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+
(aq)
+ OH
(aq)
H 2 O (l )
ACIDS donates H+
Bronsted-Lowry Definition
H 2O(l) + NH3(g) OH -(aq) + NH +4(aq)
ACIDS donates H+
(proton donor)
BASES accepts H+
(proton acceptor)
Amphoterism:
Species that can behave as an acid or base are
called amphoteric.
Amphiprotic: special term for an amphoteric
species which involves proton transfer reactions
to show behavior as either an acid or base
HPO42- + H2O H2PO4- + OHHPO42- + H2O PO43- + H3O+
Zn(OH)2 + 2 OH Zn(OH)
-
24
Lewis Definition
NH
base
+ H 2O
NH
+ OH
acid
NaF + BF 3
base
+
4
Na
+ BF
acid
Equilibrium-constant expression:
H+
Experimental concentration is
determined to be 1.00x10-7 at 25oC,
therefore:
[H 3O + ][OH- ]
Kc =
[H 2O]2
K c K w = [H 3O + ][OH- ]
K w = (1.00x 10-7 )(1.00x 10-7 )
K w = 1.00x 10-14 at 25o C
Proof:
-log Kw = -log [1.00 x 10-14] = -log ([H+][OH-])
-log Kw = 14.00 = -log[H+] + -log[OH]14.00 = pH + pOH
Calculate the [H3O+], pH, [OH-], and pOH for a 0.020 M HNO3
solution.
Is HNO3 a weak or strong acid?
What is the [H3O+] ?
100%
HNO 3 + H 2 O
H 3 O + + NO 3-
0.020M
[H O ] = 2.0 10
pH = -log(2.0 10
+
pH = 1.70
0.020M 0.020M
The weaker the acid or base, the stronger the conjugate partner.
The stronger the acid or base, the weaker the conjugate partner.
STRONGER
ACID and BASE
WEAKER
ACID and BASE
[H 3 O ][CH 3 COO ]
Kc Ka =
[CH 3 COOH]
[H 3 O ][CH 3 COO ]
Kc Ka =
[CH 3 COOH]
[OH ][NH 4 ]
Kc =
[NH3 ][H 2O]
[OH ][NH 4 ]
Kb =
[NH3 ]
HA
H+
A-
B- + H2O OH- + BH
[H ][conjugate base]
Ka =
[acid]
[OH ][conjugate acid]
Kb =
[base]
The ionization constant values for several acids are given below.
Which acid is the strongest?
Acid
Formula
Ka value
Acetic
CH3COOH
1.8 x 10-5
Nitrous
HNO2
4.5 x 10-4
Hydrofluoric
HF
7.2 x 10-4
Hypochlorous
HClO
3.5 x 10-8
Hydrocyanic
HCN
4.0 x 10-10
CH 3COOH + H 2 O H 3O + CH 3COO
[
H O ][CH COO ]
=
= 1.8 10
+
Ka
[CH 3COOH]
CH 3 COOH + H 2 O
H 3 O + + CH 3COO Initial [ ]
0.15M
Change
- xM
Equilibrium [ ] ( 0.15-x)M
+ xM
+ xM
+ xM
+ xM
If
1.0 10 , the simplifying assumption is valid
[
CH COO ]
% ionization =
-
equil
[ ]
or H +
[CH3COOH]original
equil
100%
1.6 10 3 M
% ionization =
100% = 1.1%
0.15M
Ka
1.8 x 10-5
[H+]
1.6 x 10-3
pH
2.80
% ionization
1.1
0.15 M HCN
5.11
0.0051
Kw = Ka x Kb
Kw
Kw
Kb =
Ka
Kw
Ka =
Kb
4.5 x 10-4
1.8 x 10-5
3.5 x 10-8
4.0 x 10-10
2.9 x 10-7
2.5 x 10-5
5.6 x 10-10
Kw
Kb =
Ka
H3PO4
+7
Polyprotic Acids/Bases
Many weak acids contain two or more acidic hydrogens.
Examples include H3PO4 and H3AsO4.
