Ch16-Equilibria Weak Acids Bases

Chapter 16
Equilibria in Solutions of Weak

Acids and Bases
Brady and Senese

5th Edition
1
Index
1. Ionization constants can be defined for
weak acids and bases
2. Calculations can involve finding or using Ka
and Kb
3. Salt solutions are not neutral if the ions are
weak acids or bases
4. Simplifications fail for some equilibrium
calculations
5. Buffers enable the control of pH
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
HA(aq) + H2O H3O+(aq) + A–(aq)

• All acids undergo ionization reaction with water
• Weak acids undergo this reaction as an equilibrium
process governed by the acid ionization constant, Ka.
• Strong acids are 100% efficient in non-reversible
reaction
• Ka are tabulated in table 16.1, as are pKa
• Ka = 10-pKa pKa = -log Ka
 H    A 
Ka    
HA 
16.1 Ionization constants can be defined for weak acids and bases 3
Bases and Kb
B(aq) + H2O BH+(aq) + OH–(aq)

• Undergo ionization reaction with water
• Weak bases undergo this reaction as an equilibrium
process governed by the base ionization constant, Kb
• Kb and pKb are tabulated in table 16.2
• Kb = 10-pKb pKb = -log Kb
 BH    OH  
Kb    
B 
Your Turn!
Which of the following is a product in the acid
ionization of H2CO3?
A. HCO3-
B. H2O
C. CO32-
D. All of these
E. None of these
For Conjugate Pairs Kw = Ka × Kb
Learning Check
What is the value of Kb for the following weak

conjugate bases?
 NaF
 Kw = Ka × Kb Ka for HF = 6.8 × 10-4
 1.5 × 10-11
 NaCN
 Kw = Ka × Kb Ka for HCN = 6.2 × 10-10
 1.6 × 10-5
Learning Check
What is the value of Ka for the following weak

conjugate acids?
 NH4Cl
 Kw = Ka × Kb Kb for NH3 = 1.8 × 10-5
 5.6 × 10-10
 C6H5NH3NO3
 Kw =Ka × Kb Ka = 4.1 × 10-10
 2.4 × 10-5
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
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
16.2 Calculations can involve finding or using Ka and Kb 10

Simplifications: Dropping x Term
• If the K for the reaction is small, the change to
reach equilibrium (x term) is small (less than 5%
of the value of the starting concentration)
• In binomial terms, the x variable term may be
dropped in favor of the concentration (constant)
• You must perform a proof to show that the
dropped x was justified
?

dropped x term
0.05
constant of binomial

Learning Check
Determine the pH of 0.1 M solutions of:
HC2H3O2 HC2H3O2(aq) + H2O H3O+(aq) + C2H3O2-
• Ka = 1.8 × 10-5 (aq)
x2 0.1 M N/A 0 0
 1 . 8  1 0 5 I
0.1 -x -x +x +x
C
x = 1.34 × 10-3 M
(0.1 - x) ≈ 0.1 N/A x x
pH = 2.87 E
HCN HCN(aq) + H2O H3O+(aq) + CN-(aq)
• Ka = 6.2 × 10-10 I 0.1 M N/A 0 0

x2 10
 6.210 C -x -x +x +x
0.1
x = 7.87 × 10-6 M E (0.1 - x) ≈ 0.1 N/A x x
pH = 5.10
Determining the pH of Base Solutions
• Dominant equilibrium is Kb reaction
 Write the net ionic equation
 Set up ICE table for starting quantities
 Solve for x
• Calculate pOH from the [OH-] at equilibrium, and
convert to pH

Learning Check:
Determine the pH of 0.1 M solutions of:
• N2H4 N2H4(aq) + H2O OH-(aq)+ N2H5+(aq)
• Kb = 1.7 × 10-6 0.1 M N/A 0 0
I
x 2  1.7 10 6
C -x -x +x +x
0.1
x = 4.12 × 10-4 M E (0.1-x) ≈ 0.1 N/A x x
pOH = 3.38 pH = 10.62
• NH3 NH3(aq) + H2O H3O+(aq) + CN-(aq)

