Brdy 6ed Ch17 AcidBaseEquilibria
Brdy 6ed Ch17 AcidBaseEquilibria
Brdy 6ed Ch17 AcidBaseEquilibria
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Chapter 17:
AcidBase Equilibria
in Aqueous Solutions
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Jespersen/Brady/Hyslop
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base
acid
Pe
But [H2O]pure =
Kc =
[H3 O + ][OH ]
[H2 O]2
1000 g
18.0 g/mol = 55.6 M
1.00 L
= M of 1 L of H2O
[H2O] = constant
Jespersen/Brady/Hyslop
base
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H3O+(aq) + OH(aq)
K c [H2O ] = [H ][ OH ] = K w
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H+(aq) + OH(aq)
+
K w = [H ][ OH ]
Jespersen/Brady/Hyslop
H2O
(l )
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14
=
[H
][OH
]
=
1.0
x
10
But K
w
Jespersen/Brady/Hyslop
Chemistry: The Molecular Nature of Matter, 6E
Self-Ionization of Water
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In aqueous solution,
Product of [H+] and [OH] equals Kw
[H+] and [OH] may not actually equal
each other
Acidic
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Solution Classification
Neutral [H3O+] = [OH]
[H3O+] < [OH]
Basic
Jespersen/Brady/Hyslop
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Learning Check
K w = [H ][ OH ] = 1 10
14
14
K
1
.
0
10
7
w
[ OH ] =
=
=
2
.
2
10
+
8
[H ] 4.6 10
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The pH Concept
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pOH = log[ OH ]
pK w = log K w = 14.00
Jespersen/Brady/Hyslop
log a
= b log a
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Using Logarithms
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pH + pOH = pK w = 14.00
Jespersen/Brady/Hyslop
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Acidic
pH < 7.00
Pe
Neutral
Basic
Jespersen/Brady/Hyslop
pH > 7.00
10
Your Turn!
Pe
A. 7.00
B. 6.63
C. 7.37
D. 15.3
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Jespersen/Brady/Hyslop
11
Learning Check
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11
[OH ] =
=
1.0
10
M
3
1.0 10
What are [H+] and [OH] of pH = 4.00 solution?
pH = 4.00 [H+] = 1.0 104 M
Pe
[OH] =
1.0 10
14
1.0 10 4
= 1.0 1010 M
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1. pH meter
Most accurate
Calibrate with solutions of known pH before use
Electrode sensitive to [H+]
Accurate to 0.01 pH unit
1. Acid-base indicator
Pe
3. Litmus paper
Red pH 4.7
acidic
Blue pH 4.7
basic
Strictly acidic vs. basic
Jespersen/Brady/Hyslop
13
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Jespersen/Brady/Hyslop
14
.
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Jespersen/Brady/Hyslop
15
Sample pH Calculations
Or
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Jespersen/Brady/Hyslop
16
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= 14.00 2.59
= 11.41
Jespersen/Brady/Hyslop
17
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Your Turn!
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Jespersen/Brady/Hyslop
18
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Learning Check
[H3O+][OH-] = 1 x 10-14
Pe
Jespersen/Brady/Hyslop
19
Your Turn!
[H3O+]
pH
2.3
1.0
4.3
7.7
1.0
9.40
14.00
4.60
5.23
7.00
105 M
1014 M
1010 M
109 M
107 M
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A.
B.
C.
D.
E.
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20
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Learning Check
Pe
[H3O+]= 4.7103
Jespersen/Brady/Hyslop
21
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Your Turn!
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A.
B.
C.
D.
E.
Jespersen/Brady/Hyslop
1.89
14.00
10.82
12.11
7.00
22
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Strong Acids
Assume 100% dissociated in solution HCl
Good ~ if dilute
HBr
Makes calculating [H+] and [OH]
HI
easier
HNO3
HClO3
HClO4
Pe
[H+] = 0.040 M
And pH = log (0.040) = 1.40
H2SO4
Jespersen/Brady/Hyslop
23
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Sr(OH)2
Jespersen/Brady/Hyslop
24
Learning Check
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Jespersen/Brady/Hyslop
25
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0.022 M
(So, good approximation)
Jespersen/Brady/Hyslop
26
Learning Check
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Show that the contribution of water selfionization to the total [H+] is negligible for a
0.020 M HCl solution.
[H+]total = [H+]soln + [H+]from H2O
= 0.020 M + ?
