Вы находитесь на странице: 1из 189

# .

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

Chapter 17:
AcidBase Equilibria
in Aqueous Solutions

Pe

of Matter, 6E

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## Lots of weak acids and bases

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

## Water under right Voltage

Slight conductivity

Pe

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

base

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

Pe

H2O()

H+(aq) + OH(aq)
+

K w = [H ][ OH ]

H2O

(l )

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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
Chemistry: The Molecular Nature of Matter, 6E

Self-Ionization of Water

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

The pH Concept

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

log a

= b log a

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## log(a b ) = log a + log b

a
log = log a log b
b

## General Properties of Logarithms

Using Logarithms

Taking log of both sides of eqn. gives

Pe

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

So at 25 C:

pH + pOH = pK w = 14.00

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

pH > 7.00

10

Pe

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

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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 ?

11

Learning Check

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

12

## How do we Measure pH?

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

13

Pe

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

14

.
rs
o
U n
se al
w us
is e
el o
y! nl
!! y

Pe

## Chemistry: The Molecular Nature of Matter, 6E

15

Sample pH Calculations

Or

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

16

Pe

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

17

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

18

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

Learning Check

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

[OH] = 3.2 103 M?

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

Pe

19

[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.

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

has [H3O+] = 2.3 105 M?

20

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

21

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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.

1.89
14.00
10.82
12.11
7.00

22

## Strong Acids: pH of Dilute Solutions

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

Pe

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

H2SO4

23

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

24

Learning Check

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

25

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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)

## Chemistry: The Molecular Nature of Matter, 6E

26

Learning Check

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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]

[H+]from H2O

27

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

28

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

29

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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)

30

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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)

Pe

NH4+(aq) + H2O

31

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

32

## Weak Acid/Base Equilibria

Ka

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

Often simplify as
HA (aq) A (aq) + H+ (aq)
[A ][H+ ]
=
[HA]

pK a = log K a

Pe

K a = 10

pK a

33

Pe

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

C

34

Learning Check

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

35

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

## But [H2O] = constant

so can rewrite as

constant
K b = 10 pK b

36

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

37

Pe

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

38

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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 ]

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

39

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

(at 25 C)

40

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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.

## Chemistry: The Molecular Nature of Matter, 6E

41

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

42

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

43

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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)

44

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

45

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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)

46

[Nic ][H ]
=
[HNic]

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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+]

47

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

48

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

Pe

## Notice if c >> Ka, then equilibrium concentration of

acid is approximated as initial concentration

## Chemistry: The Molecular Nature of Matter, 6E

49

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

Ex. 1 (cont)

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

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)

Pe

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

51

.
rs
o
U n
se al
w us
is e
el o
y! nl
!! y

Pe

52

Pe

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

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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 ?

## 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

Pe

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## Chemistry: The Molecular Nature of Matter, 6E

54

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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)

## Chemistry: The Molecular Nature of Matter, 6E

55

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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.

## Chemistry: The Molecular Nature of Matter, 6E

56

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

57

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

Pe

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

58

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

## Chemistry: The Molecular Nature of Matter, 6E

59

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

60

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

61

Cations as Acids

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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)

Pe

(non acidic).

62

Anions as Bases

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

Kb

K w 1.0 10 14
=
=
Ka
1.8 10 4

= 5.6 x 1011

63

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## Predicting Acid-Base Properties of Salt

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

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)

64

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

Pe

## Extremely weak base

Will not affect the pH

<7.00

65

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

[NH3] (M)

[H3O+] (M)

+x

+x

x
Chemistry: The Molecular Nature of Matter, 6E

x
66

Ex. 4 (cont)

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

67

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

## Chemistry: The Molecular Nature of Matter, 6E

68

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

69

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

70

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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 )

Pe

## The base OCl is stronger than the acid N2H5+

Solution will be basic

71

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

## For the solutions we have looked at so far,

[HA]equilibrium [HA]initial c

72

## Simplifications work when

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

[HA]initial 400 K a

## Simplifications fail when

[HA]initial 400 K a

## Now must solve one of two ways

Exact
Mathematically more complex

1. Successive approximations
Mathematically easier
Requires multiple iterations

Pe

## Chemistry: The Molecular Nature of Matter, 6E

73

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

For a quadratic equation in the form
2

ax + bx + c = 0

b b 4 ac
x=
2a
2

Pe

74

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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 ]