• Kb = 1.8 × 10-5 I 0.1 M N/A 0 0
x2
 1.810 5 C -x -x +x +x
0.1
x = 1.34 × 10-3 M E (0.1-x) ≈ 0.1 N/A x x
pOH = 2.87 pH = 11.13
Your Turn!
What is the pH of a 0.30 M solution of phenol
(C6H5OH), an ingredient in some older
mouthwashes? Ka = 1.3 × 10-10?
A. 9.2
B. 0.52
C. 9.4
D. None of these 5.20

Percent Ionization
• Weak acids ionize some amount less than 100%.
• The percentage to which it is ionized may be
calculated using the Ka for the acid and the
equilibrium concentrations
• Percentage ionized varies with starting
concentration, even for the same acid
moles ionized per liter

% ionization  100
available moles per liter

Learning Check
Determine the % ionization of 0.2 M solution of
HC2H3O2
HC2H3O2(aq)+ H2O H3O+(aq) + C2H3O2-(aq)
 Ka = 1.8 × 10-5
I 0.2 M N/A 0 0
x2
 1.810 5 C -x -x +x +x
0.2
E (0.2 - x) ≈ 0.2 N/A x x
x = 1.90 × 10-3 M

x
100  % 0.95% ionized
0.2
Learning Check
Determine the % ionization of 0.1 M solution of
HC2H3O2
HC2H3O2(aq)+ H2O H3O+(aq)+ C2H3O2-(aq)
• Ka=1.8×10-5
I 0.1 M N/A 0 0
x2
1.810 5 C -x -x +x +x
0.1
E (0.1-x) ≈ 0.1 N/A x x
x = 1.34 × 10-3 M

x
100  % 1.3% ionized
0.1
Your Turn!
What is the % ionization of 0.10 M HOCl?
(Ka = 3.0 × 10-8)
A. 0.5%
B. 0.05%
C. 5.5 × 10-6%
D. None of these

Your Turn!
What is the % ionization of 0.50 M HOCl?
(Ka = 3.0 × 10-8)
A. 0.12%
B. 6.0 × 10-6 %
C. 0.06%
D. None of these 0.025%

Learning Check
The pH of a 0.50 M solution
of an acidic drug, HD, is 3.5. Given the pH, we find
What is the value of the K a the value of x = 10-pH
for the drug? x = 10-3.5 = 3.16 × 10-4
x2
HD + H2O H3O+ + D-  Ka
0.50 x
I 0.50 NA 0 0 3.1610  4 2
Ka
C -x -x +x +x 0.5  3.16 10  4
E 0.50 - x NA x x
Ka = 2.0 × 10-7
Approaches to Common Types of Problems
• Strong acid? pH = -log[H3O+]

• Strong base? pOH = -log[OH-]
 pH + pOH = 14
• Weak acid? Write Ka rxn and solve for [H3O+]
• Weak base? Write Kb rxn and solve for [OH-]
• Weak conjugate pair (buffer)? Could use either the
Ka or the Kb reaction. We will address this later.

Predicting Acid–Base Properties of a Salt
1. If neither the cation nor the anion can affect the pH,
the solution should be neutral
2. If only the cation of the salt is acidic, the solution
will be acidic
3. If only the anion of the salt is basic, the solution will
be basic
4. If a salt has a cation that is acidic and an anion that is
basic, the pH of the solution is determined by the
relative strengths of the acid and base
 Compare Ka and Kb for the ions
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)
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
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
E (0.1 - x) ≈ 0.1 N/A x x

x2
 1.471011
0.1
pOH = 5.92
pH = 8.08
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
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.
b  b2 4ac
x
2a
16.4 Simplifications fail for some equilibrium calculations 28

Learning Check
• Determine the pH of a 0.1 M solution of NaHSO4
• HSO4- is an acid
HSO4-(aq) + H2O H3O+(aq) + SO42-(aq)
I 0.1 M N/A 0 0
x2 C
 1.110 2 -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  b2 4ac
x
x = 2.81 × 10-2 M and x = -3.91 ×10-2 M 2a
pH = 1.55

