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Chapter 17:
AcidBase Equilibria
in Aqueous Solutions

Pe

Chemistry: The Molecular Nature


of Matter, 6E
Jespersen/Brady/Hyslop

Ionization of Water and pH Concept

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Lots of weak acids and bases


How can we quantify their relative
strengths?
Need reference
Choose H2O

Water under right Voltage


Slight conductivity

Pe

Where does conductivity come from?

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

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Where does Slight Conductivity of


H2O Come From?
Trace ionization self-ionization of
water
H3O+(aq) + OH(aq)
H2O() + H2O()
acid

base

acid

Equilibrium law is:

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

Chemistry: The Molecular Nature of Matter, 6E

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Where does Slight Conductivity of


H2O Come From?
H2O() + H2O()

H3O+(aq) + OH(aq)

Since [H2O] = constant


Equilibrium law simplifies to
2

K c [H2O ] = [H ][ OH ] = K w

Where Kw = ion product constant for water

Pe

Often omit 2nd H2O molecule and write


H2O()

H+(aq) + OH(aq)
+

K w = [H ][ OH ]
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

H2O

(l )

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Where does Slight Conductivity of


H2O Come From?
H+ (aq) + OH (aq)

for pure H2O at 25 C


[H+] = [OH] = 1.0 x 107 M
Kw = (1.0 x 107)(1.0 x 107) = 1.0 x 1014
{See Table 17.1 for Kw at various T's}

Pe

H2O auto-ionization occurs in any solution


When other ions present
[H+] [OH]
+

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

[H3O+] > [OH]

Pe

Solution Classification
Neutral [H3O+] = [OH]
[H3O+] < [OH]

Basic

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

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Learning Check

In a sample of blood at 25 C, [H+] = 4.6 108


M. Find [OH] and determine if the solution is
acidic, basic or neutral.
+

K w = [H ][ OH ] = 1 10

14

14
K
1
.
0

10
7
w
[ OH ] =
=
=
2
.
2

10
+
8
[H ] 4.6 10

Pe

So 2.2 107 M > 4.6 108 M


[OH] > [H3O+]
Solution slightly basic
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

The pH Concept

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With most weak acids and bases [x] small


Must compare values and exponents
Easier to compare if you take base 10
logarithm of each side
+
Define pH = log[H ]
+
pH
Get back to concentration by [H ] = 10
In general pX = log X

Pe

Can adapt to many values

pOH = log[ OH ]

pK w = log K w = 14.00
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

log a

= b log a

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log(a b ) = log a + log b


a
log = log a log b
b

General Properties of Logarithms

Using Logarithms

Start with K w = [H+ ][ OH ]


Taking log of both sides of eqn. gives

log([H+ ][ OH ]) = log K w = log(1.0 10 14 )

Pe

log[H+ ] log[ OH ] = log K w = ( 14.00)


So at 25 C:

pH + pOH = pK w = 14.00
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

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Redefine Acidic, Basic and Neutral


Solutions in terms of pH!
As pH , [H+] ; pOH , and [OH]
As pH , [H+] ; pOH , and [OH]
pH = 7.00

Acidic

pH < 7.00

Pe

Neutral

Basic

Jespersen/Brady/Hyslop

pH > 7.00

Chemistry: The Molecular Nature of Matter, 6E

10

Your Turn!

Pe

A. 7.00
B. 6.63
C. 7.37
D. 15.3

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Kw increases with increasing temperature. At


50 oC, Kw = 5.476 x 10-14. What is the pH of a
neutral solution at 50 oC ?

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

11

Learning Check

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What are [H+] and [OH] of pH = 3.00 solution?


[H+] = 103.00 = 1.0 103 M
14
1.0 10

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

Or pH 4.00 solution has 10 times


less H+ than pH 3.00 solution
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

12

How do we Measure pH?

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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

Dyes, change color depending on [H+] in solution


Used in pH paper and titrations
Give pH to 1 pH unit

Pe

3. Litmus paper

Red pH 4.7
acidic
Blue pH 4.7
basic
Strictly acidic vs. basic
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

13

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Indicators Help Us Estimate pH

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

14

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Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

15

Sample pH Calculations

Or

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Calculate pH and pOH of blood in Ex. 1.


We found [H+] = 4.6 108 M
[OH] = 2.2 x 107 M
pH = log(4.6 x 108) = 7.34
pOH = log(2.2 x 107) = 6.66
14.00 = pKw

Pe

pOH = 14.00 pH = 14.00 7.34 = 6.66

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

16

Sample pH Calculations (contd)

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What is the pH of NaOH solution at 25 C in


which the OH concentration is 0.0026 M?
[OH] = 0.0026 M
pOH = log(0.0026) = 2.59
pH = 14.00 pOH

= 14.00 2.59

= 11.41

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

17

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Your Turn!

Pe

A sample of fresh pressed apple juice has a pH


of 3.76. Calculate [H+].
A. 7.6 x 103 M
+
pH
[H ] = 10
B. 3.76 M
C. 10.24 M
= 103.76
= 1.7 x 104 M
D. 5.9 x 109 M
E. 1.7 x 104 M

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

18

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Learning Check

What is the [H3O+] and pH of a solution that has


[OH] = 3.2 103 M?

[H3O+][OH-] = 1 x 10-14

[H3O+] = 1 x 10-14/3.2 x 10-3 =3.1 x 10-12 M

Pe

pH = -log [H3O+] = -log(3.1 x 10-12)= 11.50

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

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

Pe

A.
B.
C.
D.
E.

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What is the [OH] and pH of a solution that


has [H3O+] = 2.3 105 M?

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

20

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Learning Check

What is the pOH and the [H3O+] of a solution


that has a pH of 2.33?
pOH = 11.67

Pe

[H3O+]= 4.7103

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

21

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Your Turn!

What is the pH and the [H3O+] of a solution


that has a pOH of 1.89?
[H3O+]
pH
1.29 102 M
1.0 1014 M
1.50 1011M
7.8 1013 M
1.0 107 M

Pe

A.
B.
C.
D.
E.

Jespersen/Brady/Hyslop

1.89
14.00
10.82
12.11
7.00

Chemistry: The Molecular Nature of Matter, 6E

22

Strong Acids: pH of Dilute Solutions

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Strong Acids
Assume 100% dissociated in solution HCl
Good ~ if dilute
HBr
Makes calculating [H+] and [OH]
HI
easier
HNO3

1 mole H+ for every 1 mole HA


So [H+] = [HA] for strong acids

Thus, if 0.040 M HClO4

HClO3
HClO4

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[H+] = 0.040 M
And pH = log (0.040) = 1.40

H2SO4

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

23

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pH of Dilute Solutions of Strong


Bases
Strong Bases
NaOH
KOH
LiOH
Ca(OH)2
Ba(OH)2

2 mole OH for every 1 mole B


[OH] = 2*[B] for strong bases

Pe

Sr(OH)2

1 mole OH for every 1 mole B


[OH] = [B] for strong bases

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

24

Learning Check

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Calculate the pH of 0.011 M Ca(OH)2.

Ca(OH)2(s) + H2O Ca2+(aq) + 2 OH(aq)


[OH] = 2*[Ca(OH)2] = 2*0.011M = 0.022M
pOH = log (0.022) = 1.66
pH = 14.00 pOH
= 14.00 1.66 = 12.34
What is this in the [H+] of the solution?
[H+] = 1012.34 = 4.6 x 1013 M

Pe

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

25

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Calculations of Strong Acids and Bases


Assume auto-ionization of H2O gives
negligible contribution to [H+]soln and
[OH]soln in solution of base (or acid)
[OH]total = [OH]soln + [OH]from H2O
[OH]total = 0.022 M + 4.6 x 1013

Pe

0.022 M
(So, good approximation)
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

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 + ?