Pe
and
Kw = [H+][OH]
27
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10
13
[ OH ] =
=
= 5.0 10
+
0.0200
[H ]
Kw
Pe
Jespersen/Brady/Hyslop
28
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Learning Check
N/A
-0.1
N/A
0
0.1
0.1
0
0.1
0.1
Pe
pH = log(0.1) = 1
Jespersen/Brady/Hyslop
29
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Learning Check
0
+0.5
0.5
0
+0.52
1.0
pOH = -log(1.0) = 0
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I
C
E
(aq)
30
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Pe
NH4+(aq) + H2O
Jespersen/Brady/Hyslop
31
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Or generally
HA(aq) + H2O(l) A(aq) + H3O+(aq)
[A ][H3 O ]
K c =
[HA][H2 O]
But [H2O] = constant (55.6 M) so rewrite as
Pe
[A ][H3 O + ]
K c [H2 O] =
= Ka
[HA]
Where Ka = acid ionization constant
Jespersen/Brady/Hyslop
32
Ka
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Often simplify as
HA (aq) A (aq) + H+ (aq)
[A ][H+ ]
=
[HA]
pK a = log K a
Pe
K a = 10
pK a
Jespersen/Brady/Hyslop
33
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Jespersen/Brady/Hyslop
34
Learning Check
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Jespersen/Brady/Hyslop
35
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Or generally
B(aq) + H2O(l) BH+(aq) + OH(aq)
[BH+ ][OH ]
K c =
[B][H2O]
Pe
[BH+ ][OH ]
Kb =
[B]
pK b = log K b
Jespersen/Brady/Hyslop
36
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Learning Check
C5H5NH+(aq) + OH(aq)
[C5H5NH ][OH ]
Kb =
[C5H5N]
= 1.7 x 109
Pe
Jespersen/Brady/Hyslop
37
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Jespersen/Brady/Hyslop
38
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Kb =
[HA][OH ]
Jespersen/Brady/Hyslop
[A ]
Chemistry: The Molecular Nature of Matter, 6E
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[A ][H+ ] [HA][OH ]
+
Ka Kb =
=
[H
][OH
]= Kw
[HA]
[A ]
For any conjugate acid base pair:
Pe
K a K b = K w = 1.0 10 14
Jespersen/Brady/Hyslop
(at 25 C)
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K a K b = K w = 1.0 10 14
So
pK a + pK b = pK w = 14.00 (at 25 C)
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Equilibrium Calculations
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Jespersen/Brady/Hyslop
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Ex. 1
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Sr(OH)2
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Ex. 1
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46
[Nic ][H ]
=
[HNic]
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Ka
Ex. 1 (cont)
Pe
I
0.012
0
0
C
x
+x
+x
E
0.012 x
x
x
What is value of x?
Only source of H+ is ionization of HNic, then can get x
from [H+]
x = antilog(pH) = 10pH = 103.39
= 4.1 x 104 = [H+]
Jespersen/Brady/Hyslop
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Ex. 1 (cont)
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Ex. 1 (cont)
[Nic ][H ]
Ka =
[HNic]
[HNic] (M)
I
C
E
0.0120
0.00041
+ 0.00041
+ 0.00041
0.0120 0.00041
= 0.011590.012
0.00041
0.00041
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Ex. 1 (cont)
Now ready to calculate Ka.
x2
x2
(0.00041)2
Ka =
=
= 1.4 10 5
0.012 x 0.012
0.012
5
pK a = log(1.4 10 ) = 4.85
Next calculate:
Pe
x 0.00041
=
=
100% = 3.4%
c
0.012
Jespersen/Brady/Hyslop
50
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2. Calculating Equilibrium
Concentrations from Ka (or Kb) and Initial
Concentrations
Jespersen/Brady/Hyslop
51
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Jespersen/Brady/Hyslop
52
Your Turn!
Pe
A. 3.41
B. 4.11
C. 6.82
D. 2.89
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Jespersen/Brady/Hyslop
53
C
E
[HOCl]
[H3O+]
[OCl-]
0.20 M
-x
+x
+x
0.20 x
K a = 3.0 x 10 8
H3O + OCl
x2
=
=
0.20 x
HOCl
Assume x is small
2
x
3.0 x 10 8 =
x 2 = 6.0 x 10 9
0.20 x
x = 7.74 x 10 5
pH = -log (7.74 x 10 5 ) = 4.11
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Jespersen/Brady/Hyslop
54
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Simplifications in Acid-Base
Equilibrium Calculations
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Simplifications in Acid-Base
Equilibrium Calculations
Now lets see how this works with a weak
base
Ex. 2 Morphine, C17H19NO3, is administered medically to
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Ex. 2 (cont)
[Mor] (M)
I
C
E
0.075
x
0.075 x
[HMor+] (M)
[OH] (M)
0
+x
x
~0
+x
x
Pe
[OH ][HMor + ]
x2
Kb =
=
[Mor]
0.075 x
Assume x << 0.075,
then 0.075 + x 0.075
Plugging in for Kb and x gives
x2
= 1.6 10 6
0.075
Jespersen/Brady/Hyslop
57
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Ex. 2 (cont)
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58
Your Turn!