Solving by Successive Approximations
When the equation cannot be reduced to a quadratic,
successive approximation may be used to estimate the
answer
Step 1 Step 2 Step 3
Assume x is Substitute the Compare the
negligible value of x into new value of x
compared to the the denominator. with the previous
initial Solve the one. Are they the
concentration. equation to same?
Solve the obtain a new
equation for x. value of x.
No Yes
You’re finished.
Repeat Step 2 using You have the best
the new value of x. value of x.
Learning Check
What is the pH of a 0.1 M solution of NaHSO4 (Ka = 1.0 × 10-2) ?
Use successive approximation.
x2 2
• Drop x in binomial  1.010
2
0.1  x
x
 1.010 2 x = 0.032
0.1
• Substitute for x x2
 1.010 2
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

Learning Check (cont.)
What is the pH of a 0.1 M solution of NaHSO4 (Ka = 1.0 × 10-2) ?
Use successive approximation.
x2
 re-substitute for x  1.010 2
2 0.1 x
x
 1.0102 x = 0.027
0.1 0.026
 re-substitute for x x2
1.010 2
0.1 0.027
HSO4-(aq) + H2O H3O+(aq) + SO42- (aq)

x = 0.027
I 0.1 M N/A 0 0
pH = -log 0.027
C -x -x +x +x
pH = 1.57
E 0.1 - x ≈ 0.1 N/A x x

Buffers Enable the Control of pH
• Are a combination of a weak acid and its conjugate
weak base
• Are a special case of the common ion effect (the
presence of the conjugate base inhibits the ionization
of the Brønsted acid)
• Are resistant to changes in the pH
 Any acid added to the mixture is reacted by the base of the
buffer pair
 Added bases are reacted by the conjugate acid
16.5 Buffers enable the control of pH 33

Learning Check:
What is the pH of a buffer made by combining 0.1 M
HC2H3O2 (Ka = 1.8 × 10-5) and 0.2 M NaC2H3O2
 Inhibition limits the value of x
HC2H3O2 + H2O H3O+(aq) + C2H3O2 -(aq)
I 0.1 M N/A 0 0.2

C -x -x +x +x
E 0.1 - x ≈ 0.1 N/A x 0.2 + x ≈ 0.2
(0.2)x x = 9.00 × 10-6 M

 1.810 5
0.1
pH = 5.05
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 = pKa  log  
HA  HA 
Learning Check
What is the pH of a buffer made from 0.5 M HF (Ka = 6.8 × 10-4)

and 0.2 M NaF?
A  pKa = -log 6.8 × 10-4

pH = pK a  log  
HA 

pH  3.17  log 
0.2 

 0.5 
pH = 2.77

Buffer Characteristics
• Buffer capacity is the ability to compensate for added
acid or base, defined for each component
 acid buffer capacity = moles of conjugate base present
 base buffer capacity = moles of acid present.
• If acid is added, remove from base and add to the acid of
the pair  mol A  mol acid 
  mol HA  mol acid 
pH = pKa log
• If base is added, remove from acid of the pair and add to

the acid of the pair.
 mol A  mol base 
pH = pKa log mol HA  mol base 
 
Your Turn!
Which of the following could be used as a buffering
pair?
A. NH4Cl/NH3
B. HCl/NaCl
C. NaOH/H2O
D. All of these

Buffer Characteristics
Consider 500 mL of a sodium acetate/acetic acid buffer in which
the concentration of sodium acetate is 0.5 M and that of acetic
acid is 0.1 M. What is the pH after 10 mL of 0.1 M NaOH is
added? (Ka acetic acid = 1.8 × 10-5)
HC2H3O2 is the acid of the buffer, thus it reacts the NaOH
HC2H3O2(aq) + OH-(aq) H2O(l) + C2H3O2-(aq)
0.5 L ×0.1 M 0.1 L ×0.1 M N/A 0.5L × 0.5 M
0.05 mol 0.01 mol N/A 0.25 mol start
0.05 – 0.01 0 0.25 + 0.01
 0.25  0.01 mol 

pH  pK a  log  0.05 - 0.01 mol  pH = 5.56
 

Selecting a Buffer
• To choose buffer system, try to find a system

whose pKa is close to desired system pH
• Then, calculate necessary ratio of components to
obtain desired pH.
• Consider toxicity of the materials!

