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Acidbase
Acidbase
172
thinker
Acid
Base
acid-base reaction
1884
Arrhenius
ionize
H+
ionize
OH
H+ + OH = HOH
1923
BronstedLowry
Proton
Donor
proton
acceptor
HA + B = HB + A
conjugation
1923
Lewis
electrophil nucleophil
E + Nu = E:Nu
179
Relative strengths
of acids and bases
HClO4
ClO4
H2SO4
HSO4
HI
I
HBr
Br
The stronger the acid, the
HCl
Cl
weaker its conjugate base.
HNO3
NO3
H3O+
H2 O
HClO ClO
HSO4
SO42
HBrO
BrO
NH4+ NH3
H2SO3
HSO3
HCN
CN
H3PO4
H2PO4
HCO3 CO32
HNO2 NO2
H2O2 HO2
HF
F
HS
S2
HC2H3O2
C2H3O2
H2O
OH
Al(H2O)63+
Al(OH)(H2O)52+
ROH RO
H2CO3
HCO3
9
174 & 175 Table
17 Acid and Base
H2S 173
HS
10
11
Self-ionization of water
Water molecules autoionize
2 H2O (l) = H3O+ (aq) + OH (aq)
[H3O+] [OH]
Kc =
[H2O] (= 1000/18 = 55.6)
Kw = [H2O] Kc = 1e14 only at 25oC, its T dependent.
The ion product, Kw increases as T increases, and its value remains
the same in the presence of acid or base.
The molecule of life, H2O, and its acidity.
17 3
12
13
Strong Bases
HI
Oxyacids of halogens
HClO3 HBrO3 HIO3
HClO4 HBrO4 HIO4
Other oxyacids
H2SO4 HNO3
17 4
14
Neutralization Reactions
The neutralization reaction between strong acids and strong bases
has the net ionic reaction
H3O+ (aq)+ OH (aq) = 2 H2O
The anions are bystander ions. They do not participate the reaction.
These ions are
I, Br, Cl, NO3 , HSO4 , CClO4 , Na+, K+, Cs+, Ca2+
etc.
When dried, the ions left behind in neutralization reactions form salts.
15
The pH scale
Sorensen introduced the pH scale in 1909 using the symbol p H.
The p is from the German word potenz, power of (10).
pH = log [H+];
pOH = log [OH];
pK = log [K];
[H+] = 10 pH
[OH] = 10 pOH
K = 10 pK
0.9
0.13
16
17
Neutrality
In a neutral solution, [H+] = [OH]. (Different from Fig. 17-5)
In an acidic solution, [H+] > [OH], and a basic solution, [H+] < [OH].
18
19
Acid-Base Equilibria
Strong acids and bases completely ionize in their aqueous solutions.
HCl H+ + Cl
KOH K+ + OH
Weak acids and bases ionize but not completely in their solutions.
HCH3COO H+ + CH3COO acetic acid, vinegar spirit
HNic H+ + Nic
HNic = Niacine, C5NH5COOH, a water-soluble vitamin required by the body for
health, growth and reproduction; part of the vitamin B complex. It was first prepared in
pure form by oxidizing nicotine using conc. HNO3. Nicotine is a major chemical in
tobacco .
CH3
N
<= Nicotine
Niacine =>
Vitamine B3
COOH
20
Caffeine
Caffeine C8H10N4O2 is a weak
base, (pH of 1% soln 6.9)
taste bitter smell like tea, a
cardiac stimulant, (boost of
energy), mild diuretic, addictive,
operates using the same
mechanisms that amphetamines,
cocaine and heroin use to
stimulate the brain.
Crystals are hexagonal prisms by
sublimation, mp 238C. Sublimes
178. Fast sublimation is
obtained at 160-165 under
1 mm Hg pressure.
Many organic bases are
interesting drugs, and their
chemistry is fascinating.
21
[H+] [A]
Ka =
[HA]
A = CH3COO (acetate)
Ka acid ionization constant, important for an acid
Ka equilibrium constant with solvent effect
Ka = 10 pKa
22
HCOOH
CH3COOH
CCl3COOH
HF
HCN
H2S
H2O
Conjugate acids
of weak bases
NH4+
NH3
N(CH3)3
C5H5N
NH4OH
H2O
HS-
conjugate bases of
weak acids e.g.:
HCOO-
23
24
Application of Ka
The Ka of nicotinic acid, HNic, is 1.4e-5. A solution containing 0.22
M HNic. What is its pH? What is the degree of ionization?