Only [OH] comes from auto-ionization of H2O


H2O() H+(aq) + OH(aq)

Pe

and
Kw = [H+][OH]

So can use [OH] to determine


[H+]from H2O
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

27

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[H+] from Self Ionization (contd)


14
1
.
0

10

13
[ OH ] =
=
= 5.0 10
+
0.0200
[H ]

Kw

Pe

[H+]total = 0.020 M + 5.01013 M


0.020 M
So we see that [H+]from H2O is negligible
except in very dilute solutions of acids and
bases

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

28

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Learning Check

What is the pH of 0.1M HCl?


Assume 100% dissociation
HCl(aq) + H2O() H+(aq) + OH(aq)
I
0.1
C
-0.1
End 0

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

Chemistry: The Molecular Nature of Matter, 6E

29

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Learning Check

What is the pH of 0.5M Ca(OH)2?


Assume 100% dissociation
Ca(OH)2 (aq) Ca2+ (aq) + 2 OH
0.5
-0.5
0

0
+0.5
0.5

0
+0.52
1.0

pOH = -log(1.0) = 0

Pe

I
C
E

(aq)

pH = 14.00 pOH = 14.00 0 = 14


Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

30

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Weak Acids and Bases


Incompletely ionized
Molecules and ions exist in equilibrium
Reaction of a Weak Acid with Water
CH3COOH(aq) + H2O(l) CH3COO(aq) + H3O+(aq)
HSO3(aq) + H2O(l) SO32(aq) + H3O+(aq)
(l)

NH3 (aq) + H3O+ (aq)

Pe

NH4+(aq) + H2O

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

31

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Weak Acid/Base Equilibria


Acid + Water Conjugate Base + Hydronium Ion

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

Chemistry: The Molecular Nature of Matter, 6E

32

Weak Acid/Base Equilibria

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

Chemistry: The Molecular Nature of Matter, 6E

33

Pe

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Table 17.2 Weak Monoprotic Acids at 25


C

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

34

Learning Check

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What is the pKa of HOAC if Ka = 3.5 x 104?


HOCN(aq) + H2O(l) OCN(aq) + H3O+(aq)
or
HOCN(aq) OCN(aq) + H+(aq)
[OCN ][H+ ]
Ka =
4
=
3.5
x
10
[HOCN]

Pe

pKa = log Ka = log(3.5 x 104) = 3.46

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

35

Reaction of a Weak Base with Water

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CH3COO(aq) + H2O(l) CH3COOH(aq) + OH(aq)


NH3(aq) + H2O(l) NH4+ (aq) + OH(aq)

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

But [H2O] = constant


so can rewrite as

Where Kb = base ionization


constant
K b = 10 pK b

Chemistry: The Molecular Nature of Matter, 6E

36

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Learning Check

What is the pKb of C5H5Nif Ka = 3.5 x 104?


C5H5N(aq) + H2O()
+

C5H5NH+(aq) + OH(aq)

[C5H5NH ][OH ]
Kb =
[C5H5N]

= 1.7 x 109

Pe

pKb = log Kb = log(1.7 x 109) = 8.76

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

37

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Table 17.3 Weak Bases at 25 C

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

38

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Conjugate Acid-Base Pairs and


Values of Ka and Kb
1. Consider ionization reaction of generic acid
and water
HA(aq) + H2O() A(aq) + H3O+(aq)
[A ][H + ]
Ka =
[HA]

2. Consider reaction of a salt containing anion


of this acid (its conjugate base) with water

Pe

A(aq) + H2O() HA(aq) + OH(aq)

Kb =

[HA][OH ]

Jespersen/Brady/Hyslop

[A ]
Chemistry: The Molecular Nature of Matter, 6E

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Now adding reactions we get


HA(aq) + H2O(l) A(aq) + H3O+(aq)
A(aq) + H2O(l) HA(aq) + OH(aq)
2 H2O (l) H3O+ (aq) + OH (aq)

[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)

Chemistry: The Molecular Nature of Matter, 6E

40

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Using properties of logarithms


log(a b ) = log a + log b

K a K b = K w = 1.0 10 14

Then taking log of both sides of equation gives:


log(K a K b ) = log K w = log(1.0 10 14 )

log K a log K b = log K w = ( 14.00)

So

pK a + pK b = pK w = 14.00 (at 25 C)

Pe

Inverse relationship between strengths of acid and


base members of a conjugate pair.
The stronger the conjugate acid, the weaker the
conjugate base.
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

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Equilibrium Calculations

Pe

Need to develop strategy for dealing with


weak acid/base equilibrium calculations
Two general types of calculations:
1. Calculating Ka or Kb from initial concentrations
of acid or base and measured pH in solution
2. Calculating equilibrium concentrations given
Ka or Kb and initial concentrations

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

42

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1. Calculating Ka and Kb from Initial


Concentrations and Equilibrium Data
Need to evaluate mass action expression =
reaction quotient Q at equilibrium
concentrations
Since Q = Kc when at equilibrium

Can either be given initial concentrations and


one equilibrium concentration
Usually pH or pOH

Pe

OR can be given initial concentrations and


% ionization
moles ionized per liter
% ionization =
100%
moles available per liter
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

43

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Ex. 1

Pe

Niotinic acid (niacin) is a monoprotic acid


with the formula HC6H4NO2. A solution that
is 0.012 M in nicotinic acid has a pH of 3.39
at 25 C. What are the acid-ionization
constant, Ka, and pKa for this acid at 25 C?
What is the degree of ionization of nicotinic
acid in this solution? Let HNic = nicotinic
acid and Nic = anion.
HNic(aq) + H2O(l) Nic(aq) + H3O+(aq)
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

44

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pH of Dilute Solutions of Strong


Bases
Strong Bases
NaOH
KOH
LiOH
Ca(OH)2
Ba(OH)2

2 mole OH for every 1 mole B


[OH] = 2*[B] for strong
bases

Pe

Sr(OH)2

1 mole OH for every 1 mole B


[OH] = [B] for strong bases

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

45

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Ex. 1

Pe

Niotinic acid (niacin) is a monoprotic acid


with the formula HC6H4NO2. A solution that
is 0.012 M in nicotinic acid has a pH of 3.39
at 25 C. What are the acid-ionization
constant, Ka, and pKa for this acid at 25 C?
What is the degree of ionization of nicotinic
acid in this solution? Let HNic = nicotinic
acid and Nic = anion.
HNic(aq) + H2O(l) Nic(aq) + H3O+(aq)
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

46

[Nic ][H ]
=
[HNic]

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Ka

Ex. 1 (cont)

[HNic] (M) [Nic] (M) [H3O+] (M)

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

Chemistry: The Molecular Nature of Matter, 6E

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Ex. 1 (cont)

Since Nic is formed in 1:1 ratio with


H+, then
[Nic] = x = 4.1 x 104
Finally only reason HNic disappears is
because it ionizes, so loss of [HNic] = x
[Nic ][H+ ]
xx
x2
Ka =
=
=
[HNic]
0.012 x 0.012 x

Pe

But we know [Nic], so can put into


concentration table and solve for each
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

48

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Ex. 1 (cont)
[Nic ][H ]
Ka =
[HNic]

[HNic] (M)

I
C
E

[Nic] (M) [H+] (M)

0.0120

0.00041

+ 0.00041

+ 0.00041

0.0120 0.00041
= 0.011590.012

0.00041

0.00041

Pe

Notice if c >> Ka, then equilibrium concentration of


acid is approximated as initial concentration
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

49

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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

moles ionized per liter


% ionization =
100%
moles available per liter

x 0.00041
=
=
100% = 3.4%
c
0.012
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

50

Almost any problem where you are given


Ka or Kb falls into one of 3 categories:
1. Only solute is weak acid
2. Only solute is weak base
3. Two solutes, one is weak acid, other is
conjugate base (buffer problem-section 17.7)

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2. Calculating Equilibrium
Concentrations from Ka (or Kb) and Initial
Concentrations

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.
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Chemistry: The Molecular Nature of Matter, 6E

52

Your Turn!

Pe

A. 3.41
B. 4.11
C. 6.82
D. 2.89

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HClO is a weak acid with Ka = 3.0 x 10-8.


What is the pH of a 0.20 M solution of
hypochlorous acid ?