+
H 2 CO 3(aq) + H 2 O (l) HCO3(aq)
+ H 3 O (aq)
2+
HCO3(aq)
+ H 2 O (l) CO 3(aq)
+ H 3 O (aq)
2
CO3(aq)
+ H 2 O(l) HCO3(aq)
+ HO(aq)
HCO3(aq)
+ H 2 O (l) H 2 CO3(aq) + HO(aq)
K a1
K b1
Kw
K a2
K b2
K a1 = 4.4 x 10 -7
K a2 = 4.7 x 10 -11
K b1 = 2.1 x 10-4
K b2 = 2.3 x 10-8
+
H3PO4(aq) + H2O(l) H2 PO-4(aq) + H3O(aq)
+
H2 PO-4(aq) + H2O(l) HPO24(aq)
+ H3O(aq)
24(aq)
HPO
+ H2O(l) PO
34(aq)
+
(aq)
+ H 3O
Ka3 = 3.60 x 10
-13
PO 34(aq)
+ H 2 O (l) HPO 24(aq)
+ HO (aq)
K b1
HPO 24(aq)
+ H 2 O (l) H 2 PO -4(aq) + HO (aq)
K b2
K a1
K a2
K a3
Kw
K b1
K b2
K b3
K b3
HCO3(aq)
+ H 2 O(l) H 2 CO3(aq) + OH(aq)
2+
HCO3(aq)
+ H 2 O(l) CO3(aq)
+ H3O(aq)
K b2 = 2.38 x 10-8
K a2 = 4.80 x 10-11
+
H 2 PO-4(aq) + H 2 O(l) HPO24(aq)
+ H3O(aq)
K a2 = 6.20 x 10-8
K b3 = 1.33 x 10-12
+
HPO24(aq)
+ H 2 O(l) PO34(aq)
+ H 3O(aq)
K a3 = 3.6 x 10-13
HPO24(aq)
+ H 2 O(l) H 2 PO-4(aq) + OH(aq)
K b2 = 1.61 x 10-7
3+
6 ( aq )
2+
+
Fe(H2 O)5 (OH)(aq)
+ H (aq)
K a = 2.0 x 10-3
Ca(NO3)2
6.9
Zn(NO3)2
5.5
Al(NO3)3
3.5
CH3COOH(aq) + H 2 O( l)
+
CH3COO(aq)
+ H 3O(aq)
K a = 1.8 x 10-5
+
CH3COOH(aq) + H 2O(l)
CH3COO(aq)
+ H3O(aq)
(aq)
CH3COOH(aq) + H 2 O ( l)
CH3COO
+ H 3O
+
(aq)
Buffers
Solutions that contain BOTH acid component and
its conjugate base
Conjugate base is present in the initial concentration
of components
Examples :
Acetic acid added with sodium acetate
Ammonium chloride added with aqueous ammonia solution
Henderson-Hasselbalch Equation
Simplified equation for pH calculation involving
buffers
Henderson-Hasselbalch Equation
What is pH of a buffer that is 0.12 M in lactic acid, HC3H5O5,
and 0.10 M in sodium lactate?
Ka = 1.40 x 10-4
C 4 H 4 O 3 COOH
I
C
E
(aq)
+ H 2O (l)
C 4 H 4 O 3 COO
0.12 M
-x
0.12 - x
(x)(0.10 + x)
Ka =
(0.12 x)
(aq)
+
+ H 3 O (aq)
0.10 M
+x
0.10 + x
+x
x
(0.10)
pH = pK a +
(0.12)
The most important aspect of buffer solutions is that they resist drastic
changes of pH upon adding strong acids or bases!
Henderson-Hasselbalch Equation
HA + H2O A- + H3O+
HH equation only used when salt is present that is, present separately, not the
[salt] from ICE calculation
The salt-component must be added separately, or generated by neutralizing the
main component
In calculations involving buffers, ICE table must be in terms of MOLES especially if
volumes are not same. However, equating with Ka must be in MOLARITY.
HH equation is allowed only when simplifying assumptions are valid
Preparation of Buffers
Buffers can be prepared in three ways
Adding a solid salt component to a liquid
Ex. NaCH3COO solid added to a solution of acetic acid (aceticacetate buffer)
Preparation of Buffers
How many grams of NH4Cl must be added to 2.0 L
of 0.10 M NH3 to form a buffer of pH 9.00?
Kb NH3 = 1.8 x 10-5
What volume of 0.5 M NaOH must be added to 50 mL
of 0.1 M benzoic acid (C6H5COOH) to make 100.0 mL of
0.05 M benzoate buffer that is pH 4.5?
Ka benzoic acid = 6.3 x 10-5
Preparation of Buffers
Prepare a 100.0 mL 0.1 M phosphate buffer, pH 8.00.
