Et Et N Et 10 88 Alkyl groups on ammonia increases the base strengthThe first one markedly.4 + H3 O+ Τ∆So 0. Not only electron availability on the nitrogen also solvation of the cation must be stabilised.64 10.67 10.BASES More convenient to use pKa also for bases Ka = [B] [ H3 O+ ] [ BH+ ] The smaller value of pKa for BH+ the weaker B is as a base NH4 + +H2 O NH3 ∆Go 12. Tertiary amines less easily solvated.77 Me Me N Me 9.25 10. the second slightly but the third actually decrease base strength. ∆S is low as both sides has the same kind of ions.25 ∆Ho 12.2 Kcal Enthalpy changes are more important than entropy changes. equally solvated. In chlorobensen or gas phase: But NH2 < But 2 NH < But 3 N .6 pKa 9.

and the main effect on the base strength is the mesomeric stabilisation of the aniline molecule with respect to the cation. NO2 CF3 F3 C F3 C N F3 C O R C O C N C O O NH 2 R C NH 2 H acidic H Amide nitrogens are non basis due to mesomeric EW effect (pKa ≈ 0. with two carbonyls . Pthalimide. R4 N+ OH.6 (Compare with cyclohexylamine pKa 10.84 4.15 5.10 p-Me-C6 H4 NH 2 Alkyl groups do only effect little whatever position. .EW inductive groups reduce the base strength: Cl.6 and protonation gives three exactly equal resonance structures. Ph2NH pka ≈ 0. In protonated form is this stabilisation not available.67 m-Me-C6 H4 NH 2 C6 H5 NMe2 5.7) Unshared electrons on N can interact with the delocalised π-electrons in the ring.as a ion pair has a base strength alike alkali bases Guanidine has pKa of ≈ 13.5).62 4. is acidic and non-basic.8 and Ph3N is not basic at all. Anilines NH 2 NH 2 NH 2 NH 2 NH 2 H NH 2 + H pKa ≈ 4. pKa Alkyl groups C6 H5 NH 2 4.38 o-Me-C6 H4 NH 2 C6 H5 NHMe 4.

3 (sp).17 p. the electron are drawn closer to the nitrogen nucleus. Hybridisation + N N H N N R3 N > > RC N N (A) N H H N H (B) H N H (C) Base strength Pyrrole (B) have aromatic character..4. because the orto groups inhibit resonance interaction by steric reason.5.28 m.3 resembling of diethylamine. α-Carbons is more basic.substituted anilines. which gives a weaker base. Hetrocyclic bases Pyridine (A) aromatic (sp2) pKa 5.Ex Nitro.2 less basic than ex. Compare also MeCN pKa ≈ -4.4.N-dimethylaniline or 2.4. Pyrrolidine (C) on the other hand have pKa ≈11. .4.29 o.6-trinitro-aniline.N-dimethyl aniline is much more stronger base than N.20 p.72 m.45 p. triethylamine (sp3) As nitrogen becomes more multiply bonded its lone pair of electrons is accommodated in an orbital with more s character.0. H H O O N O N N O O CH3 O N N N O CH3 O N O Stronger base N O O O 2.5.4.hydroxy.2.6-trinitro-N. the electron pair is incorporated in the aromatic 6 π-system. C6 H5 NH 2 4.and methoxy.0.30 NH 2 NH 2 NH 2 N OMe OMe O Orto position gives greatest effect due to strongest inductive effect but also by direct interaction by steric and H-bonding.49 m.98 NH 2 N O O O HO-C6 H4 NH 2 MeO-C6 H4 NH 2 o.4.62 O2 N-C6 H4 NH 2 o..