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

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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Your Turn! - Solution

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

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Simplifications in Acid-Base
Equilibrium Calculations

Pe

Now lets see how this works with a weak


base
Ex. 2 Morphine, C17H19NO3, is administered
medically to relieve pain. It is a naturally
occurring base, or alkaloid. What is the pH of a
0.075 M solution of morphine at 25 C? The
base-ionization constant, Kb, is 1.6x106 at 25
C. Let Mor = base morphine and HMor+ =
conjugate acid.
Mor(aq) + H2O(l) OH(aq) + HMor+(aq)
Jespersen/Brady/Hyslop

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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

Pe

relieve pain. It is a naturally occurring base, or


alkaloid. What is the pH of a 0.075 M solution of
morphine at 25 C? The base-ionization constant, Kb,
is 1.6x106 at 25 C. Let Mor = base morphine and
HMor+ = conjugate acid.

Mor(aq) + H2O(l) OH(aq) + HMor+(aq)


Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

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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
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Chemistry: The Molecular Nature of Matter, 6E

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Ex. 2 (cont)

x 2 1.6 10 6 0.075 = 1.2 10 7


= 3.5 x 104 M
x = 1.2 10 7
x [OH] = 3.5 x 104 M

check assumption 3.5 x 104 < 0.075

Pe

pOH = log (3.5 x 104) = 3.46


pH = 14.00 pOH

= 14.00 3.46 = 10.54


Notice if c >> Kb,
then [base]equilibrium [base]initial
Also if c >> Ka
then [HA]equilibrium [HA]initial
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

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Your Turn!

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The base ionization constant for methylamine


is 4.4 x 10-4. What is the pH of a 0.050 M
solution of this base ?

Pe

A. 1.03
B. 2.33
C. 11.67
D. 12.97

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Chemistry: The Molecular Nature of Matter, 6E

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Your Turn! - Solution


K b = 4.4 x 10 4

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

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Solutions of Salts: Ions as Weak


Acids and Bases

Pe

Acids and Bases not limited to molecular


substances
Ionic Salts can be basic or acidic
Need to know how to predict this

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Chemistry: The Molecular Nature of Matter, 6E

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Cations as Acids

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1. Cations that are conjugate acids of weak


molecular bases are weak acids and can affect
pH of solution (make pH < 7.00).
Ex. NH4+ , HMor+, etc.

2. Metals with high charge density are weak acids


as we saw in last chapter.
Ex. Small, highly charged like Al3+ and TM ions
[Al(H2O)6]3+(aq) + H2O() H3O+(aq) +
[Al(H2O)5(OH)]2+(aq)

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3. Metals with small charges are neutral


(non acidic).

Ex. Alkali and alkaline earth metals (except Be2+)


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Anions as Bases

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1. The anion of a strong acid is too weak a


base to influence the pH of solution.
Ex. HCl dissociates 100%, conjugate base extremely
weak
Little or no tendency to attract H+ to it.

1. The anion of a weak acid is a weak base


and can influence the pH of solution. It will
tend to make the solution basic (pH > 7.00).
Ex. Formic acid, HCHO2, Ka = 1.8 x 104

Pe

Formate anion, CHO2, is basic with

Kb

K w 1.0 10 14
=
=
Ka
1.8 10 4
Jespersen/Brady/Hyslop

= 5.6 x 1011

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Predicting Acid-Base Properties of Salt


1. If neither cation nor anion can affect pH,
solution neutral.
Ex. NaCl

1. If only cation is acidic, solution is acidic.


Ex. NH4I

1. If only anion is basic, solution is basic.


Ex. NaCHO2 (sodium formate)

Pe

1. If both cation is acidic and anion is basic, pH


depends on relative strengths of
acid and base.
Ex. NH4CHO2 (ammonium formate)
Jespersen/Brady/Hyslop

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Learning Check Ex. 3

Predict whether a 0.10 M solution of NH4Br will


be acidic, basic or neutral.
NH4+ is conjugate acid of weak base
ammonia
Its a weak acid
Will tend to make solution acidic

Br is conjugate base of strong acid HBr

Pe

Extremely weak base


Will not affect the pH

Conclusion: Solution acidic

pHJespersen/Brady/Hyslop
<7.00

Chemistry: The Molecular Nature of Matter, 6E

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Ex. 4

What is the pH of a 0.10 M solution of NH4Br?


For NH3, Kb = 1.8 x 105.
NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)
K w 1.0 10 14
Ka =
=
5
Kb
= 5.6 x 1010
1.8 10
[NH4+] (M)
0.10

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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At equilibrium equal amounts of [H3O+] and


[NH3] are present (both come from same
source)
[H3O+] = [NH3] = x
The equilibrium law for this reaction is
+
[NH3 ][H ] (x )( x )
10
Ka =
=
= 5.6 10
+
[NH4 ]

0.10

Pe

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
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67

Your Turn!

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What is the pH of a solution of 0.125 M


methylammonium chloride ? The base
ionization constant for methylamine is
4.4 x 10-4.

Pe

A. 5.77
B. 2.13
C. 9.747
D. 4.87
E. 11.87

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Your Turn! - Solution


14

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

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Solutions Containing Salt of Weak


Acid and Weak Base
Many salts contain:
Cation that is conjugate acid of weak base and
Anion that is conjugate base of weak acid
Both can affect pH of solution
Now must compare Ka of acid salt and Kb of basic salt

Pe

Could be neutral if both acid and base ~ same strength


Could be acidic if cation is stronger acid
Could be basic if anion is stronger base

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Ex. 5 Predict whether a solution of


hydrazinium hypochlorite, N2H5OCl, will
be acidic, basic or neutral. 14
For N2H5 :

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

Comparing equilibrium constants we see that:


K a (N2H5+ ) < K b (OCl )

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5.9 10 9 < 3.3 10 7

The base OCl is stronger than the acid N2H5+


Solution will be basic
Jespersen/Brady/Hyslop

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Equilibrium Calculations when


Simplifications Fail
Weak acid, HA, ionizes in water to give ions
HA(aq) + H2O(l) A(aq) + H3O+(aq)

[A ][H ]
Ka =
[HA]

[HA]equilibrium = [HA]initial x

Pe

where x = amount dissociated to ions = [A] = [H+]

For the solutions we have looked at so far,


[HA]equilibrium [HA]initial c
Jespersen/Brady/Hyslop

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Simplifications work when

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[HA]initial 400 K a

Simplifications fail when

[HA]initial 400 K a

Now must solve one of two ways


1. Quadratic equation

Exact
Mathematically more complex

1. Successive approximations
Mathematically easier
Requires multiple iterations

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Jespersen/Brady/Hyslop

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The Quadratic Equation


For a quadratic equation in the form
2

ax + bx + c = 0

the values of x that satisfy this equation are

b b 4 ac
x=
2a
2

Take only the positive root for the answer

Pe

Negative [HA] is meaningless

Always gives you the correct answer


Jespersen/Brady/Hyslop

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Ex. 6 What is the pH of a 0.15 M solution of


dichloro-acetic acid, HC2HCO2Cl2, in water?
For dichloroacetic acid, Ka = 5.0 x 102.
HC2HCO2Cl2(aq) + H2O(l) C2HCO2Cl2(aq) + H3O+(aq)
The equilibrium law for this reaction is

Ka =

+
[C 2HCO2Cl2 ][H

[HC 2HCO2Cl2 ]

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[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
75

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Ex. 6 Quadratic (cont)


Substituting equilibrium concentrations into
equilibrium law gives:
(x )( x )
= 0.050
0.15 x
Can we neglect x in denominator?
[HA]initial
0.15
=
= 3.0
Ka
0.050

Pe

Clearly not >400!