Given:
H3PO4
pKa1 = 2.12
pKa2 = 7.21
pKa3 = 12.38
+
H 2 PO -4(aq) + H 2 O (l) HPO 24(aq)
+ H 3O (aq)
pH = pK a2
pK a2 = 7.21
(moles HPO 24 - )
+ log
(moles H 2 PO -4 )
(100.0 mL)
moles H 2 PO + moles HPO =
(0.1 M)
(1000 mL )
1L
4
24
CH 3 COOH
I
C
(50.00 mL)
(0.05 M)
-x
(aq)
+ H 2O (l)
CH 3 COO
(aq)
+
+ H 3 O (aq)
(10.00 mL)
(0.05 M)
+x
+x
( 40 .00 mL)(0.05 M)
( total volume = 60.00 mL)
pH = pK a + log
(60.00 mL)(0.05 M)
(total volume = 60.00 mL)
Buffer Capacity
Amount of acid or base (usually in mL) needed to
change the pH of a buffer solution by 1 degree.
Acid-Base Neutralizations:
Indicators, Titrations
and
pH curves
Acid-Base Indicators
The point at which chemically equivalent amounts of acid and
base have reacted is called the equivalence point.
The point at which a chemical indicator changes color is called
the end point.
HIn (aq) + H 2 O ( l )
color 1
In (aq) + H 2 O ( l )
color a
+
In (aq)
+ H 3O (aq)
Acidic indicator
color 2
HIn (aq)
+ OH (aq)
color b
Basic indicator
Acid-Base Indicators
The equilibrium constant expression for an indicator
would be expressed as:
[H3O+ ][In- ]
K In =
[HIn]
[HIn]
[H3O ] = KIn [In ]
+
Acid-Base Indicators
Color change ranges of some acid-base indicators
Indicator
Methyl violet
Methyl orange
Litmus
Phenolphthalein
Color in
acidic
Color in
range
pH range basic range
Yellow
0-2
Purple
Pink
3.1 4.4
Yellow
Red
4.7 8.2
Blue
Colorless 8.3 10.0
Red
Titration Curves
Strong Acid titrated with Strong Base
Given: 25.00 mL of 0.5 M HClO4, calculate the pH of the resulting
solution after adding the following volumes of 0.5 M NaOH:
Volume of
0.5 M NaOH
(mL)
Mmoles
NaOH
Mmoles
HClO4
remaining
Total
Volume
(mL)
[H+]final
pH
0.00
0.0
12.5
25.0
0.5000
0.301
5.00
2.5
10.0
30.0
0.3333
0.477
10.00
5.0
7.5
35.0
0.2143
0.669
15.00
7.5
5.0
40.0
0.1250
0.903
20.00
10.0
2.5
45.0
0.0555
1.256
25.00
12.5
50.0
1x10-7
7.000
30.00
15.0
55.0
2.2x10-13
12.657
Phenolphthalein
9
8
pH 7
Litmus
6
5
4
Methyl orange
3
2
Methyl violet
1
0
0
10
15
20
25
Volume Titrant (0.5 M NaOH)
30
35
40
Titration Curves
Weak Acid titrated with Strong Base
Given: 25.00 mL of 0.5 M CH3COOH, calculate the pH of the resulting
solution after adding the following volumes of 0.5 M NaOH:
Volume of
0.5 M
NaOH (mL)
Mmoles
NaOH
Mmoles
CH3COOH
remaining
Mmoles
CH3 COOproduced
Total
Volume
(mL)
pH
0.00
0.0
12.5
25.0
0.301
5.00
2.5
10.0
2.5
30.0
4.143
10.00
5.0
7.5
5.0
35.0
4.569
15.00
7.5
5.0
7.5
40.0
4.921
20.00
10.0
2.5
10.0
45.0
5.348
25.00
12.5
12.5
50.0
9.071
30.00
15.0
12.5
55.0
12.658
WA-SB curve
14
13
12
11
10
Phenolphthalein
9
8
pH
Litmus
6
5
4
Methyl orange
3
2
Methyl violet
1
0
0
10
15
20
Titrant volume
25
30
35
40
WA-SB curve
14
13
12
11
10
9
8
pH
7
6
5
4
3
2
1
0
0
10
15
20
Titrant volume
25
30
35
40
14
13
acetic curve
12
lactic curve
11
HClO curve
10
Phenolphthalein
9
8
7
Litmus
6
5
4
Methyl orange
3
2
Methyl violet
1
0
0
10
15
20
25
30
35
40
Titration
Curve of
Different
Acids vs
Strong Base