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A. 1.03
B. 2.33
C. 11.67
D. 12.97
Jespersen/Brady/Hyslop
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CH3NH3 + OH
x2
=
=
0.05 x
CH3NH2
Assume x is small
x
4.4 x 10 =
x 2 = 2.2 x 10 5
0.05 x
3
x = 4.69 x 10 3
pOH = -log (4.69 x 10
) = 2.33
pH=14.00 pOH = 14.00 2.33 = 11.67
Pe
Jespersen/Brady/Hyslop
60
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Jespersen/Brady/Hyslop
61
Cations as Acids
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Anions as Bases
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Kb
K w 1.0 10 14
=
=
Ka
1.8 10 4
Jespersen/Brady/Hyslop
= 5.6 x 1011
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pHJespersen/Brady/Hyslop
<7.00
65
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Ex. 4
x
0.10 x
0.10
Pe
I
C
E
Jespersen/Brady/Hyslop
[NH3] (M)
[H3O+] (M)
+x
+x
x
Chemistry: The Molecular Nature of Matter, 6E
x
66
Ex. 4 (cont)
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0.10
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x 2 = 0.10 5.6 10 10
x =
11
= 7.5 x 106
5.6 10
pH = log(7.5 x 106) = 5.13
Jespersen/Brady/Hyslop
67
Your Turn!
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A. 5.77
B. 2.13
C. 9.747
D. 4.87
E. 11.87
Jespersen/Brady/Hyslop
68
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1.0 x 10
Ka =
4
4.4 x 10
CH
NH
H
O
3 2 3
x2
=
=
+
0.125 x
CH3NH3
Assume x is small
Pe
2
x
11
2
12
2.27 x 10 =
x = 2.84 x 10
0.125 x
x = 1.68 x 10 6
pH = -log (1.68 x 10 6 ) = 5.77
Jespersen/Brady/Hyslop
69
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Jespersen/Brady/Hyslop
70
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K w 1.0 10
9
Ka =
=
=
5
.
9
10
Kb
1.7 10 6
For OCl :
K w 1.0 10 14
7
Kb =
=
=
3
.
3
10
Ka
3.0 10 8
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[A ][H ]
Ka =
[HA]
[HA]equilibrium = [HA]initial x
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[HA]initial 400 K a
[HA]initial 400 K a
Exact
Mathematically more complex
1. Successive approximations
Mathematically easier
Requires multiple iterations
Pe
Jespersen/Brady/Hyslop
73
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ax + bx + c = 0
b b 4 ac
x=
2a
2
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Ka =
+
[C 2HCO2Cl2 ][H
[HC 2HCO2Cl2 ]
Pe
[HC2HCO2Cl2 ]
(M)
C
E
0.15
x
0.15 x
Jespersen/Brady/Hyslop
= 0.050
[C2HCO2Cl2]
(M)
[H3O+] (M)
+x
+x
x
Chemistry: The Molecular Nature of Matter, 6E
x
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ax + bx + c = 0
2
3
x + 0.050 x 7.5 10 = 0
Pe
0.050
Jespersen/Brady/Hyslop
77
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Jespersen/Brady/Hyslop
78
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!! y
x 2 = (c x )(K a )
x=
K a (c x )
Pe
no
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and
x=
cK a
Pe
x 2 = (c x )(K a )
x=
0.050(0.15 0.0866)
Jespersen/Brady/Hyslop
K a (c x )
= 0.0563 M
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= 0.0639 M
x =
0.050(0.15 .0639)
= 0.0684 M
x =
0.050(0.15 .0684)
= 0.0656 M
x =
0.050(0.15 .0656)
= 0.0650 M
x =
0.050(0.15 .0650)
= 0.0652 M
Pe
x =
81
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Buffered Solution
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Buffers
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Jespersen/Brady/Hyslop
85
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[C 2H3 O 2 ][H + ]
= 1.8 x 105
=
[HC 2H3 O 2 ]
Pe
Ka
Jespersen/Brady/Hyslop
86
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Equilibrium
x
0.55 x 0.55
[C2H3O2] (M)
[H+] (M)
0.45
+x
0
+x
x
Pe
0.45+x 0.45
Have large amounts of both HA and A
x will be very small (x << c) compared to initial [HA]
and [A], so can neglect and simplify
Substitute equilibrium concentrations into equilibrium
law
(x )(0.45)
= 1.8 10 5
0.55
Jespersen/Brady/Hyslop
87
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(1.8 10 )(0.55)
5
x =
= 2.2 10 M
0.45
x = [H+] = 2.2 x 105