Learning Check
Choose a buffer system to maintain a pH of 5.5. Describe its
composition completely.
• Select acid with pKa ≈ 5.5  mol A 

5.5  pKa  log
• Thus, look for Ka ≈ 3.2×10-6 mol HA
 
• H2C8H4O4, phthalic acid has mol 2 
C H O
Ka2 = 3.9×10-6 (pKa = 5.41) 5.5  5.41 log 8 4 4

 mol HC H O  
• We could use NaHC8H4O4 and  8 4 4 
Na2C 8H 4O 4  mol C8 H4 O4 2 
1.23
 mol HC H O  
 8 4 4 

Your Turn
What is the pH of a buffer made by combining 0.10
mol of H2CO3 (Ka = 4.5 × 10-7) and 0.20 mol of
NaHCO3 in a 3.0 L vessel.
A. 6.05
B. 6.35
C. 6.65
D. None of these

Mixtures of Acids
• Acids will not react with one another, but they
each have a Ka reaction with water
• The most efficient reaction (higher Ka) occurs 1st.
• Carry the common ion (H3O+) concentration as a
starting quantity in subsequent reactions
• Determine the pH at the end.
16.6 Polyprotic acids ionize in two or more steps 43

Learning Check
Determine the pH of a mixture of 0.05 M HCl and 0.2 M HF
(0,0H5+Cxl)(+x)H/(0F,2→-x)N=R6,8E-04
x^2+(0,05+ka)x-Ka*0,2=0
HCl(aq) + H 2O H3O+(aq) + Cl-(aq)
0.05 a= N/A 1 0 0 I
-0.05 b= N/A 0,05068 +0.05 +0.05 C
c= -0,00014
0 N/A 0.05 0.05 end
HF(aq) x+= H2O0,002555 H3O+(aq) + F-(aq) 0.05x
6.8104
0.2 [H3O+]N
=/A0,052555 0.05 0 I 0.2
-x pH= -x 1,279388 +x +x C x = 2.72 × 10-3
(0.2 - x) ≈ 0.2 N/A (0.05 + x) ≈ 0.5 x E

[H+] = 0.05 + (2.72 × 10-3) = 0.0527 M pH = 1.28
Your Turn
What is the pH of a mixture of 0.10 M HCl and 0.10
M HCN?
A. 1
B. 1.2
C. 2.4
D. None of these

Mixtures of Bases
• Bases will not react with one another, but they

each react with water according to their Kb
• The most efficient reaction (higher Kb) occurs 1st
• The common ion (OH-) concentration is a starting
quantity in subsequent reactions
• Use the [OH-] to find pOH at the end, then find
pH

Learning Check
Determine the pH of a mixture of 0.05 M NH3 (Kb = 1.8 × 10-5) and
= 1.47 × 10-11 )
0.2 M NaF (Kb x^2+1,8E-05x-0,05*1,8E-05=0
NH3 + NaF → NR
a= 1
NH3 + H2O(l) OH-(aq) + NH4+(aq)
b= 1,80E-05
0.05 cN=/A 0 I
-90 ,00E-07 x2 -5
 1.810
-x N/A +x +x C 0.05-x
0.05-x xN=/A 9,x397E-04 x E
F-(aq) + H2O(l) OH-(aq) + HF (aq) x = 9.49 × 10-4
0.2 N/A 9.40×10-4 0 I

-y -y +y +y C
(0.2 - y) ≈ 0.2 N/A (9.40 × 10-4 + y) y E pOH = 3.02

y 9.410-4   1.4710 -11 y = 3.13 × 10-9
pH = 10.98
0.2
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