Cant neglect x so multiply both sides by (0.15
x) to clear fractions
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

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Ex. 6 Quadratic (cont)


= (0.15 x )(0.050) = (0.15 0.050) 0.050 x

Or in terms of general quadratic equation


2

ax + bx + c = 0
2
3
x + 0.050 x 7.5 10 = 0

Where a = 1, b = 0.050, and c = 7.5 x 103


Now put into quadratic formula
2
b b 4ac
x =
2a
(0.050)2 4(1)( 7.5 10 3 )
x =
2(1)
x = 0.065 M and x = 0.115 M

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0.050

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Ex. 6 Quadratic (cont)


Since only positive root has physical meaning,
we use this answer
[H+] = x = 0.065 M
[C2HCO2Cl2] = x = 0.065 M

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[HC2HCO2Cl2] = 0.15 0.065 = 0.085 M


pH = log(0.065) = 1.19

Jespersen/Brady/Hyslop

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Solving by Successive Approximations


For solution with initial concentration c, amount
dissociated x, and equilibrium law
( x )(x )
= Ka
c x

x 2 = (c x )(K a )

x=

K a (c x )

Step 1: Assume x << c, & solve equation for x using c


for equilibrium concentration.

Step 2: Calculate (c x ) and use this as the new


equilibrium concentration. Recalculate x.

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Step 3: Compare the new value of x with the previous


value. Are they the same?
Yes

Done. You have best


value of x.
Jespersen/Brady/Hyslop

no

Repeat step 2 with new


value.
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Ex. 6 Successive Approximations (cont)


Step 1: Assuming x << c, equilibrium law
simplifies to
2
x
= Ka
c

and

x=

cK a

For our example


x=

0.15 * 0.050 = 0.0866 M use this as x below

Step 2: Now subtract this calculated value of x


from c, substitute into equilibrium law and
solve for new x

Pe

x 2 = (c x )(K a )

For our example


x=

x=

0.050(0.15 0.0866)
Jespersen/Brady/Hyslop

K a (c x )
= 0.0563 M

Chemistry: The Molecular Nature of Matter, 6E

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Ex. 6 Successive Approximations (cont)


Step 3: Now compare old and new values of x.
For our example 0.0866 M 0.0563 M
So, go around again
0.050(0.15 .0563)

= 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

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x =

Usually converges in 3 4 iterations


So x = 0.065 M to two significant figures
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Buffered Solution

A solution that resists a change in its pH when


either [OH] or [H+] are added
Made up of two solutes

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EITHER a weak acid and its conjugate base as a


soluble salt
CH3COOH and CH3COONa (CH3COO)
HF and NaF
(F)
OR
A weak base and its conjugate acid as a soluble salt
(NH4+)
NH3 and NH4Cl
(N2H5+)
N2H4 and N2H5Cl
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Buffers

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Most important buffer:


HCO3 and H2CO3
In blood
Absorbs acids and bases produced by
metabolism
Maintains a remarkably constant pH
Important as cells live only in a very narrow
pH range.

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How a Buffer Works

Consider weak acid HA and its conjugate base A


Must be able to neutralize both strong acid and
strong base
Must have both weak acid and weak base anion
present in same solution
If we add acid to solution, it reacts with basic anion
H+ (aq) + A (aq) HA (aq)
Thus preventing a buildup of acid

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If we add base to solution, it reacts with acid


HA (aq) + OH (aq) A (aq) + H2O
Thus preventing a buildup of base
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Calculating pH of a Buffer Solution


One common buffer is acetic acid/acetate
ion buffer
In this case reactions that occur are

Acetic acid neutralizes added base

CH3COOH (aq) + OH (aq) CH3COO (aq) + H2O (aq)

Acetate ion neutralizes added acid

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CH3COO (aq) + H+ (aq) CH3COOH (aq)

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Ex. 7 A buffered solution contains 0.55 M acetic


acid (CH3COOH, Ka = 1.8 x 105) and 0.45 M
sodium acetate (NaCH3COO). Calculate the pH
of this solution.
When both solute species present, use either Ka or
Kb to perform calculations. Since we have Ka we
will use this.
CH3COOH (aq) CH3COO (aq) + H+ (aq)

[C 2H3 O 2 ][H + ]
= 1.8 x 105
=
[HC 2H3 O 2 ]

Pe

Ka

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Ex. 7 Buffer (cont)


Concentra- [HC2H3O2H] (M)
tion (M)
Starting
0.55
Change

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
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Ex. 7 Buffer (cont)


Solving for x gives
5

(1.8 10 )(0.55)
5
x =
= 2.2 10 M
0.45
x = [H+] = 2.2 x 105

Pe

pH = log(2.2 x 105) = 4.66

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Permissible Simplifications in Buffer


Calculations
Two simplifications that we make regularly for
BUFFER SOLUTIONS
1. Use initial concentrations of both weak acid and
conjugate base as equilibrium calculations
2. Can use either Molar concentrations or moles in Ka
(or Kb) expression for amount of conjugate acidbase pair

Pe

Ka

[H + ][ A ] [H + ] mol A L 1 [H + ] mol A
=
=
=
( mol HA )
[HA ]
( mol HA ) L 1
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Preparation of Buffer with Given pH


Usually scientist decides what pH is needed for
particular system
Then chooses buffer that gives you that pH

What factors govern the pH of a Buffer


solution?
Look at Ka equation and solve for [H+]
+

Pe

[H ][A ]
Ka =
[HA]

[H ] = K a

Jespersen/Brady/Hyslop

[HA]
[A ]

[H ] = K a

Chemistry: The Molecular Nature of Matter, 6E

mol HA
mol A
90

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Preparation of Buffer with Given pH


Thus the two factors that affect [H+] are
1. Ka of the weak acid
2. Ratio of acid to ion

[HA]

[A ]

Pe

Specifically we use initial molar concentrations or


initial number of moles
[HA]initial
+
[H ] = K a
[A ]initial
or
+

[H ] = K a

Jespersen/Brady/Hyslop

(mol HA)initial

(mol A )initial

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Preparation of Buffer with Given pH

Pe

If prepare buffer so that [HA] = [A],


[HA]initial
then ratio
= 1
[A ]initial
This means [H+] = Ka and pH = pKa
Often useful to express the entire thing in
logarithmic form

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Henderson Hasselbalch Equation

[A ]
pH = pK a + log
[HA]

Selecting the Weak Acid for Preparing a


Buffer Solution?
[HA]initial

1
Usually make buffer so

[A ]initial

Pe

So pKa mainly determines pH of buffer

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To prepare a buffer at a specific pH


1. Select weak acid with pKa near desired pH
1. Adjust ratio of

[HA]initial

[A ]initial

to get desired pH

Desirable range for ratio is

[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

is desirable range of pH for a buffer


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Ex. 8. A solution buffered at pH 3.90 is


needed for a reaction. Would formic acid and
its salt, sodium formate, make a good choice
for this buffer? If so, what mole ratio of the
acid (HCHO2) to conjugate base anion
(HCO2) is needed?
From Table 17.2 we see that the pKa of formic
acid is 3.74.
This is within pH = pKa 1 range

Pe

2.90 to 4.90
So we can use this buffer system
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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

Take antilog (10x) of both sides

[CHO2 ]
= 100.16 = 1.4
[HCHO2 ]

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Ex. 8 (cont)

Solve for ratio of moles acid/moles anion


[HCHO2 ]
1
=
= 0.69

[CHO2 ] 1.4454

moles of HCHO2 = 0.69 * moles of HCO2


Alternatively we can solve using concentrations and Ka

Pe

pH =3.90 means [H+] = 103.90 = 1.26 x 104


Ka = 1.8 x 104
+

[H ] = K a

(mol HCHO2 )initial

(mol CHO2 )initial

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Ex. 8 (cont)
Rearranging gives

(mol HCHO2 )initial

(mol CHO2 )initial

[H+ ] 1.26 10 4
=
=
=

4
Ka
1.8 10

0.699

Pe

= 0.70 to two sig. figs


Slight difference due to rounding errors
Still within 0.01

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Your Turn!

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Determine the pH of a buffer solution


containing 0.250 M benzoic acid and 0.600 M
sodium benzoate. Ka for benzoic acid is
6.3 x 10-5.