Pe
Jespersen/Brady/Hyslop
88
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Pe
Ka
[H + ][ A ] [H + ] mol A L 1 [H + ] mol A
=
=
=
( mol HA )
[HA ]
( mol HA ) L 1
Jespersen/Brady/Hyslop
89
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Pe
[H ][A ]
Ka =
[HA]
[H ] = K a
Jespersen/Brady/Hyslop
[HA]
[A ]
[H ] = K a
mol HA
mol A
90
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[HA]
[A ]
Pe
[H ] = K a
Jespersen/Brady/Hyslop
(mol HA)initial
(mol A )initial
91
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Pe
Jespersen/Brady/Hyslop
92
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[A ]
pH = pK a + log
[HA]
1
Usually make buffer so
[A ]initial
Pe
Jespersen/Brady/Hyslop
93
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[HA]initial
[A ]initial
to get desired pH
[HA]initial 10
1
10 [A ]initial
1
Outside this, run into problems with solubilities or
low buffer capacity
In log terms this translates:
pH = pKa 1
Pe
94
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Pe
2.90 to 4.90
So we can use this buffer system
Jespersen/Brady/Hyslop
95
Ex. 8 (cont)
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[A ]
pH = pK a + log
[HA]
First Rearrange Henderson-Hasselbalch equation
[A ]
pH pK a = log
[HA]
Plug in values for pH and pKa
[CHO2 ]
log
= 3.90 3.74 = 0.16
[HCHO2 ]
Pe
[CHO2 ]
= 100.16 = 1.4
[HCHO2 ]
Jespersen/Brady/Hyslop
96
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Ex. 8 (cont)
[CHO2 ] 1.4454
Pe
[H ] = K a
Jespersen/Brady/Hyslop
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Ex. 8 (cont)
Rearranging gives
[H+ ] 1.26 10 4
=
=
=
4
Ka
1.8 10
0.699
Pe
Jespersen/Brady/Hyslop
98
Your Turn!
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Pe
A. 10.18
B. 6.60
C. 3.82
D. 4.58
Jespersen/Brady/Hyslop
99
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pK a = log(6.3 x 10 ) = 4.20
C6H5 COO H3O
pH = pK a + log
C6H5 COOH
Pe
0.600M
=4.20 + log
= 4.58
0.250M
Jespersen/Brady/Hyslop
100
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Buffer Capacity
Pe
2.
101
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Pe
Jespersen/Brady/Hyslop
102
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Ex. 9 (cont)
OH(aq)
mol
CH3COO(aq)
mol
0.060 mol
0.45
0.060
+0.060
0.00
= 0.51
Pe
103
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Ex. 9 (cont)
[C 2H3O2 ][H ]
Ka =
= 1.8 10 5
[HC 2H3O2 ]
0.51
x
0.49 x
0.49
+x
0.51 x
0.51
Pe
I
C
E
Jespersen/Brady/Hyslop
~0
x
x
104
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Ex. 9 (cont)
(1.8 10 )(0.49)
[H ] =
= 1.73 10 5
0.51
pH = log(1.73 x 105) = 4.76
Or pH has changed by only
pH = 4.76 4.66 = 0.10 unit
Pe
Jespersen/Brady/Hyslop
105
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Pe
An enormous difference!
Buffers prevent wide swings in pH unless
a huge excess of strong acid or base are
added
Jespersen/Brady/Hyslop
106
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Ex. 10
Ka =
[NH3 ][H ]
+
[NH 4 ]
= 5.6 10 10
Pe
Jespersen/Brady/Hyslop
107
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Ex. 10 (cont)
Step 2: Calculate pH
+
[H ] = K a
[HA]initial
[A ]initial
[A ]
or pH = pK a + log
[HA]
0.030M
pH = pK a + log
=
9
.
25
+
log
0.040M
[NH+4 ]
[NH3 ]
Pe
Jespersen/Brady/Hyslop
108
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Ex. 10 Method 2
(aq)
[NH4 ][OH ]
5
Kb =
= 1.8 10
[NH3 ]
pKb = log(1.8 x 105) = 4.74
Pe
[OH ] =
K b [NH3 ]
1.8 10 0.030M
5
=
=
1
.
35
10
0.040M
[NH+4 ]
Jespersen/Brady/Hyslop
109
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Calculate pOH
Calculate pH
Pe
Jespersen/Brady/Hyslop
110
Ex. 10 Part B
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[NH+4 ][OH ]
Kb =
= 1.8 10 5
[NH3 ]
Moles
Before
[NH4+] (mol)
[HO] (mol)
0.030
0.040
~0
0.010
(from H+)
Pe
Reaction
[NH3] (mol)
After
0.030 0.010
= 0.020
Jespersen/Brady/Hyslop
+0.010
0.040 + 0.010 =
0.050
x
111
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5
K
[NH
]
1
.