Learning Check
What is the pH of a 0.1 M solution of H3PO4?
-3 -8; -13
Ka1 = 7.1 × 10 ; Ka2 = 6.3 × 10 Ka3 = 4.5 × 10
H3PO4(aq) + H2O(l) H3O+(aq) + H2PO4-(aq)
I 0.1 M N/A 0 0
C -x -x +x +x
E (0.1 - x) N/A x x
x2
 7.110 3 x = 0.0233 M
(0.1 x)
Since Ka1 > 20 Ka2, the amount of H3O+ contributed by

step 2 is negligible
pH=1.63
Learning Check
What is the concentration of all ions present in a 0.1 M H2CO3
at equilibrium? Ka1 = 4.5 × 10-7; Ka2 = 4.7 × 10-11
H2CO3(aq) + H2O H3O+(aq) + HCO3-(aq)

I 0.1 N/A 0 0
C -x -x +x +x
E 0.1 - x N/A x x
x2
 4.510 7 x = 0.000212 M
(0.1 x)
H2CO3(aq) + H2O H3O+(aq) + HCO3-(aq)

0.00978 M N/A 2.12 × 10-4 M 2.12 × 10-4 M

Learning Check (Cont.)
What are the concentrations of all ions present in a 0.1 M
H2CO3 at equilibrium? Ka 1=4.5×10-7; Ka 2=4.7×10-11
2-
HCO3-(aq) + H2O H3O+(aq) + CO3 (aq)
I 2.12 × 10-4 N/A 2.12 × 10-4 0
C -y -y +y +y
E 2.12 × 10-4 - y N/A (2.12 × 10-4 + y) y
(0.000212  y)y
 4.71011 y = 4.7×10-11 M
(0.000212  y)
HCO3-(aq) + H2O H3O+(aq) + CO32-(aq)
2.12 × 10-4 N/A 2.12 × 10-4 4.7 × 10-11
[H2CO3] = 0.00978M
- + -4
[HCO3 ] = [H3O ] = 2.12 × 10 M
2- -11
[CO3 ] = 4.7×10 M
Your Turn
What is the expected pH in a 0.10 M solution of H3X?
-7 -9 -12
Ka1 = 3.3 × 10 , Ka2 = 2.5 × 10 , Ka3 = 2.2 × 10
A. 7.5
B. 6.3
C. 4.8
D. 3.7
E. None of these

Salts of Polyprotic Acids
• Are amphoteric, and most are basic in water.

• To predict the behavior in water, the Ka to its Kb.
• Example: Is an aqueous solution of NaHCO3
likely to be basic or acidic?
 NaHCO3 is a salt of neutral Na+ and amphoteric HCO3-
 Ka = 4.7 × 10-11; Kb = 10-14/4.5 × 10-11 = 2.22 × 10-4
 Since Kb > Ka, the salt is basic in water

Learning Check
What is the pH of a 0.1 M solution of NaHCO3?
Ka = 4.7 × 10-11; Kb = 10-14/4.7 × 10-11 = 2.22 × 10-4.
HCO3-(aq) + H2O(l) OH-(aq) + H2CO3(aq)

I 0.1 N/A 0 0
C -x -x +x +x
E 0.1 - x N/A x x
x2
 2.2210 4 x = 0.00460
(0.1 x)
pOH = 2.34
pH = 11.66
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
16.7 Acid-base titrations have sharp changes in pH at the equivalence point 55

Titration of Acetic Acid by NaOH
12
11
10
9
8
pH
7
6
5
4
3
0 10 20 30
Volume NaOH (mL)

Titration of Nitric Acid by NaOH
11
7
pH
1
0 10 20 30
Volume NaOH (mL)
Titration of Phosphoric Acid by NaOH
12
10
8
H
p
2
0 20
10Volume NaOH(mL) 30

Titration of Sulfuric Acid with NaOH
14
12
10
8
pH
6
4
2
0
0 10 20 30
Volume NaOH (mL)

Reactions of Acids and Bases
• Produce conjugate acid and bases
• May not create neutral products:
 Strong Acids + Strong Bases → Neutral Salts
 Weak Acids + Strong Bases → Basic Salts
 Strong Acids + Weak Bases → Acid Salts
 Weak Acids + Weak Bases → Amphoteric Salts
Check Ka vs. Kb for dominance (We will not do titration calculations
based on this type of reaction)
• Occur in order of strongest acid to weakest acid and
strongest base to weakest base.

