Arrhenius theory HCl(g) H+(aq) + Cl-(aq) NaOH(s) Na+(aq) + OH-(aq) Na+(aq) + OH-(aq) + H+(aq) + Cl-(aq) H2O(l) + Na+(aq) + Cl-(aq)

aq) H+(aq) + OH-(aq) H2O(l) Arrhenius theory did not handle non OHbases such as ammonia very well.
H2O H2O

Brnsted-Lowry Theory of Acids and Bases

An acid is a proton donor. A base is a proton acceptor.

cid ase ate a ugate b g u j con conj

base

acid

NH3 + H2O NH4+ + OHacid base

NH4+ + OHNH3 + H2O ?? ??

base

acid

conjugate conjugate base acid

NH3 + H2O Kc=

NH4+ + OH-

[NH4+][OH-] [NH3][H2O] [NH4+][OH-] = 1.810-5 [NH3]

Kb= Kc[H2O] =

acid

base

conjugate base

conjugate acid

CH3CO2H + H2O Kc=

CH3CO2- + H3O+

[CH3CO2-][H3O+] [CH3CO2H][H2O] [CH3CO2-][H3O+] = 1.810-5 [CH3CO2H]

Ka= Kc[H2O] =

base

acid

conjugate conjugate base acid

H2 O + H 2 O

H3O+ + OH-

Kc=

[H3O+][OH-] [H2O][H2O]

KW= Kc[H2O][H2O] = [H3O+][OH-] = 1.010-14

The potential of the hydrogen ion was defined in 1909 as the negative of the logarithm of [H+]. pH = -log[H3O+] pOH = -log[OH-]

KW = [H3O+][OH-]= 1.010-14 -logKW = -log[H3O+]-log[OH-]= -log(1.010-14) pKW = pH + pOH= -(-14) pKW = pH + pOH = 14

HCl

CH3CO2H Acetic Acid

Thymol Blue Indicator pH < 1.2 < pH < 2.8 < pH Lactic Acid Glycine

Acetic Acid

Ka=

[CH3CO2-][H3O+] = 1.810-5 [CH3CO2H] pKa= -log(1.810-5) = 4.74

Kb=

[CH3NH3+][HO-] = 4.310-4 [CH3NH2] pKb= -log(4.210-4) = 3.37

CH3CO2- + H2O
base acid

CH3CO2H + OH[NH3] [H3O+] [NH4+] 1.010-14 1.810-5 =?

NH4 + H2O
+

acid

base

NH3 +

H3O+

Ka=

Ka=

[NH3] [H3O+] [OH-] [NH4

+]

[OH-]

KW Kb

= 5.610-10

K a K b = Kw

Determining a Value of KA from the pH of a Solution of a Weak Acid. Butyric acid, HC4H7O2 (or CH3CH2CH2CO2H) is used to make compounds employed in artificial flavorings and syrups. A 0.250 M aqueous solution of HC4H7O2 is found to have a pH of 2.72. Determine KA for butyric acid.

Solution: For HC4H7O2 KA is likely to be much larger than KW. Therefore assume self-ionization of water is unimportant. HC4H7O2 + H2O C4H7O2 + H3O+ 0 +x M xM 0 +x M xM

HC4H7O2 + H2O

C4H7O2 + H3O+

Initial conc. Changes Equilibrium Concentration

0.250 M -x M (0.250-x) M

Ka = ?

HC4H7O2 + H2O Log[H3O+] = -pH = -2.72 [H3O+] = 10-2.72 = 1.910-3 = x [H3O+] [C4H7O2-] [HC4H7O2]

C4H7O2 + H3O+ HA + H2O Degree of ionization = H 3 O+ + A[H3O+] from HA [HA] originally

Ka=

1.910-3 1.910-3 (0.250 1.910-3)

Percent ionization =

[H3O+] from HA [HA] originally

100%

Ka= 1.510-5

Check assumption: Ka >> KW.

Phosphoric acid: A triprotic acid.

Ka1 >> Ka2

All H3O+ is formed in the first ionization step.

H2PO4- essentially does not ionize further.

H3PO4 + H2O H2PO4 + H2O
-

H3O+ + H2PO4H3 O+ + HPO4

2-

Ka = 7.110-3 Ka = 6.310-8

Assume [H2PO4-] = [H3O+].

[HPO42-] Ka2 regardless of solution molarity.

HPO42- + H2O

H3O+ + PO43-

Ka = 4.210-13

Calculating Ion Concentrations in a Polyprotic Acid Solution. For a 3.0 M H3PO4 solution, calculate: (a) [H3O+]; (b) [H2PO4-]; (c) [HPO42-] (d) [PO43-]

H3PO4 + H2O Initial conc. Changes Equilibrium Concentration 3.0 M -x M (3.0-x) M

H2PO4- + H3O+ 0 +x M xM 0 +x M xM

H3PO4 + H2O [H3O+] [H2PO4-] [H3PO4]

H2PO4- + H3O+ xx (3.0 x) Initial conc. = 7.110-3 Changes Equilibrium Concentration x = 0.14 M Ka=

H2PO4- + H2O 0.14 M -y M (0.14 - y) M

HPO42- + H3O+ 0 +y M yM 0.14 M +y M (0.14 +y) M

Ka=

Assume that x << 3.0 x2 = (3.0)(7.110-3)

[H3O+] [HPO42-] [H2PO4

-]

y (0.14 + y) (0.14 - y)

= 6.310-8

[H2PO4-] = [H3O+] = 0.14 M

y << 0.14 M

y = [HPO42-] = 6.310-8

HPO4- +

H2O

PO43- + H3O+ Sulfuric acid: A diprotic acid.

Ka=

[H3

O+ ]

[HPO4

2-]

[H2PO4-]

(0.14)[PO4 6.310-8

3-]

= 4.210-13 M

[PO4

3-]

1.910-19

H2SO4 + H2O HSO4- + H2O

H3O+ + HSO4H3O+ + SO42-

Ka = very large Ka = 1.96

Lewis Acid
A species (atom, ion or molecule) that is an electron pair acceptor.

Lewis Base
A species that is an electron pair donor.

base

acid

adduct