8
10
0.020M
6
b
3
[OH ] =
=
=
7
.
2
10
0.050M
[NH+4 ]
Pe
pH = log(0.010) = 2.00
and pH = 2.00 7.00 = 5.00 pH units
Jespersen/Brady/Hyslop
112
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Polyprotic Acids
Polyprotic acids
H2C6H6O6
H2C2O4
Pe
H3C6H5O7
H2C4H4O5
H2C4H4O6
Jespersen/Brady/Hyslop
113
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Polyprotic Acids
H3PO4
Carbonic acid
H2CO3
Sulfuric acid
H2SO4
Sulfurous acid
H2SO3
(aq)
+ H2PO4
(aq)
Pe
K a1
K a2
K a3
114
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Polyprotic Acids
Or in simpler terms
[H+ ][H2PO 4 ]
K a1=
= 7.5 10 3
[H3PO 4 ]
[H+ ][HPO 24 ]
[H2PO 4 ]
= 6.2 10 8
Pe
Jespersen/Brady/Hyslop
K a3=
[H+ ][HPO34 ]
[HPO24 ]
= 3.6 10 13
115
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Polyprotic Acids
K a1 > K a2 > K a3
Pe
Why?
More difficult to remove H+ from negatively charged ion than
from neutral molecule
Further, larger negative charge on anionic acid makes it
harder to remove H+
Jespersen/Brady/Hyslop
116
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Pe
117
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acid.
Begin with chemical equations and Ka
expressions
H2C6H6O6(aq) H+(aq) + HC6H6+O6(aq)
Pe
K a1
[H ][HC 6H6 O6 ]
=
= 6.7 10 5
[H2C 6H6 O6 ]
2
HC6H6O6(aq) H+(aq) + C6H[H
O
(aq)
+
2
6 6 ][C
H
O
6 6 6 ]
Jespersen/Brady/Hyslop
K a2 =
[HC 6H6 O6 ]
= 2.7 10 12
118
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Pe
119
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a2
[H2C6H6O6], M
Pe
I
C
E
= 2.7 10 12
[HC6H6O6 ], M [H+], M
0.075
x
x
x
x
0.075 x 0.075
Jespersen/Brady/Hyslop
120
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Ex. 11 (cont)
Substituting into K a1 gives
K a1
x 2 = (6.7 10 5 )(0.075)
x =
(6.7 10 5 )(0.075) =
(5.03 10 6 ) = 2.24 10 3
Pe
Jespersen/Brady/Hyslop
121
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Ex. 11 (cont)
a2
[HC 6H6 O6 ]
= 2.7 10
12
Pe
122
I
C
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Ex. 11 (cont)
[HC6H6O6], M
[C6H6O62 ], M
[H+], M
2.2 103
y
0
y
y
2.2 103
y
2.2 103 y
2.2 103
2.2 103 + y
2.2 103
[HC 6H6 O6 ]
Pe
y = K a2 = 2.7 10
[C6H6O62] = 2.7 1012 M
= 2.7 10 12 =
12
2
[C 6H6 O6
(2.2 10 3 )(y )
(2.2 10 3 )
123
Ex. 11 (cont)
Pe
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124
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Ex. 11 (cont)
Pe
125
Your Turn!
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Pe
A. 2.07 x 10-4
B. 5.6 x 10-11
C. 3.38 x 10-8
D. 4.3 x 10-7
Jespersen/Brady/Hyslop
126
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CO32- + H3O+
Ka2
HCO3 H3O +
=
= 4.3 x 10 7
H2 CO3
Pe
2
x
4.3 x 10 7 =
assume x is small
0.10M x
x = HCO3 = H3O + = 2.07 x 10 4
CO3 H3O +
= 5.6 x 10 11
Ka 2 =
HCO3
CO23 2.07 x 10 4 + x
5.6 x 10 11 =
2.07 x 10 4 x
CO23 = 5.6 x 10 11 x was assumed to be small
Jespersen/Brady/Hyslop
127
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Pe
Jespersen/Brady/Hyslop
128
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K b1=
[OH ][HC 2O 4 ]
[C2O 4
Kw
=
K a2 ( H2C2O 4 )
Pe
K b2 =
[OH ][H2C2O 4 ]
[HC2O 4 ]
Jespersen/Brady/Hyslop
Kw
=
K a1 ( H2C2O 4 )
129
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Ex. 12 (cont)
K b2
K w 1.0 10 14
13
=
=
=
1
.