Your Turn
How many ionizable hydrogens are indicated by the
titration of the acid?
A. 1
B. 2
C. 3 pH
D. Can’t tell from the data
Volume of Titrant

An Approach to Titration Problems
• Write the net ionic equation
• Dilute the starting quantities
• React the limiting reagent
• Analyze what remains:
 Excess strong acid? pH = -log[H3O+];
 Excess strong base? pOH = -log[OH-]
 Excess weak acid? Write Ka rxn and solve for [H3O+]
 Excess weak base? Write Kb rxn and solve for [OH-]
 Buffer? Use buffer equation
• Endpoint: determined through stoichiometry
Learning Check
If 25 mL of 2.5 M HCl are titrated with 2.2 M NaOH. What
is the pH at 0 mL?
H3O+(aq) + OH-(aq) 2H2O
Volume [Acid] Volume [Base] Volume [product]

Acid Base Total
25 (25/25) × 2.5 0 (0/25) × 2.2 25 + 0 0
[start] 2.5 0 Neutral. N/A
react? None - no base yet.
Treat as aqueous acid solution. Here is strong acid.

pH = -log 2.5 M = -0.40
If 25 mL of 2.5 M HCl are titrated with 2.2 M NaOH, what
is the pH at 15 mL?
H3O+(aq) + OH-(aq) 2H2O(l)
Volume [Acid] Volume [Base] Volume total

Acid Base
25 (25/40) × 2.5 15 (15/40) × 2.2 25 + 15 = 40 mL
[start] 1.56 0.825
Reaction -0.825 -0.825
remain 0.735 0
Here again, excess strong acid.

pH = -log 0.735 = 0.13
If 25 mL of 2.5 M HCl are titrated with 2.2 M NaOH, what is
the pH at 30 mL?
H3O+(aq) + OH-(aq) 2H2O(l)
Volume [Acid] Volume [Base] Volume total

acid base
25 (25/55) × 2.5 30 (30/55) × 2.2 25 + 30 = 55
[start] 1.14 1.2
Reaction -1.14 -1.14
Remain 0 0.06
Here, excess strong base

pOH = -log 0.06 = 1.22 pH = 14 – pOH = 12.78
Learning Check
If 25 mL of 2.5 M HC2H3O2 are titrated with 3.2 M
NaOH, what is the pH at 0 mL?
Volume [Acid] Volume [base] Volume [C2H3O -]

2
acid base total
25 (25/25) × 2.5 0 (0/25) × 3.2 25 + 0 0
[Start] 2.5 0 0
Reaction None- excess weak acid

If 25 mL of 2.5 M HC2H3O2 are titrated with 3.2 M NaOH,
what is the pH at 0 mL? (con)
Write the Ka reaction for the weak acid
HC2H3O2(aq) + H2O(l) H3O+(aq) + C2H3O2-(aq)
HC2H3O2(aq) H2O(l) H3O+(aq) C2H3O2-(aq)

[Start] 2.5 M N/A 0 0
Reaction -x -x +x +x
[Equil] 2.5 - x N/A x x
x2
 1.8105 ; x  6.70810 3   H3O  
2.5 - x  
pH  log x  2.17
If 25 mL of 2.5 M HC2H3O2 are titrated with 3.2 M
NaOH, what is the pH at 15 mL?
Volume [acid] Volume [base] Volume [C2H3O -]
2
acid base total
25 (25/40) × 2.5 15 (15/40) × 3.2 25 + 15 0
[start] 1.56 1.20 0
rxt -1.20 -1.20 +1.20
remain 0.36 0 1.20
We have a buffer mix, so use buffer equation
pH  log(1.8105 )  log
1.20 
  5.27
 0.36 
If 25 mL of 2.5 M HC2H3O2 are titrated with 3.2 M NaOH,
what is the pH at 30 mL?
Volume [acid] Volume [base] Volume [C2H3O -]
2
acid base total
25 (25/55) × 2.5 30 (30/55) × 3.2 25 + 30 0
[start] 1.136 1.745 0
rxt -1.136 -1.136 + 1.136
remain 0 0.609 1.136
We have excess strong base, so the rule of 20 applies.