Solution:
HNic = H+ + Nic
0.22-x
x
x
x2
Ka = = 1.4e-5
0.22 x
(use approximation, small indeed)
x = (0.22*1.4e-5) = 0.0018
25
pH of a weak acid
The pH of C M acid HA (Ka) solution.
Method:
HA =
C-x
H + + A
x
x
x2
Ka =
Cx
x 2 + Ka x C Ka = 0
Ka + Ka2 + 4 C Ka
x =
2
pH = log x
y2
Kb =
Cy
y 2 + Kb x C Kb = 0
Kb + Kb2 + 4 C Kb
y =
2
pOH = -log y
26
x 2 + Ka x C Ka = 0
Ka + Ka2 + 4 C Ka
x =
2
x2 + 1.4e-5 x 1.4e-8 = 0
Deg.f ionizn
0.22
0.012
0.001
0.79%
3.4 %
11.1 %
27
Deg.f ionizn
0.22
0.012
0.001
0.79%
3.4 %
11.1 %
Concentration of acid
17 Acid and Base
28
Polyprotic acids
Polyprotic acids such as sulfuric and carbonic acids have more than
one hydrogen to donate.
H2SO4 = H+ + HSO4
HSO4 = H+ + SO42
H2CO3 = H+ + HCO3
HCO3 = H+ + CO32
Ka1 = 4.3e-7
Ka2 = 4.8e-11
29
Aspartame nutrasweet
A dipeptide methyl ester :
L-aspartyl-L-phenylalanine methyl ester
C14H18N2O5 (molar mass = 294.31)
Aspartame has two ionizable protons
30
HSO4
0.10-y
completely ionized
SO42
y
Ka2 = 0.012
Assume y = [SO42]
HSO4 = H+ +
0.10y
0.10+y
(0.10+y) y
= 0.012
(0.10-y)
[SO42] = y = 0.01M
[H+] = 0.10 + 0.01 = 0.11 M;
[HSO4] = 0.10-0.01 = 0.09 M
Y2 + 0.112 y 0.0012 = 0
- 0.112+0.1122 + + 4*0.0012
y = = 0.0098
2
= H+
x+y
HS
x-y
+
S2
y
(x+y) (x-y)
= 1.02e-7
(0.10-x)
[H2S] = 0.10 x = 0.10 M
[HS] = [H+] = x y = 1.0e4 M;
[S2] = y = 1.0e-13 M
See Example 16.4
Ka1 = 1.02e-7
Assume x = [HS]
Ka2 = 1.0e-13
Assume y = [S2]
(x+y) y
= 1.0e-13
(x-y)
0.1>> x >> y:
x+ y = x-y = x
x = 0.1*1.02e-7 = 1.00e-4
y = 1e-13
32
Beware of Misconceptions
These equations show dynamic equilibria at the molecular level in a
system. These equations are not separate reactions, but they
indicate possible combination and dissociation in both directions.
H2S = H+ +
HS Ka1 = 1.02e-7
HS = H+ +
S2
H2O = H+ +
OH- Kw = 1e-14
Ka2 = 1.0e-13
H2S(g)
HS
H2 S
OH- +
H2O
+
H
+
H
H
OH
H2 O H S
H
O
+
2
H2S
H
H2O
2
22S
OH
OH
S
2S
HS17 Acid and Base
33
Base-ionization constant
For a base BOH,
For acid, HA
BOH = B+ + OH
HA = H+ + A
[B+] [OH]
Kb =
[BOH]
The pKb is defined similar to pKa
pKb = log Kb,
Kb = 10
pKb
[H+] [A]
Ka =
[HA]
The pKa is defined similar to the pH,
pKa = log Ka
Ka = 10 pKa
From slide 3
June 18
34
Formula
NH3
C6H5NH2
(CH3)2NH
C2H5NH2
N2H4
H2NOH
CH3NH2
C5H5N
NH2CONH2
Kb
1.8e-5
4.2e-10
5.1e-4
4.7e-4
1.7e-6
1.1e-8
4.4e-4
1.4e-9
1.5e-14
35