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Ch16-Equilibria Weak Acids Bases PDF
Ch16-Equilibria Weak Acids Bases PDF
1
Index
16.1 Ionization constants can be defined for weak
acids and bases
16.2 Calculations can involve finding or using Ka
and Kb
16.3 Salt solutions are not neutral if the ions are
weak acids or bases
16.4 Simplifications fail for some equilibrium
calculations
16.5 Buffers enable the control of pH
16.6 Polyprotic acids ionize in two or more steps
16.7 Acid-base titrations have sharp changes in pH at
the equivalence point
2
Acids and Ka
16.1 Ionization constants can be defined for weak acids and bases 5
For Conjugate Pairs Kw = Ka × Kb
16.1 Ionization constants can be defined for weak acids and bases 6
Learning Check
16.1 Ionization constants can be defined for weak acids and bases 7
Learning Check
16.1 Ionization constants can be defined for weak acids and bases 8
Your Turn!
Given that Ka for benzoic acid (C6H5CO2H) = 6.28 × 10-5,
what is the Kb for sodium benzoate, NaC6H5CO2, a
common preservative?
A. 6.28 × 10-5
B. 6.28 × 10-19
C. 1.59 × 10-10
D. None of these
16.1 Ionization constants can be defined for weak acids and bases 9
Determining the pH of Aqueous Weak Acid
Solutions
• Dominant equilibrium is Ka reaction
Write the net ionic equation
Look up the Ka value for the acid
Set up ICE table
Solve for x
• Calculate pH from the hydronium concentration at
equilibrium
3.16 10
2
I 0.50 NA 0 0 4
Ka
C -x -x +x +x 0.5 3.16 10 4
E 0.50 - x NA x x
Ka = 2.0 × 10-7
16.2 Calculations can involve finding or using Ka and Kb 21
Approaches to Common Types of Problems
16.3 Salt solutions are not neutral if the ions are weak acids or bases 23
Predicting Effects of Ions on pH
• Most metal cations are neutral or extremely weak
acids
• Conjugate acids of weak bases are acidic
• Conjugate bases of weak acids are basic
• Conjugate bases of the strong acids are neutral
(except HSO4- which is still fairly acidic)
16.3 Salt solutions are not neutral if the ions are weak acids or bases 24
Learning Check
0.1 M solutions of the following are acid/ base/ neutral
or amphoteric? …
HCl • acid
NaCl • neutral
NaCN • base
HCN • acid
Na2S • base
Na3PO4 • base
NH4Cl • acid
16.3 Salt solutions are not neutral if the ions are weak acids or bases 25
Learning Check
Determine the pH of a 0.1 M solution of the salt NaF
• Basic due to F- F- (aq) + H2O OH-(aq) + F(aq)
• Kb = Kw/Ka I 0.1 M N/A 0 0
Ka HF = 6.8 x 10-4 C -x -x +x +x
pH = 8.08
16.3 Salt solutions are not neutral if the ions are weak acids or bases 26
Your Turn!
What is the pH of a 0.30 M solution of NaCN (Kb of
CN- = 2.5 × 10-5)?
A. 2.56
B. 11.4
C. 0.523
D. None of the above
16.3 Salt solutions are not neutral if the ions are weak acids or bases 27
Using the Quadratic Equation
• Dropping x in binomial terms usually works when the
concentration of the binomial is > 400 × K
• If the value of x > 5% of the initial concentration, we
are often left with a complicated expression
• If the expression can be reduced to the form
ax2 + bx + c = 0, it may be solved explicitly using the
quadratic equation.
2
b b 4ac
x
2a
I 0.1 M N/A 0 0
x2 C
1.1 102 -x -x +x +x
0.1 x E (0.1 - x) N/A x x
x2 + (1.1×10-2)x - 1.1×10-3 = 0
b b 2 4ac
x
x = 2.81 × 10-2 M and x = -3.91 ×10-2 M 2a
pH = 1.55
No Yes
You’re finished.
Repeat Step 2 using
You have the best
the new value of x.
value of x.
16.4 Simplifications fail for some equilibrium calculations 30
Learning Check
What is the pH of a 0.1 M solution of NaHSO4 (Ka = 1.0 × 10-2) ?
Use successive approximation.
x2
• Drop x in binomial 1.0 102
2
0.1 x
x
1.0 102 x = 0.032
0.1
• Substitute for x x2
1.0 102
0.1 0.032
HSO4-(aq) + H2O H3O+(aq) + SO42- (aq)
x = 0.026
I 0.1 M N/A 0 0
C -x -x +x +x
E 0.1 – x ≈0.1 N/A x x
re-substitute for x x2
1.0 102
0.1 0.027
(0.2)x
1.8 105 x = 9.00 × 10-6 M
0.1
pH = 5.05
16.5 Buffers enable the control of pH 34
Simplification of Buffer pH Calculations
• The acid reaction is inhibited by the presence of the
conjugate base
• The change of the concentrations of the buffer pair do not
deviate much from their initial values
HA(aq) + H2O(aq) H3O+(aq) + A–(aq)
[H3O ][A ]
Ka
[HA]
A
log K a log H3O + log
HA
A A
log H3O log K a log pH = pK a log
HA HA
16.5 Buffers enable the control of pH 35
Learning Check
y 9.4 10-4 1.47 10 -11 y = 3.13 × 10-9
pH = 10.98
0.2
16.6 Polyprotic acids ionize in two or more steps 47
Polyprotic Acids
• Have more than one ionizable hydrogen
• Each successive ionization has a specific
ionization constant (Ka)
• Function as a mixture of acids: the first ionization
inhibits the second ionization, etc…
• For H3PO4:
H3PO4(aq) + H2O H3O+(aq) + H2PO4-(aq) Ka1
H2PO4-(aq) + H2O H3O+(aq) + HPO42-(aq) Ka2
HPO42-(aq) + H2O H3O+(aq) + PO43-(aq) Ka3
x2
7.1 103 x = 0.0233 M
(0.1 x)
x2
2.22 104 x = 0.00460
(0.1 x)
pOH = 2.34
pH = 11.66
16.6 Polyprotic acids ionize in two or more steps 54
Titration
• The controlled addition of one substance (titrant) to a
known quantity of another substance (titrate) until the
stoichiometric requirements are met
• Equivalence point - the volume of titrant needed to
achieve an equimolar concentration of titrant and of
titrate
• Endpoint - the volume of titrant necessary to achieve
the stoichiometric ratio of reactants
• The endpoint may be the last of several equivalence
points in the case of polyprotic acids
7
6
5
4
3
0 10 20 30
Volume NaOH (mL)
11
7
pH
1
0 10 20 30
Volume NaOH (mL)
16.7 Acid-base titrations have sharp changes in pH at the equivalence point 57
Titration of Phosphoric Acid by NaOH
12
10
8
pH
2
0 10 Volume NaOH (mL)
20 30
6
4
2
0
0 10 20 30
Volume NaOH (mL)
Volume of Titrant
[Start] 2.5 0 0
Reaction None- excess weak acid
HF Ka = 6.8 × 10-4
16.7 Acid-base titrations have sharp changes in pH at the equivalence point 70
Color Indicators
• Indicators change color within specific pH ranges
because each indicator is a weak organic acid
• As the concentrations of conjugate base vary, the
color varies
• We usually choose an indicator whose pKa= pH at the
endpoint of the reaction
• Select an indicator whose color change is light to dark
at this pH to optimize visual detection