ACIDS AND BASES

- Arrhenius review
- Bronsted and Lowry:
- Acids are proton donors
- Bases are proton acceptor
 Proton = H+

- In Arrhenius time no covalent bonding

- HA + H2O   H+3O + A-
Acid Hydronium
- H 3O  
+
A- + H+
- NaOH  water  Na+ + OH-

Figure 1

Acoridng to Arrhenius ammonia is not a base, but according to Brosted it is a base

- Single compound behaving as an acid or base under certain circumstances = AMPHOTERIC

- Water is amphoteric

THEORY OF CONJUGATION:

- In acid/base reaction – products are conjugate base / conjugate acid

- Conjugate acid:
 Belongs to base
 One more Hydrogen than its base
 One more + charge than its base
 One less – charge than its base
- Conjugate base:
 Belongs to acid
 One less Hydrogen than its acid
 One less + charge than its acid
 One more – charge than its acid
- Figure #2

Lewis:

- Bases are electron lone pair donor

- Acceptor of the lone pair = acid
 - This theory is very wide, “bases are electron pair donor”, wherever and not necessarily a proton
like Bronsted said
- If there is electron deficit inside… donated in pair! Pair acceptor = formation or breaking of bond
because it is an orbital

- Oxyacid: hydrogen oxidizes

- Oxidation state

- Number of oxygens atoms minus the number of ionizable hydrogens

- if 2 or more: strong acid- 1 or less weak acid
- Number of groups of COOH increases acid strength also increases
- Figure #3
- Lone pair or a pi bond is indication of electron density

- Strong acid dissociates completely - Ka becomes large –

- No HA, thus denominator becomes 0

- Weak acid dissociates partial – large denominator due to greater number of HA

- Smaller the pka number the stronger the acid

- Strong acids have weak conjugate bases
- Weak acids have strong conjugate bases
- S pka increases acidic strength decreases…. 1:04 ‘ !!!!!! important for multiple choices

FACTORS THAT DETERMINE ACID STRENGTH

- Anything that stabilizes conjugate base (A:-) makes the starting acid H-A more acidic

ELEMENTAL EFFECTS:

- Left to right on P.T. electronegativity increases

- As it increases ionization of OH becomes much easier
- Ex. C-H N-H O-H X-H
- Electronegativity increases, bond length decreases, higher electronegativity, H loses
- Electrons spend more time trying to be electronegative 1 hr 12 min

- Down the group

- Electronegativity decreases
- Acid strength size of F -> Cl -> I , size of anion increases to the extent that iodine becomes polar
 - Therefore, I is solid at R.T.
- Size of anion increases therefore acidity increases!
- C-H pka ~ 50
- N-H pka ~ 38
- O-H ~16
- X-H (F) pka 3.2
- Down the group:
- H-Cl -7
- H-Br -9
- H- -10
- Listen to this part!!

INDUCTIVE EFFECTS:

- Strong acid can easily be ionized

- Electron density is pulled
- Inductive effect relates to ability to
- Pull electron density – through sigma bond
- Figure #4

From picture plus figure #5

- Negative charge – electron density – is localized on oxygen – no resonance

- Negative charge and electron density is delocalized because of resonance, stabilizes the
conjugate case
- Acidity of CH3COOH is increased, stronger than ethanol.

HYBRIDIZATION EFFECTS

Fugure #6

- Increased % character  bond strength  decrease the bond length  increase the stability of
conjugate base  increases acidity

Common acids used

- HCl, H2SO4 AND HNO3 , COMMONLY USED….

MISSED HIS NOTES

T5oh

***back from notes

- Lewis Acids and Bases

- Figure #8
- Leis acid is an electron pair acceptor – no proton involved
- Lewis acids must be able to accept an electron pair
- All B & L acids are lewis acids also but reverse is not necessarily true

LEWIS ACIDS

- Like BF3 and AlCl3

o Are free to accept lone pair to complete octet
- H2O and CH3OH
- Are both B & L and Lewis acids
- But BF3 and AlCl3 are Lewis Acids
- Fugure #9
- Leis acid is also called an electrophile

LEWIS BASE is also called nucleophile

Figure#10

STEPS:

- Identify Lewis Acid and Base

- Draw a curved arrow from lone pair of the base to the electron deficient atom of the acid
- Count electron pair and break a bond when needed to correct the number of valence electrons
- Figure #11
-