Pe

[HC2HCO2Cl2 ]
(M)

C
E

0.15
x

0.15 x

= 0.050

[C2HCO2Cl2]
(M)

[H3O+] (M)

+x

+x

x
Chemistry: The Molecular Nature of Matter, 6E

x
75

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

## Chemistry: The Molecular Nature of Matter, 6E

76

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

= (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

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

Pe

0.050

## Chemistry: The Molecular Nature of Matter, 6E

77

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

Pe

## [HC2HCO2Cl2] = 0.15 0.065 = 0.085 M

pH = log(0.065) = 1.19

78

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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.

Pe

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

value. Are they the same?
Yes

value of x.

no

## Repeat step 2 with new

value.
Chemistry: The Molecular Nature of Matter, 6E

79

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## Ex. 6 Successive Approximations (cont)

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

and

x=

cK a

x=

## 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)

K a (c x )
= 0.0563 M

80

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

Pe

x =

## Usually converges in 3 4 iterations

So x = 0.065 M to two significant figures

## Chemistry: The Molecular Nature of Matter, 6E

81

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

Buffered Solution

## A solution that resists a change in its pH when

either [OH] or [H+] are added

Pe

## 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

82

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

Buffers

Pe

## 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.

83

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

Pe

## If we add base to solution, it reacts with acid

HA (aq) + OH (aq) A (aq) + H2O
Thus preventing a buildup of base

84

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## Calculating pH of a Buffer Solution

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

Pe

85

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

86

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

87

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

88

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

89

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

[HA]
[A ]

[H ] = K a

mol HA
mol A
90

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

(mol HA)initial

(mol A )initial

91

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

92

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

[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

93

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## To prepare a buffer at a specific pH

1. Select weak acid with pKa near desired pH

[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

94

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

## Chemistry: The Molecular Nature of Matter, 6E

95

Ex. 8 (cont)

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

[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 ]

96

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

Ex. 8 (cont)

[HCHO2 ]
1
=
= 0.69

[CHO2 ] 1.4454

## moles of HCHO2 = 0.69 * moles of HCO2

Alternatively we can solve using concentrations and Ka

Pe

Ka = 1.8 x 104
+

[H ] = K a

## Chemistry: The Molecular Nature of Matter, 6E

97

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

Ex. 8 (cont)
Rearranging gives

[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

98

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

## Chemistry: The Molecular Nature of Matter, 6E

99

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

100

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

Pe

2.

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

Large volume of buffer = larger buffer capacity

101

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

102

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

Ex. 9 (cont)

## Step 2: Calculate amts of HA and A from reaction

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

Use ICE table

103

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

Ex. 9 (cont)

## Step 3: Calculate New pH

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

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

0.49

0.51

x
0.49 x
0.49

+x
0.51 x
0.51

Pe

I
C
E

~0
x
x
104

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

105

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

106

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

## Chemistry: The Molecular Nature of Matter, 6E

107

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

108

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

[OH ] =

K b [NH3 ]

1.8 10 0.030M
5
=
=
1
.
35

10
0.040M
[NH+4 ]

109

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

Calculate pOH

Calculate pH

Pe

110

Ex. 10 Part B

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

+0.010

0.040 + 0.010 =
0.050

x
111

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

112

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

Polyprotic Acids

donate only 1 H+

Polyprotic acids

H2C6H6O6

H2C2O4

Pe

H3C6H5O7

H2C4H4O5

H2C4H4O6

113

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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)

## Chemistry: The Molecular Nature of Matter, 6E

K a1
K a2
K a3

114

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

Polyprotic Acids
Or in simpler terms

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

K a2=

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

= 6.2 10 8

Pe

K a3=

[H+ ][HPO34 ]
[HPO24 ]

= 3.6 10 13

115

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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+

116

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

## Significance: Can treat polyprotic acids as

monoprotic acids and ignore 2nd (and 3rd) step
Must check assumption at end of calculation

117

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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 ]

K a2 =

[HC 6H6 O6 ]