5
4
10
K a1
6.5 10 2
Pe
K b1
K w 1.0 10 14
10
=
=
= 1.6 4 10
5
K a2
6.1 10
Jespersen/Brady/Hyslop
130
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Ex. 12 (cont)
[HC
O
]
2
4
lost in 2nd step
K >> K
b1
b2
Pe
But
so we expect
[HC2O4]formed in 1st step >> [HC2O4]lost in 2nd step
131
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[C2O42], M
[HC2O4 ], M
[OH], M
0.10
x
0
x
x
0
x
x
0.10 x 0.10
[C2O 4
Pe
K b1 =
[OH ][HC 2O 4 ]
2
= 1.6 10
10
( x )( x )
0.10
132
x =
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11
= 4.0 10
Pe
133
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b2
[H2C2O4 ], M
[OH], M
4.0 106
y
0
y
y
4.0 106
y
4.0 106 y
4.0 106
=
[OH ][H2 C 2 O 4 ]
[HC 2 O 4 ]
Pe
[HC2O4], M
4.0 106+ y
4.0 106
= 1.5 10 13 =
y = K b2 = 1.5 10 13 = [H2C2O 4 ]
Jespersen/Brady/Hyslop
( y ) ( 4.0 10 6 )
(4.0 10 )
134
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Pe
135
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Ex. 12 (cont)
Pe
136
At
Endpoint
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Before
Endpoint
Titration
Buret
After
Endpoint
long tube
marked with volumes
0.10 mL increments
Analyte
Solution in flask
Titrant
Solution in buret
Pe
Indicator
137
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Equivalence point
Pe
Jespersen/Brady/Hyslop
138
Pe
rs
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Titration Curve
Jespersen/Brady/Hyslop
139
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Pe
Jespersen/Brady/Hyslop
140
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Pe
141
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H+(aq) mmol
OH(aq) mmol
50.0 mL 0.100 M =
5.00 mmol
10.0 mL 0.200 M =
2.00 mmol
2.00 mmol
2.00 mmol
= 3.00 mmol
= 0.00 mmol
Pe
3.00mmol
[H ] =
= 0.0500M
(50.00 + 10.00)mL
pH = log(0.0500) = 1.30
+
Jespersen/Brady/Hyslop
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3. At Equivalence Point
Before
50.0 mL 0.100 M
= 5.00 mmol
5.00 mmol
= 0.00 mmol
Pe
Rxn
After
All acid neutralized
What pH?
Jespersen/Brady/Hyslop
OH(aq) mmol
25.0 mL 0.200 M
= 5.00 mmol
5.00 mmol
= 0.00 mmol
143
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Pe
What is pH?
Na+ has no acid or base properties
Cl is anion of strong acid, so very weak base
Neither Na+ nor Cl affect pH
So solution is neutral
pH = 7.00
True for equivalence point of all strong acids
reacting with strong bases
Jespersen/Brady/Hyslop
144
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50.0 mL 0.200 M
= 10.00 mmol
5.00 mmol
= 0.00 mmol
5.00 mmol
= 5.00 mmol
Pe
Before
Rxn
After
Jespersen/Brady/Hyslop
145
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mmol
OH
excess
5.00mmol
[OH ] =
=
volume of solution (mL ) (50.0 + 50.0) mL
5.00 mmol
[OH ] =
= 0.0500M
100.0 mL
Pe
146
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Pe
Steep
Jespersen/Brady/Hyslop
147
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Pe
1. At equivalence point
2. After equivalence point
Jespersen/Brady/Hyslop
148
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+
[CH3COO ][H ]
Use Ka to calculate pH
K
=
a
CH3COOH CH3COO + H+
[CH 3 COOH]
[CH3COO] (M)
[H3O+] (M)
0.200M
+x
+x
0.20 x 0.20
Pe
[CH3COOH] (M)
C
E
Jespersen/Brady/Hyslop
149
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[CH3COO ][H ] (x )( x )
Ka =
=
= 1.8 10 5
[CH3COOH]
0.200
2
x = 0.20 1.8 10
x =
[HA ]i K =
3.6 10
= 1.9 10
Pe
Jespersen/Brady/Hyslop
150
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OH +
[H + ][CH3 COO ]
=
[CH3 COOH]
Pe
151
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Pe
+
Before
0
25.0mL
10.0mL
0.200M =
0.200M =
5.00 mmol
2.00 mmol
2.00 mmol
2.00 mmol +2.00 mmol
Rxn
= 3.00 mmol = 0.00 mmol = 2.00 mmol
After
Jespersen/Brady/Hyslop
152
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[CH3COO]
[H3O+]
3.00mmol/35.0mL
2.00mmol/35.0mL
+x
+x
3.00mmol/35.0mL 2.00mmol/35.0mL
Pe
+ 2.00mmol
[H + ][CH3 COO ]
[H ]
Ka =
35.00mL
5
[CH3 COOH]
1.8 10 =
+
3.00mmol
[H
]( 2.00mmol )
5
1.8 10 =
35.00mL
( 3.00mmol )
(
3.00mmol )
+
5
[H ] = 1.8 10
= 2.7 10 5 M
( 2.00mmol )
Jespersen/Brady/Hyslop
153