Pe

A. 10.18
B. 6.60
C. 3.82
D. 4.58

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Your Turn! - Solution


5

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
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Buffer Capacity

Amount of strong acid or base that buffer can absorb


before its buffering ability is destroyed
Determined by actual concentrations of acid and basic
anion (or base and acidic cation) in solution
1. Must decide what amount of change in pH can
tolerate
Usually pH 0.1 or 0.2 units
Never more than pH 1

How much H+ or OH needed to neutralize

Pe

2.

Larger [HA] and [A] = larger buffer capacity


Large volume of buffer = larger buffer capacity
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Ex. 9. A student has available 1.00 L of buffered


solution from Ex. 7 0.55 M acetic acid
(CH3COOH, Ka = 1.8 x 105) and 0.45 M sodium
acetate (NaCH3COO). What is the pH of this
buffer after 0.060 mol of OH are generated by
the reaction?
Step 1. Calculate pH of buffer
From Ex. 7, we see that before OH is generated the

Pe

pH of the buffer is 4.66 or


[H+] = 2.2 x 105 M

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Ex. 9 (cont)

Step 2: Calculate amts of HA and A from reaction


CH3COOH(aq) + OH(aq) CH3COO(aq) + H2O(aq)
[CH3COOH]
mol

Before 0.55 mol


0.060
Rxn
= 0.49
After

OH(aq)
mol

CH3COO(aq)
mol
0.060 mol
0.45
0.060
+0.060
0.00
= 0.51

Pe

Now use these new concentrations to calculate the pH


Use ICE table
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Ex. 9 (cont)

Step 3: Calculate New pH


CH3COOH (aq) CH3COO (aq) + H+ (aq)

[C 2H3O2 ][H ]
Ka =
= 1.8 10 5
[HC 2H3O2 ]

[CH3COOH] mol [CH3COO] mol [H+] mol


0.49

0.51

x
0.49 x
0.49

+x
0.51 x
0.51

Pe

I
C
E

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

~0
x
x
104

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Ex. 9 (cont)

Substitute equilibrium concentrations into


+
equilibrium law
[H ](0.51)
5
= 1.8 10
0.49
Solving for [H+] gives
5

(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

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Effectiveness of a Buffer System


If we added this 0.060 mol of OH to 1.00
L of pure water the pH would be
[OH] = 0.060 M
pOH = log(0.060) = 1.22
pH = 14.00 1.22 = 12.78
or
pH = 12.78 7.00 = 5.78

Pe

An enormous difference!
Buffers prevent wide swings in pH unless
a huge excess of strong acid or base are
added
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Ex. 10

Calculate the pH of a buffer solution that is


0.040 M NH4Cl (aq) and 0.030 M NH3 (aq).
Step 1: Equilibrium:
NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)

Ka =

[NH3 ][H ]
+
[NH 4 ]

= 5.6 10 10

Pe

pKa = log(5.6 x 1010) = 9.25

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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

pH = 9.25 + log(0.75) = 9.13

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Ex. 10 Method 2

Alternatively, you can use Kb and equilibria


to calculate [OH], pOH, and finally pH
NH3 + H2O (l) NH4+ (aq) + OH
+

(aq)
[NH4 ][OH ]
5
Kb =
= 1.8 10
[NH3 ]
pKb = log(1.8 x 105) = 4.74

Pe

Solving for [OH] gives

[OH ] =

K b [NH3 ]

1.8 10 0.030M
5
=
=
1
.
35

10
0.040M
[NH+4 ]

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Ex. 10 Method 2 (cont)

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Calculate pOH

pOH = log(1.35 x 105) = 4.87

Calculate pH

Pe

pH = 14.00 4.87 = 9.13

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110

Ex. 10 Part B

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Can 1.00 L of this buffer system deal with the


addition of 0.010 mol of H+? What is the final
pH in this case?
NH3 + H2O (l) NH4+ (aq) + OH (aq)

[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

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111

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Ex. 10 Part B (cont)

Now plug in concentrations into Kb equation


and solve for [OH]

5
K
[NH
]
1
.
8

10
0.020M

6
b
3
[OH ] =
=
=
7
.
2

10
0.050M
[NH+4 ]

pOH = log(7.2 x 106) = 5.14


pH = 14.00 5.14 = 8.86
pH = 8.86 9.13 = 0.27 pH units
If we added this 0.010 mol of H+ to 1.00 L of
pure water, the pH would be

Pe

pH = log(0.010) = 2.00
and pH = 2.00 7.00 = 5.00 pH units
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Polyprotic Acids

Up until now, monoprotic acids


donate only 1 H+

Polyprotic acids

donate more than 1 H+

Ascorbic Acid (vitamin C)

H2C6H6O6

Oxalic acid (rhubarb)

H2C2O4

Pe

Many Polyprotic acids occur in nature

Citric acid (citrus fruit)

H3C6H5O7

Malic acid (apples)

H2C4H4O5

Tartaric acid (grapes)

H2C4H4O6

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Polyprotic Acids

Some Inorganic Polyprotic acids:


Phosphoric acid

H3PO4

Carbonic acid

H2CO3

Sulfuric acid

H2SO4

Sulfurous acid

H2SO3

These acids undergo ionization in steps


H3PO4(aq) + H2O(l) H3O

(aq)

+ H2PO4

(aq)

Pe

H2PO4(aq) + H2O(l) H3O+(aq) + HPO42(aq)


HPO42(aq) + H2O(l) H3O+(aq) + PO43(aq)
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Chemistry: The Molecular Nature of Matter, 6E

K a1
K a2
K a3

114

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Polyprotic Acids
Or in simpler terms

H3PO4(aq) H+(aq) + H2PO4(aq)

[H+ ][H2PO 4 ]
K a1=
= 7.5 10 3
[H3PO 4 ]

H2PO4(aq) H+(aq) + HPO42(aq)


K a2=

[H+ ][HPO 24 ]
[H2PO 4 ]

= 6.2 10 8

Pe

HPO42(aq) H+(aq) + PO43(aq)

Jespersen/Brady/Hyslop

K a3=

[H+ ][HPO34 ]
[HPO24 ]

Chemistry: The Molecular Nature of Matter, 6E

= 3.6 10 13

115

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Polyprotic Acids

Note: each ionization makes contribution to [H+]


Must relate successive Kas and [HA] to equilibrium [H+]

Looks hard to solve, but simple approximation makes


it easy
1. Ka for each successive step becomes smaller
and smaller

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+
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For many inorganic polyprotic acids, each successive


loss of H+ 104 to 106 times more difficult than
previous step
1st ionization step of polyprotic acid produces up to
~ a million times more H3O+ ions than 2nd step
Result: essentially all of H+ comes from 1st ionization
step
[H+]total = [H+]1st step + [H+]2nd step
But [H+]1st step >> [H+]2nd step

Pe

So [H+]total [H+]1st step

Significance: Can treat polyprotic acids as


monoprotic acids and ignore 2nd (and 3rd) step
Must check assumption at end of calculation
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Ex. 11 Polyprotic Acid Equilibria


Ascorbic acid (Vitamin C, H2C6H6O6) is a diprotic acid
with Ka1 = 6.7 105 and Ka2 = 2.7 1012. Calculate
[H+], pH, H2C6H6O6 and C6H6O62 in 0.075 M ascorbic

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 ]

Chemistry: The Molecular Nature of Matter, 6E

= 2.7 10 12
118

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Ex. 11 (cont) Polyprotic Acids


Assumptions we have to make:
1. Only need to worry about 1st ionization step for [H+]
[H+]equilm [H+]first step
2. Only need to worry about 1st ionization step for
[HC6H6O6]

Pe

[HC6H6O6]equilm = [HC6H6O6]formed in 1st step


[HC6H6O6]lost in 2nd step
K a1 > > K a2
But
so we expect
[HC6H6O6]formed in 1st step >> [HC6H6O6]lost in 2nd step
Thus we assume that
[HC6H6O6]equilm [HC6H6O6]formed in 1st step
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Ex. 11 (cont) Now Solve it:


Begin with chemical equations and Ka expressions

H2C6H6O6 (aq) H+ (aq) + HC6H6O6 (aq)


K a1

[H+ ][HC 6H6 O6 ]


=
= 6.7 10 5
[H2C 6H6 O6 ]

HC6H6O6 (aq) H+ (aq) + C6H6O62 (aq)


K

a2

[H2C6H6O6], M

Pe

I
C
E

[H+ ][C 6H6 O26 ]


[HC 6H6 O6 ]

= 2.7 10 12

[HC6H6O6 ], M [H+], M

0.075

x
x

x
x

0.075 x 0.075
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Ex. 11 (cont)
Substituting into K a1 gives
K a1

[H+ ][HC 6H6 O6 ]


(x )( x )
5
=
= 6.7 10 =
[H2C 6H6 O6 ]
(0.075)

x 2 = (6.7 10 5 )(0.075)
x =

(6.7 10 5 )(0.075) =

(5.03 10 6 ) = 2.24 10 3

So [H+] = [HC6H6O6] = 2.2 103 M

Pe

pH = log [H+] = log (2.2 103) = 2.65

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Ex. 11 (cont)

Calculate [C6H6O62] using expression for K a2


HC6H6O6 (aq) H+ (aq) + C6H6O62 (aq)

a2

[H+ ][C 6H6 O26 ]

[HC 6H6 O6 ]

= 2.7 10

12

Pe

From step 1 and our assumptions


[H+]equilibrium [H+]first step

[HC6H6O6]equilibrium [HC6H6O6]formed in 1st step


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E

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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

Substituting into K a2 gives


a2

[HC 6H6 O6 ]

Pe

[H+ ][C 6H6 O26 ]

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)

[H+]second step = [C6H6O62] = 2.7 1012 M


[H+]equilibrium = [H+]first step + [H+]second step
[H+]equilibrium = 2.2 103 M + 2.7 1012 M
[H+]equilibrium = 2.2 103 (correctly rounded)

Pe

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NOTE: In solution containing polyprotic acid


as only solute, [ion] formed in second step of
ionization = K a2
Checking our assumptions:
In 2nd step , H+ and C6H6O62 are formed from
HC6H6O6
This means

So our 1st approximation is valid


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Ex. 11 (cont)

Now lets look at the 2nd assumption


[HC6H6O6]equilm = [HC6H6O6]formed in 1st step
[HC6H6O6]lost in 2nd step
[HC6H6O6]formed in 1st step = 2.2 103 M
[HC6H6O6]lost in 2nd step = 2.7 1012 M

[HC6H6O6]equilm = 2.2 103 M 2.7 1012 M

Pe

[HC6H6O6]equilm = 2.2 103 M (correctly


rounded)

So 2nd approximation is valid


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125

Your Turn!

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What is the molar concentration of carbonate


ion in a 0.10 M solution of carbonic acid ?
Ka1 = 4.3 x 10-7 ; Ka2 = 5.6 x 10-11

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

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Your Turn! - Solution


H2CO3 + H2O
HCO3- + H2O
Ka1

HCO3- + H3O+ Ka1

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
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Salts of Polyprotic Acids give Basic


Solutions

Pe

Same principles apply to conjugate bases of


polyprotic acids
Here, use equations of bases, K b1 K b2
and
Simplifying assumptions are essentially the
same except substitute [OH] for [H+]

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Ex. 12. What is the pH of a 0.10 M solution of


sodium oxalate, Na2C2O4? What are the
concentrations of OH, H+, HC2O4, H2C2O4
(oxalic acid) in the equilibrium mixture?

C2O42 (aq) + H2O HC


O
(
aq
)
+
OH
(aq)
2 4

K b1=

[OH ][HC 2O 4 ]
[C2O 4

Kw
=
K a2 ( H2C2O 4 )

Pe

Since C2O42 is conjugate base of HC2O4 second Ka


applies
HC2O4 (aq) + H2O H2C2O4 (aq) + OH (aq)

K b2 =

[OH ][H2C2O 4 ]

[HC2O 4 ]

Jespersen/Brady/Hyslop

Kw
=
K a1 ( H2C2O 4 )

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Ex. 12 (cont)

Since HC2O4 is conjugate base of H2C2O4 first


Ka applies
First must calculate successive Kbs to see if
our usual approximations are valid

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

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Ex. 12 (cont)

Assumptions we need to make:


1. [OH]total = [OH]1st step + [OH]2nd step
But [OH]1st step >> [OH]2nd step
So [OH]total [OH]1st step

2. [HC2O4]equilibrium = [HC2O4]formed in 1st step

[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

Thus we assume that


[HC2O4]equilibrium [HC2O4]formed in 1st step
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Ex. 12 (cont) Polybasic Salts


In order to calculate pH of solution we only need
to consider first equilibrium
I
C
E

[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

x 2 = (1.6 10 10 )(0.10) = 1.6 10 11


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x =

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Ex. 12 (cont) Polybasic Salts


1.6 10

11

= 4.0 10

[OH] = [HC2O4] = x = 4.0 106 M


pOH = log [OH] = log (4.0 106) = 5.39

Pe

pH = 14.00 pOH = 14.00 5.39 = 8.61


So the solution will be basic
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Ex. 12 (cont) Polybasic Salts


Now to calculate [H2C2O4]
I
C
E

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 )

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Ex. 12 (cont) Polybasic Salts


Checking our assumptions:
In 2nd step , OH and H2C2O4 are formed from
HC2O4
This means:
[OH]second step = [H2C2O4] = 1.5 1013 M
[OH]equilibrium = [OH]first step + [OH]second step
[OH]equilibrium = 4.0 106 M + 1.5 1013 M

Pe

[OH]equilibrium = 4.0 106 (correctly rounded)

So our 1st Approximation is valid


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Ex. 12 (cont)

Now lets look at the 2nd assumption:


[HC2O4]equilibrium = [HC2O4]formed in 1st step
[HC2O4]lost in 2nd step
[HC2O4]formed in 1st step = 4.0 106 M
[HC2O4]lost in 2nd step = 1.5 1013 M

[HC2O4]equilibrium = 4.0 106 1.5 1013M

Pe

[HC2O4]equilibrium = 4.0 106 M (correctly


rounded)

So 2nd approximation is valid


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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

Dye to help visualize


equivalence point
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Acid Base Titrations


Common lab technique
Endpoint

When a color change of indicator occurs

Equivalence point

When stoichiometric amounts of acid and base have


combined

Pe

Ideally choose indicator so equivalence point =


endpoint

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Plot of pH of solution at various stages in


titration (y-axis) vs. volume of titrant added
Calculate pH at four points in titration:
1.
2.
3.
4.

Before titration begins = Initial pH


During titrations, but before equivalence point
At equivalence point
After equivalence point

Pe

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Titration Curve

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Titration of Strong Acid with Strong Base


Ex. 13 50.00 mL of 0.100 M HCl is titrated with
0.200 M NaOH using Phenol Red as the
indicator (pH range 6.4 8.2)
1. Before titration begins: Initial pH
Determined by initial concentration of acid in flask
[H+] = 0.100 M
pH = log[H+] = log(0.100) = 1.00
Initial pH is low

Pe

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Ex. 13 Strong Acid with Strong Base

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2. During titration: before equivalence

Pe

Some acid neutralized


Remaining H+ determines pH
10 mL of 0.200 M NaOH added
H+ + OH H2O
For every 1 mol OH added, 1 mol of H+ is neutralized
or reacted
mmol H+remaining = mmol H+initial mmol H+reacted
So convert mL M = mmol for each and subtract
To get [H+] after addition
+
mmol
H
remaining
+
[H ]remaining =
Vtotal

VolTotal = Volacid in flask + Volbase added


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Ex. 13 Strong Acid with Strong Base

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2. During titration: before equivalence


50.00 mL of 0.100 M HCl
10.00 mL of 0.200 M NaOH added
H+(aq) + OH(aq) H2O(aq)
Before
Rxn
After

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
+

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3. At Equivalence Point

Ex. 13 Strong Acid with Strong Base


50.00 mL of 0.100 M HCl
25.00 mL of 0.200 M NaOH added
H+(aq) + OH(aq) H2O(aq)
H+(aq) mmol

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

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Ex. 13 Strong Acid with Strong Base


3. At equivalence point

What species are present?