= 2.7 10 12
118

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

119

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## Ex. 11 (cont) Now Solve it:

Begin with chemical equations and Ka expressions

K a1

=
= 6.7 10 5
[H2C 6H6 O6 ]

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

## Chemistry: The Molecular Nature of Matter, 6E

120

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

Pe

121

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

Ex. 11 (cont)

## Calculate [C6H6O62] using expression for K a2

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

a2

[HC 6H6 O6 ]

= 2.7 10

12

Pe

## From step 1 and our assumptions

[H+]equilibrium [H+]first step

122

I
C
E

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

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

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

124

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

Pe

rounded)

125

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

126

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

127

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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+]

128

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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?

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 ]

Kw
=
K a1 ( H2C2O 4 )

129

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

130

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

131

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

132

x =

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

133

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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 ]

( y ) ( 4.0 10 6 )

(4.0 10 )

134

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

135

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

Pe

rounded)

## Chemistry: The Molecular Nature of Matter, 6E

136

At
Endpoint

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

Before
Endpoint

Titration
Buret

After
Endpoint

long tube
marked with volumes
0.10 mL increments

Analyte

Titrant

Solution in buret

Pe

Indicator

## Dye to help visualize

equivalence point

137

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## Acid Base Titrations

Common lab technique
Endpoint

## When a color change of indicator occurs

Equivalence point

combined

Pe

endpoint

138

## 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

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

Titration Curve

139

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

140

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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
+
mmol
H
remaining
+
[H ]remaining =
Vtotal

141

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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
+

## Chemistry: The Molecular Nature of Matter, 6E

142

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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?

OH(aq) mmol
25.0 mL 0.200 M
= 5.00 mmol
5.00 mmol
= 0.00 mmol

143

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

144

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

145

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

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

146

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

Strong Base

Pe

Steep

147

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

148

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

149

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

150

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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 +

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

151

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

152

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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 )

153

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

154

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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 +

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

OH

CH3COO
0

+2.50 mmol
= 2.50 mmol

155

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

## True for any weak acid with strong base

pH = pKa halfway to equivalence

## Chemistry: The Molecular Nature of Matter, 6E

156

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

base CH3COO

157

## Ex. 14 Weak Acid with Strong Base

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

CH3COOH +
CH3COO
OH

Rxn

25.00 mL
0.200 M =
5.00 mmol
5.00 mmol
= 0.00 mmol

Pe

Before

After

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

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

159

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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 ]

= 5.6 10 10

x2
=
0.100

160

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## Ex. 14 Weak Acid and Strong Base

3. At the equivalence point

x =

= (0.100) 5.6 10
5.6 10

11

10

) = 5.6 10

11

= 7.5 10 M

Pe

## So at the equivalence point, pH is determined by

the conjugate base equilibrium
161

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

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

162

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

163

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

Pe

164

Pe

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

Strong Base

165

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

166

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

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

167

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

) = 3.23

168

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

169

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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+

N2H4 +
H+

N2H5+
Before

25.0mL
0.200M =
5.00 mmol

Rxn

After

Pe

12.5mL
0.200M =
2.50 mmol

170

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

## Chemistry: The Molecular Nature of Matter, 6E

171

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

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

acid N2H5+

172

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

173

Ka =

I
C
E

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

174

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## Ex. 15 Weak Base with Strong Acid

4. After equivalence point

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

175

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

176

Pe

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

Strong Acid

177

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

178

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

1.00 mmol

179

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

pK a = 4.74

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

180

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

181

pH =

rs
o
U n
se al
w us
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

182

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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)

+ In

(aq)

base form
(another color)

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

183

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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

184

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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]

## Chemistry: The Molecular Nature of Matter, 6E

185

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

A. If [In] = 10[HIn]

[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

[In ]
log
1
[HIn ]

## Chemistry: The Molecular Nature of Matter, 6E

186

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

B. If [HIn] = 10[In]

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

## Taking log of both sides gives

pK In = pH log(10 1 )

pK In = pH ( 1)

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

187

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

## 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
Want indicator whose pKIn = pHeq pt 1

188

rs
o
U n
se al
w us
is e
el o
y! nl
!! y

Indicator

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