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[H ] mol A
Ka =
Or, in this example mol HA
+
Pe
[H ] mol CH3COO
Ka =
= 1.8 10 5
mol CH3COOH
Jespersen/Brady/Hyslop
154
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OH +
Rxn
12.5mL
0.200M =
2.50 mmol
2.50 mmol
= 2.50 mmol
= 0.00 mmol
Pe
Before
CH3COOH
+
25.0mL
0.200M =
5.00 mmol
2.50 mmol
After
Jespersen/Brady/Hyslop
OH
CH3COO
0
+2.50 mmol
= 2.50 mmol
155
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+
[H+ ][CH3COO ]
[H
]( 2.50mmol )
5
Ka =
= 1.8 10 =
[CH3COOH]
2.50mmol
[H+ ] = K a = 1.8 10 5
Pe
156
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3. At equivalence point
Pe
pH > 7
pH at equivalence is always >7 in weak acidstrong base titration
157
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3. At equivalence pointStoichiometry
25.00 mL of 0.200 M acetic acid
25.00 mL of 0.200 M NaOH added
OH + CH3COOH CH3COO + H2O
Rxn
25.00 mL
0.200 M =
5.00 mmol
5.00 mmol
= 0.00 mmol
Pe
Before
After
Jespersen/Brady/Hyslop
25.0 mL
0.200 M =
5.00 mmol
5.00 mmol
= 0.00 mmol
0.00 mmol
+ 5.00 mmol
= 5.00 mmol
158
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is e
el o
y! nl
!! y
0.00 mmol
[OH ] =
= 0.00M
50.0 mL
Pe
mmol
CH
COO
formed
5.00mmol
3
[CH3 COO ] =
=
= 0.100M
total Volume (mL )
50.00mL
Jespersen/Brady/Hyslop
159
rs
o
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is e
el o
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!! y
Kb =
[CH 3 COOH][OH ]
[CH3COO ]
I
C
[CH3COO], M
[CH3COOH], M
[OH], M
0.100M
+x
+x
0.100 x 0.100
Pe
K w 1.0 10 14
10
=
=
=
5
.
6
10
Ka
1.8 10 5
Kb =
[CH 3 COOH][OH ]
[CH3COO ]
Jespersen/Brady/Hyslop
= 5.6 10 10
x2
=
0.100
160
rs
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w us
is e
el o
y! nl
!! y
x =
= (0.100) 5.6 10
5.6 10
11
10
) = 5.6 10
11
= 7.5 10 M
Pe
rs
o
U n
se al
w us
is e
el o
y! nl
!! y
25 mL of 0.200 M CH3COOH
35mL of 0.200M NaOH
Now all acid used up
Pe
162
rs
o
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w us
is e
el o
y! nl
!! y
5.00 mmol
5.00 mmol
= 0.00 mmol
OH
7.00 mmol
5.00 mmol
= 2.00 mmol
CH3COO
0.00 mmol
+ 5.00 mmol
= 5.00 mmol
Pe
After
Jespersen/Brady/Hyslop
163
rs
o
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is e
el o
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!! y
25 mL of 0.200M CH3COOH
35mL of 0.200M NaOH
Excess mmol of OH = 2.00 mmol
Total volume = 25.00mL + 35.00mL = 60.00mL
2.00mmol
[OH ] =
= 0.0333M
60.00mL
Pe
164
Pe
rs
o
U n
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w us
is e
el o
y! nl
!! y
Jespersen/Brady/Hyslop
165
rs
o
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is e
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!! y
Pe
1. At equivalence point
2. After equivalence point
Jespersen/Brady/Hyslop
166
rs
o
U n
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w us
is e
el o
y! nl
!! y
K b=
][
OH
]
+
[ N2H4]
=1 . 710
[N2H4] (M)
[N2H5+] (M)
[OH] (M)
0.200
+x
+x
Pe
[N2 H
E 0.200 x 0.200
Jespersen/Brady/Hyslop
167
rs
o
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w us
is e
el o
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!! y
x = 0.200 1.7 10
x =
= 3.4 10
3.4 10 7 = 5.83 10 4
Pe
) = 3.23
168
rs
o
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w us
is e
el o
y! nl
!! y
[N2H5 ][OH ]
Kb =
= 1.7 10 6
[N2H4 ]
Pe
169
rs
o
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w us
is e
el o
y! nl
!! y
N2H5+
Before
25.0mL
0.200M =
5.00 mmol
Rxn
After
Pe
12.5mL
0.200M =
2.50 mmol
Jespersen/Brady/Hyslop
170
rs
o
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se al
w us
is e
el o
y! nl
!! y
[N2H5 ][OH ]
37.5mL
Kb =
= 1.7 10 6 =
[N2H4 ]
2.50mmol
37.5mL
[OH ] = K b = 1.7 10 M
Pe
171
rs
o
U n
se al
w us
is e
el o
y! nl
!! y
3. At equivalence point
Pe
pH < 7
pH at equivalence is always < 7 in weak base strong acid titration
172
rs
o
U n
se al
w us
is e
el o
y! nl
!! y
N2H5+
Before 25.0mL0.200M
= 5.00 mmol
Rxn
Pe
After
5.00 mmol
= 0.00 mmol
25.0mL0.200M
= 5.00 mmol
[N2H5
5.00mmol
]=
= 0.100M
50.0mL
Jespersen/Brady/Hyslop
173
I
C
E
rs
o
U n
se al
w us
is e
el o
y! nl
!! y
[N2H5 ]
K w 1.0 10 14
9
=
=
=
5
.