Na+, Cl, and H2O

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
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4. After Equivalence Point

Ex. 13 Strong Acid with Strong Base


50.00 mL of 0.100 M HCl
50.00 mL of 0.200 M NaOH added
Now OH is in excess
[OH]excess determines pH

mmol OH excess = mmol OH added mmol H+initial


H+(aq) + OH(aq) H2O(aq)
H+(aq) mmol
OH(aq) mmol
50.0 mL 0.100 M
= 5.00 mmol

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

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Ex. 13 Strong Acid with Strong Base


4. After titration: after equivalence
50 mL of 0.200 M NaOH added
First calculate pOH

mmol
OH
excess
5.00mmol

[OH ] =
=
volume of solution (mL ) (50.0 + 50.0) mL
5.00 mmol
[OH ] =
= 0.0500M
100.0 mL

pOH = log (0.0500) = 1.301

Pe

Next use Kw to determine pH and/or [H+]


pH = pKw pOH = 14.00 1.301 = 12.70
[H+] = 1012.70 = 2.0 1013 M
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Titration Curve of Strong Acid with


Strong Base

Pe

Steep

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Titration of Weak Acid with Strong Base


Calculate pH at four different regions:
1. Before titration begins
2. During titration, but before equivalence point

pH at the half-equivalence point very easy

Pe

1. At equivalence point
2. After equivalence point

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Titration: Weak Acid with Strong Base

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Ex. 14 25.00 mL of 0.200 M acetic acid


(CH3COOH) is titrated with 0.200 M NaOH;
Ka(CH3COOH) = 1.8 105
1. Before titration begins

Simply solution of weak acid, CH3COOH

+
[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

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Ex. 14 Weak Acid and Strong Base


Initial pH

[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

pH = log(1.9 x 103) = 2.72

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Ex. 14 Weak Acid with Strong Base

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2. During titration: before equivalence


10 mL of 0.200 M NaOH added
Some acid neutralized
Buffer problem
Have both HA and A present

OH +

CH3COOH CH3COO + H2O


Ka

[H + ][CH3 COO ]
=
[CH3 COOH]

Pe

Need to determine mmol of OH, CH3COOH and


CH3COO
Then calculate concentrations of each species
Use equilibrium expression and solve for [H +] and pH
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Ex. 14 Weak Acid with Strong Base

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2. During titration: before equivalence


25.00 mL of 0.200 M acetic acid
10 mL of 0.200 M NaOH added
OH + CH3COOH CH3COO + H2O

Pe

Vtotal = (25.00 + 10.00) mL = 35.00 mL


CH3COOH
CH3COO
OH

+
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
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Ex. 14 Weak Acid and Strong Base

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2. During titration: before equivalence


Now solve the buffer problem
[CH3COOH]

[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 )

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Ex. 14 Weak Acid and Strong Base


2. During titration: before equivalence
Since ratio of two substances that are both in
same solution, Vtotal will be same for both and
cancel
Can use ratio of moles A to moles HA instead
+

[H ] mol A
Ka =
Or, in this example mol HA
+

Pe

[H ] mol CH3COO
Ka =
= 1.8 10 5
mol CH3COOH

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Ex. 14 Weak Acid with Strong Base

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2b. During titration: halfway to equivalence


25.00 mL of 0.200 M acetic acid
12.5 mL of 0.200 M NaOH added

OH +

CH3COOH CH3COO + H2O

Vtotal = (25.00 + 12.50) mL = 37.50 mL

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

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Ex. 14 Weak Acid and Strong Base


2a. During titration: halfway to equivalence
25.00 mL of 0.200 M acetic acid
12.5 mL of 0.200 M NaOH added

+
[H+ ][CH3COO ]
[H
]( 2.50mmol )
5
Ka =
= 1.8 10 =
[CH3COOH]
2.50mmol

[H+ ] = K a = 1.8 10 5

Pe

pH = pK a = log 1.8 10 5 = 4.74

True for any weak acid with strong base


pH = pKa halfway to equivalence
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3. At equivalence point

Ex. 14 Weak Acid and Strong Base


25.00 mL of 0.200 M acetic acid
25.00 mL of 0.200 M NaOH added
All of acid is neutralized
What species are present?
Na+, CH3COO, and H2O

Na+ has no acid or base properties


CH3COO ion is weak base, so solution basic

Pe

pH > 7
pH at equivalence is always >7 in weak acidstrong base titration

To calculate pH must look at equilibria of weak


base CH3COO
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Ex. 14 Weak Acid with Strong Base

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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

Vtotal = (25.00 + 25.00) mL = 50.00 mL


CH3COOH +
CH3COO
OH

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

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Ex. 14 Weak Acid and Strong Base


3. At equivalence pointDilution Factor
25.00 mL of 0.200 M acetic acid
25 mL of 0.200 M NaOH added
Total Volume = 25.00 + 25.00 = 50.00 mL
Concentrations After Reaction
mmol CH3 COOH remaining
0.00mmol
[CH3 COOH] =
=
= 0.00M
total solution Volume (mL )
50.00mL

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
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Ex. 14 Weak Acid with Strong Base

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3. At the equivalence pointWeak Base


CH3COO + H2O CH3COOH + OH

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

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Ex. 14 Weak Acid and Strong Base


3. At the equivalence point

CH3COO + H2O CH3COOH + OH

x =

= (0.100) 5.6 10
5.6 10

11

10

) = 5.6 10

11

= 7.5 10 M

pOH = log 7.6 10 6 M = 5.12

pH = pK w pH = 14.00 5.12 = 8.88

Pe

So at the equivalence point, pH is determined by


the conjugate base equilibrium
161

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Ex. 14 Weak Acid and Strong Base


4. After equivalence point

25 mL of 0.200 M CH3COOH
35mL of 0.200M NaOH
Now all acid used up

CH3COO + H2O CH3COOH + OH

Pe

Addition of more OH favors left side of equilibrium


So effectively only source of OH is excess added
OH
Analogous to Strong Acid/Strong Base
titration after equivalence point
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Ex. 14 Weak Acid with Strong Base

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4. After equivalence point--Stoichiometry


25.00 mL of 0.200 M acetic acid
35.00 mL of 0.200 M NaOH added
OH + CH3COOH CH3COO + H2O
CH3COOH
Before
Rxn

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

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Ex. 14 Weak Acid and Strong Base


4. After equivalence pointExcess Base

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

pOH = log( 0.0333) = 1.48

Pe

pH = pK w pH = 14.00 1.48 = 12.52


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Pe

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Titration Curve of Weak Acid with


Strong Base

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Titration of Weak Base with Strong Acid


Calculate pH at four different regions:
1. Before titration begins
2. During titration, but before equivalence point

pH at the half-equivalence point very easy

Pe

1. At equivalence point
2. After equivalence point

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Titration of Weak Base with Strong Acid

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Ex. 15 25.00 mL of 0.200 M Hydrazine (N2H4) is titrated with


0.200 M HCl; Kb(N2H4) = 1.7 106
1. Before titration begins

Simply solution of weak base, N2H4

Use Kb to calculate pOH, then pH

N2H4 + H2O N2H5+ + OH

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
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Ex. 15 Weak Base with Strong Acid


1. Before titration begins
x2
Kb =
= 1.7 10 6
0.200
2

x = 0.200 1.7 10
x =

= 3.4 10

3.4 10 7 = 5.83 10 4

Pe

pOH = log 5.83 10

) = 3.23

pH = pK w pOH = 14.00 3.23 = 10.76

168

Ex. 15 Weak Base with Strong Acid

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2. During titration, before equivalence


25.00 mL of 0.200 M N2H4
12.5 mL of 0.200 M HCl added
Some base neutralized
Buffer problem
Have both B and HB+ present
N2H4 + H2O N2H5+ + OH