pOH = -log 0.609 pH = 14 - 0.22 = 13.78

Your Turn
What is the pH after 25.2 mL of 3.5 M NaOH have
been added to 25.00 mL of 4.2 M HF?
A. 1.76
B. 13.5
C. 14.5
D. None of these 3.89
HF Ka = 6.8 × 10-4
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

Ch16-Equilibria Weak Acids Bases

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Ch16-Equilibria Weak Acids Bases

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Chapter 16

Equilibria in Solutions of Weak

Brady and Senese

HA(aq) + H2O H3O+(aq) + A–(aq)

B(aq) + H2O BH+(aq) + OH–(aq)

What is the value of Kb for the following weak

What is the value of Ka for the following weak

16.2 Calculations can involve finding or using Ka and Kb 10

16.2 Calculations can involve finding or using Ka and Kb 11

HCN HCN(aq) + H2O H3O+(aq) + CN-(aq)

• Ka = 6.2 × 10-10 I 0.1 M N/A 0 0

16.2 Calculations can involve finding or using Ka and Kb 13

• NH3 NH3(aq) + H2O H3O+(aq) + CN-(aq)

16.2 Calculations can involve finding or using Ka and Kb 15

moles ionized per liter

16.2 Calculations can involve finding or using Ka and Kb 16

moles ionized per liter

moles ionized per liter

16.2 Calculations can involve finding or using Ka and Kb 19

16.2 Calculations can involve finding or using Ka and Kb 20

• Strong acid? pH = -log[H3O+]

16.2 Calculations can involve finding or using Ka and Kb 22

E (0.1 - x) ≈ 0.1 N/A x x

16.4 Simplifications fail for some equilibrium calculations 28

16.4 Simplifications fail for some equilibrium calculations 29

16.4 Simplifications fail for some equilibrium calculations 31

HSO4-(aq) + H2O H3O+(aq) + SO42- (aq)

16.4 Simplifications fail for some equilibrium calculations 32

16.5 Buffers enable the control of pH 33

I 0.1 M N/A 0 0.2

(0.2)x x = 9.00 × 10-6 M

What is the pH of a buffer made from 0.5 M HF (Ka = 6.8 × 10-4)

A  pKa = -log 6.8 × 10-4

16.5 Buffers enable the control of pH 36

• If base is added, remove from acid of the pair and add to

16.5 Buffers enable the control of pH 38

 0.25  0.01 mol 

16.5 Buffers enable the control of pH 39

• To choose buffer system, try to find a system

16.5 Buffers enable the control of pH 40

• Select acid with pKa ≈ 5.5  mol A 

16.5 Buffers enable the control of pH 41

16.5 Buffers enable the control of pH 42

16.6 Polyprotic acids ionize in two or more steps 43

-x pH= -x 1,279388 +x +x C x = 2.72 × 10-3

(0.2 - x) ≈ 0.2 N/A (0.05 + x) ≈ 0.5 x E

16.6 Polyprotic acids ionize in two or more steps 45

• Bases will not react with one another, but they

16.6 Polyprotic acids ionize in two or more steps 46

0.2 N/A 9.40×10-4 0 I

16.6 Polyprotic acids ionize in two or more steps 48

Since Ka1 > 20 Ka2, the amount of H3O+ contributed by

H2CO3(aq) + H2O H3O+(aq) + HCO3-(aq)

H2CO3(aq) + H2O H3O+(aq) + HCO3-(aq)

16.6 Polyprotic acids ionize in two or more steps 50

16.6 Polyprotic acids ionize in two or more steps 52

• Are amphoteric, and most are basic in water.

16.6 Polyprotic acids ionize in two or more steps 53

HCO3-(aq) + H2O(l) OH-(aq) + H2CO3(aq)

16.7 Acid-base titrations have sharp changes in pH at the equivalence point 55

16.7 Acid-base titrations have sharp changes in pH at the equivalence point 56

16.7 Acid-base titrations have sharp changes in pH at the equivalence point 58

16.7 Acid-base titrations have sharp changes in pH at the equivalence point 59

16.7 Acid-base titrations have sharp changes in pH at the equivalence point 60