9
10
Kb
1.7 10 6
[N2H5+] (M)
[N2H4] (M)
[H+] (M)
0.100M
+x
+x
0.100 x 0.100
Pe
2
9
10
2
x
=
0
.
100
5
.
9
10
=
5
.
9
10
x
5.9 10 9 =
0.100
x = [H+ ] = 5.9 10 10 = 2.43 10 5
174
rs
o
U n
se al
w us
is e
el o
y! nl
!! y
Pe
Jespersen/Brady/Hyslop
175
rs
o
U n
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w us
is e
el o
y! nl
!! y
2.00mmol
2.00mmol
[H ] =
=
= 0.0333M
(25 + 35)mL
60mL
+
Pe
pH = log(0.0333) = 1.48
Jespersen/Brady/Hyslop
176
Pe
rs
o
U n
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w us
is e
el o
y! nl
!! y
Jespersen/Brady/Hyslop
177
Your Turn!
rs
o
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!! y
Pe
A. -1.01
B. 3.13
C. 1.01
D. -3.13
Jespersen/Brady/Hyslop
178
rs
o
U n
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w us
is e
el o
y! nl
!! y
Pe
179
rs
o
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w us
is e
el o
y! nl
!! y
pH = 4.74 + log
CH3COOH
Pe
1.0mmol
= 4.74 + log
= 3.68
11.5mmol
pH = 3.68 - 2.67 = +1.01
Jespersen/Brady/Hyslop
180
rs
o
U n
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w us
is e
el o
y! nl
!! y
Ka2
Pe
181
pH =
rs
o
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is e
el o
y! nl
!! y
pK a1 + pK a2
2
pH = pKa2
pOH from Kb
equilm of A2
pH = pKa1
3V/2
2V
Pe
V/2
Jespersen/Brady/Hyslop
182
rs
o
U n
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w us
is e
el o
y! nl
!! y
H+
Pe
HIn
(aq)
Acid form
(one color)
Jespersen/Brady/Hyslop
+ In
(aq)
base form
(another color)
[H + ][In ]
K In =
[HIn ]
183
rs
o
U n
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w us
is e
el o
y! nl
!! y
[H ][In ]
K In =
[HIn ]
K In = [H ]
Pe
Jespersen/Brady/Hyslop
184
rs
o
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w us
is e
el o
y! nl
!! y
(aq)
Pe
[In ]
Color observed depends on ratio [HIn]
A. If have 10 times as much In as HIn
Then In dominates solution is blue
[In ]
log
1
[HIn]
Jespersen/Brady/Hyslop
185
rs
o
U n
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w us
is e
el o
y! nl
!! y
A. If [In] = 10[HIn]
pK In = pH 1
Pe
[In ]
log
1
[HIn ]
Jespersen/Brady/Hyslop
186
rs
o
U n
se al
w us
is e
el o
y! nl
!! y
B. If [HIn] = 10[In]
pK In = pH ( 1)
Pe
187
rs
o
U n
se al
w us
is e
el o
y! nl
!! y
Pe
Jespersen/Brady/Hyslop
188
rs
o
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w us
is e
el o
y! nl
!! y
Bromcresol
green
Yellow
Blue
3.8 5.4
Methyl red
Red
Yellow
4.2 6.3
Blue
6.0 7.6
8.3 10.0
Pe
Jespersen/Brady/Hyslop
189