1

Chapter 17 Objectives: Weak Acids, Weak Bases, Salts, and Buffers

Terms: acid ionization constant (K
a
), base ionization constant (K
b
), salt, neutralization reactions, common
ion effect, buffer solution, buffer capacity, Henderson-Hasselbach Equation, titration, stoichiometric point,
equivalence point, analyte, titrant, indicator, end point

Objectives:
Calculate the pH and pOH of aqueous solutions of acids, bases, salts, and buffers.
Use the autoprotolysis constant of water to calculate base ionization constants and acid ionization
constants.
Use K
a
and K
b
to predict the relative strengths of acids and bases.
Predict whether an ion in aqueous solution is acidic, basic, or neutral.
Use the Henderson-Hasselbach equation when calculating the pH of a buffer solution.
Explain the importance of buffer solutions and buffer capacity.
Use titration data to calculate the K
a
or K
b
.
Select the appropriate indicator for the titration of an acid or base.

Problems: 1, 2, 4, 7, 8, 9, 13, 15, 17, 21, 27, 31, 37, 41, 10, 11, 12, 43, 47, 51, 53, 59, 69, 75




































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Calculating the pH and pOH of Aqueous Solutions
Assume all solutions at 25C unless otherwise indicated.

What is the pH of 0.60 M acetic acid solution?
First step: Am I working with a strong acid (or base)? (If not, I need the list of K
a
(or K
b
) values and an ICE
chart!)
Write the equation:


Write the acidity constant expression and the value of K
a
:

K
a
= =


Set up an ICE chart:
[CH
3
CO
2
H] M [CH
3
CO
2
-
] M [H
3
O
+
] M
I 0.60 0 0
C
E

Set up the problem:



Put the problem in the form ax
2
+bx +c =0




Solve for x and determine the valid solution:




Calculate the pH

Making assumptions
Sometimes by looking at the equations we can make assumptions and simplify our equations
without significantly changing the answer

Let's assume that x <<<< 0.60 so that 0.60 - x 0.60
Now solve the equation for x making that assumption:





Calculate the pH:




Was our assumption valid (within 5%)?

If the K
a
or K
b
is <10
-4
the assumption is usually valid.
3
Calculating pH and pOH of solutions of weak bases!

What is the pH of 0.060 M pyridine solution?
First step: Am I working with a strong acid (or base)? (If not, I need the list of K
a
(or K
b
) values and an ICE
chart!)
Write the equation:



Write the basicity constant expression and the value of K
b
:

K
b
= =


Set up an ICE chart:
[C
5
H
5
N] M [C
5
H
5
NH
+
] M [OH
-
] M
I 0.060 0 0
C
E

Set up the problem:



Make an assumption and solve for x:




Calculate the pH (Remember pH = -log[H
3
O
+
] and you just solved for [OH
-
] therefore calculate the
pOH first!)


Calculating the pH of Salt Solutions

Can we calculate how the pH of the 0.10 M sodium acetate solution? Of course!
Step 1: Write the equations



Step 2: Calculate K
b
of CH
3
CO
2
-
(We use the K
w
and the K
a
of acetic acid.)




Step 3: Prepare an ICE table

[CH
3
CO
2
-
] [CH
3
CO
2
H] [OH
-
]
I
C
E

Step 4: Set up equation - Can any assumptions be made?


4
Step 5: Solve for [OH
-
]



Step 6: Calculate the pH


Calculating the pH of Buffer Solutions
Buffer solutions are prepared from a weak acid and salt of the conjugate base or from a weak base
and the salt of the conjugate acid.

What is the pH of a solution containing 0.50 M CH
3
CO
2
H and 0.50 M NaCH
3
CO
2
?
Write the equation.



Look up the K
a
and write the acidity constant expression.



Prepare ICE chart
[CH
3
CO
2
H] [CH
3
CO
2
-
] [H
3
O
+
]
I 0.50 0.50 0
C -x +x +x
E

Set up the equation. Can we make some assumptions?



Solve for x:




Calculate the pH.


Note: The [H
3
O
+
] =K
a
and pH =pK
a
of acetic acid.

If we have a solution containing equal molar amounts of a weak acid and its conjugate base (initially)
the pH =pK
a
. (Similarly, if we have a solution containing equal molar amounts of a base and its
conjugate acid, the pOH = pK
b
)
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What if the concentrations are not equilmolar?
What is the pH of a solution containing 0.40 M CH
3
CO2H and 0.20 M NaCH
3
COO?
Write the equation.


Look up the K
a
and write the acidity constant expression.


Prepare ICE chart
[CH
3
CO
2
H] [CH
3
CO
2
-
] [H
3
O
+
]
I 0.40 0.20 0
C -x +x +x
E
Set up the equation. (Can we make some assumptions?)



Solve for x:



Calculate the pH.

Henderson- Hasselbach Equation



Why do buffers buffer?
What happens to pH of a buffer solution if we add NaOH (1.00 g) to 100 mL of a 0.50 M CH
3
CO
2
H/
0.50M NaCH
3
CO
2
buffer?


What acid base reaction occurs?



CH
3
CO
2
H NaOH NaCH
3
CO
2

Concentration before reaction
Volume
Moles before reaction of NaOH
Moles reacted
Moles after addition of NaOH
Volume (assume no change)
Concentration after reaction.

Use the Henderson- Hasselbach Equation to calculate pH.


\Strong Acid Strong base Titration

What is present in solution at the stoichiometric (equivalence) point?

+
initial
initial
a
[acid]
base] [conjugate
log pK pH

+
initial
initial
b
[base]
acid] [conjugate
log pK pOH
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What is the pH of the stoichiometric point?

How do things differ a weak acid is titrated?

Where is the stoichiometric point?
What is the pH at the stoichiometric point?
Why is part of the graph flat?
What is the pKa of the weak acid?
What is a good indicator for this titration?