[N2H5 ][OH ]
Kb =
= 1.7 10 6
[N2H4 ]

Pe

Need to determine mmol of OH, N2H4 and N2H5+


Then calculate concentrations of each species
Use equilibrium expression and solve for [OH], pOH and pH
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Ex. 15 Weak Base with Strong Acid

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2. During titration: halfway to equivalence


25.00 mL of 0.200 M N2H4
12.5 mL of 0.200 M HCl added
N2H4 + H+ N2H5+

Vtotal = (25.00 + 12.50) mL = 37.50 mL


N2H4 +
H+

N2H5+
Before

25.0mL
0.200M =
5.00 mmol

Rxn

2.50 mmol 2.50 mmol +2.50 mmol

After

= 2.50 mmol = 0.00 mmol = 2.50 mmol

Pe

12.5mL
0.200M =
2.50 mmol

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Ex. 15 Weak Base and Strong Acid

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2. During titration: before equivalence


25.00 mL of 0.200 M N2H4
12.5 mL of 0.200 M HCl added
2.50mmol
[OH ]

[N2H5 ][OH ]
37.5mL
Kb =
= 1.7 10 6 =
[N2H4 ]
2.50mmol

37.5mL

[OH ] = K b = 1.7 10 M

Pe

pOH = log 1.7 10 M = 5.77


pH = pK w pOH = 14.00 5.77 = 8.23 = pK a
pH = pKa halfway to equivalence
True, any weak base, strong acid titration
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3. At equivalence point

Ex. 15 Weak Base and Strong Acid


25.00 mL of 0.200 M N2H2
25.00 mL of 0.200 M HCl added
All of base is neutralized
What species are present?
N2H5+, Cl and H2O

Cl has no acid or base properties


N2H5+ ion is a weak acid, so solution acidic

Pe

pH < 7
pH at equivalence is always < 7 in weak base strong acid titration

To calculate pH must look at equilibria of weak


acid N2H5+
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Ex. 15 Weak Base with Strong Acid

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2. At equivalence point N2H4 + H+ N2H5+


25.00 mL of 0.200 M N2H4
25.00 mL of 0.200 M HCl added

Vtotal = (25.00 + 25.00) mL = 50.00 mL


N2H4 +
H+

N2H5+
Before 25.0mL0.200M
= 5.00 mmol
Rxn

5.00 mmol +5.00 mmol


= 0.00 mmol = 5.00 mmol

Pe

After

5.00 mmol
= 0.00 mmol

25.0mL0.200M
= 5.00 mmol

[N2H5

5.00mmol
]=
= 0.100M
50.0mL

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Ex. 15 Weak Base with Strong Acid


Ka =

I
C
E

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3. At the equivalence point N2H5+ N2H4 + H+


[N2H4 ][H+ ]
+

[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

pH = log 2.43 10 5 = 4.61


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Ex. 15 Weak Base with Strong Acid


4. After equivalence point

25.00 mL of 0.200 M N2H4

Pe

35.00 mL of 0.200 M HCl added


Total Volume = (25 + 35) mL = 60.0 mL
H+ added after equivalence point has nothing with
which to react
Solution becomes more and more acidic
[H+] from unreacted HCl used to calculate pH after
accounting for dilution

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Ex. 15 Weak Base with Strong Acid


4. After equivalence point--Stoichiometry
Initial mmol N2H4+ = 25.00mL0.200M = 5.00mmol
Total mmol H+ = 35.00mL0.200M = 7.00mmol
Excess mmol H+ = total mmol H+ mmol N2H4+
Excess mmol H+ = (7.00 5.00)mmol = 2.00 mmol

2.00mmol
2.00mmol
[H ] =
=
= 0.0333M
(25 + 35)mL
60mL
+

Pe

pH = log(0.0333) = 1.48

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Pe

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Titration Curve: Weak Base with


Strong Acid

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Your Turn!

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What is the change in pH when 10.0 mL of


0.100M NaOH is added to 50.0 mL of 0.250M
acetic acid? The acid ionization constant for
acetic acid is 1.8 x 10-5. The initial pH of the
acetic acid is 2.67.

Pe

A. -1.01
B. 3.13
C. 1.01
D. -3.13

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Your Turn! - Solution

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First, determine the initial mmoles of acid and base:


10.0 mL NaOH x 0.100M = 1.00 mmol NaOH
50.0 mL CH3COOH x 0.250M = 12.5 mmol CH3COOH
mmol of acid remaining after addition of base:
12.5 mmol 1.00 mmol = 11.5 mmol

Pe

mmol of acetate ion produced:


1.00 mmol
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Your Turn! - Solution cont.


pK a = 4.74

CH5 COO H3O +

pH = 4.74 + log
CH3COOH

Since you have a ratio you do not


need to calculate the molarity of the solution

Pe

1.0mmol
= 4.74 + log
= 3.68

11.5mmol
pH = 3.68 - 2.67 = +1.01
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Titration Curves of Polyprotic Acids


Consider Ascorbic acid, diprotic acid, H2A
titrated with a strong base
Now 2 equilibria
H2A HA + H+ Ka1
HA A2 + H+

Ka2

As long as Ka1 and Ka2 are several orders of


magnitude different (Ka1 1000 Ka2)

Pe

Neutralization occurs in stepwise manner


Titration curve shows 2 sharp increases in pH
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pH =

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Titration Curves of Polyprotic Acids

pK a1 + pK a2
2

pH = pKa2

pOH from Kb
equilm of A2

pH = pKa1

3V/2

2V

Pe

V/2

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Acid Base Indicators

Dyes that are weak acids, weak bases; organic


molecules
Acid/conjugate base pairs are different colors
Very intense
If you put a small amount of HIn in solution
Will be one color if acidic (phenolphthalein = colorless)
Another color if basic (phenolphthalein = bright magenta)
Color will change when pH rises or falls
(aq)

H+

Pe

HIn

(aq)

Acid form
(one color)

Jespersen/Brady/Hyslop

+ In

(aq)

base form
(another color)

[H + ][In ]
K In =
[HIn ]

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Acid Base Indicators


Want indicator that changes colors at pH
corresponding to equivalence point of
titration
Midpoint of color change is where [HIn] =
[In]
+

[H ][In ]
K In =
[HIn ]

K In = [H ]

Pe

So want pKIn = pHat equivalence point

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Acid Base Indicators


Consider Bromthymol blue

HIn (aq) H+ (aq) + In


HIn is yellow
In is blue
pKIn = 7.1

(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]

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A. If [In] = 10[HIn]

Acid Base Indicators


[H + ][In ]
10
+
K In =
= [H ]
[HIn ]
1

Taking log of both sides gives


pK In = pH log(10)

pK In = pH 1

So color will change to In color (blue) when


pH = pKIn + 1
B. If have 10 times as much HIn as In

Pe

HIn dominates solution is yellow

[In ]
log
1
[HIn ]

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B. If [HIn] = 10[In]

Acid Base Indicators


[H + ][In ]
1
+
K In =
= [H ]
[HIn ]
10

Taking log of both sides gives


pK In = pH log(10 1 )

pK In = pH ( 1)

So color will change to HIn color (yellow)


when pH = pKIn 1

Pe

Color of solution changes between pKIn 1


and pKIn + 1
Range of color change pH = pKIn 1
For bromthymol blue this means pH 6 - 8
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Acid Base Indicators


For titration curves,

Pe

Equivalence point (steep part of curve) usually


marked by pH change of 4 units
Usually within 1 2 drops of added titrant (base)
Indicators need pH change of 2 units to see
complete color change
Result: endpoint = equivalence point as long as
you choose your indicator wisely
Want indicator whose pKIn = pHeq pt 1

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Acid Base Indicators


Indicator

Acid color Base color pH range

Bromcresol
green

Yellow

Blue

3.8 5.4

Methyl red

Red

Yellow

4.2 6.3

Blue

6.0 7.6

Bromthymol blue Yellow

8.3 10.0

Pe

Phenolphthalein Colorless Pink

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