Fundamentals of Analytical Chemistry: 8th ed.

Chapter 14

Chapter 14

14-1 (a) The initial pH of the NH3 solution will be less than that for the solution containing

NaOH. With the first addition of titrant, the pH of the NH3 solution will decrease rapidly

and then level off and become nearly constant throughout the middle part of the titration.

In contrast, additions of standard acid to the NaOH solution will cause the pH of the

NaOH solution to decrease gradually and nearly linearly until the equivalence point is

approached. The equivalence point pH for the NH3 solution will be well below 7,

whereas for the NaOH solution it will be exactly 7.

(b) Beyond the equivalence point, the pH is determined b the excess titrant. Thus, the

curves become identical in this region.

14-2 Completeness of the reaction between the analyte and the reagent and the concentrations

of the analyte and reagent.

14-3 The limited sensitivity of the eye to small color differences requires that there be a

roughly tenfold excess of one or the other form of the indicator to be present in order for

the color change to be seen. This change corresponds to a pH range of ± 1 pH unit about

the pK of the indicator.

14-4 Temperature, ionic strength, and the presence of organic solvents and colloidal particles.

14-5 The standard reagents in neutralization titrations are always strong acids or strong bases

because the reactions with this type of reagent are more complete than with those of their

weaker counterparts. Sharper end points are the consequence of this difference.
Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

14-6 The sharper end point will be observed with the solute having the larger Kb.

1.00  10 14
(a) For NaOCl, Kb  8
 3.3  10 7
3.0  10

1.00  10 14
For hydroxylamine Kb  6
 9.1 10 9 Thus, NaOCl
1.1 10

1.00  10 14
(b) For NH3, Kb   1.75  10 5
5.7  10 10

1.00  10 14
For sodium phenolate, K b  10
 1.00  10 4 Thus, sodium phenolate
1.00  10

(c) For hydroxyl amine Kb = 9.110-9 (part a)

1.00  10 14
For methyl amine, Kb  11
 4.3  10 4 Thus, methyl amine
2.3  10

1.00  10 14
(d) For hydrazine Kb  8
 9.5  10 7
1.05  10

1.00  10 14
For NaCN, Kb  10
 1.6  10 3 Thus, NaCN
6.2  10

14-7 The sharper end point will be observed with the solute having the larger Ka.

(a) For nitrous acid Ka = 7.110-4

For iodic acid Ka = 1.710-1 Thus, iodic acid

(b) For anilinium Ka = 2.5110-5

For benzoic acid Ka = 6.2810-5 Thus, benzoic acid

(c) For hypochlorous acid Ka = 3.010-8

For pyruvic acid Ka = 3.210-3 Thus, pyruvic acid

(d) For salicylic acid Ka = 1.0610-3

For acetic acid Ka = 1.7510-5 Thus, salicylic acid

Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

+ - [H 3 O  ][In - ]
14-8 HIn + H2O  H3O + In  Ka
[HIn]

pKa = 7.10 (Table 14-1)

Ka = antilog(-7.10) = 7.9410-8

[HIn]/[In-] = 1.43

Substituting these values into the equilibrium expression and rearranging gives

[H3O+] = 7.9410-81.43 = 1.1310-7

pH = -log(1.1310-7) = 6.94

+ + [H 3 O  ][In]
14-9 InH + H2O  In + H3O  Ka
[InH  ]

For methyl orange, pKa = 3.46 (Table 14-1)

Ka = antilog(-3.46) = 3.4710-4

[InH+]/[In] = 1.64

Substituting these values into the equilibrium expression and rearranging gives

[H3O+] = 3.4710-41.64 = 5.6910-4

pH = -log(5.6910-4) = 3.24

14-10 [H3O+] = Kw and pH = -log(Kw)1/2 = -½logKw

At 0oC, pH = -½ log(1.1410-15) = 7.47

At 50oC, pH = -½ log(5.4710-14) = 6.63

At 100oC, pH = -½ log(4.910-13) = 6.16

Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

14-11 At 0oC, pKw = -log(1.1410-15) = 14.94

At 50oC, pKw = -log(5.4710-14) = 13.26

At 100oC, pKw = -log(4.910-13) = 12.31

14-12 pH + pOH = pKw and pOH = -log[OH-] = -log(1.0010-2) = 2.00

(a) pH = pKw - pOH = 14.94 - 2.00 = 12.94

(b) pH = 13.26 - 2.00 = 11.26

(c) pH = 12.31 - 2.00 10.31

14.0 g HCl 1.054 g soln 1 mmol HCl

14-13   = 4.047 M
100 g soln mL soln 0.03646 g HCl

[H3O+] = 4.047 M and pH = -log4.047 = -0.607

9.00 g NaOH 1.098 g soln 1 mmol NaOH

14-14   = 2.471 M
100 g soln mL soln 0.04000 g NaOH

[OH-] = 2.471 M and pH = 14.00 - (-log2.471) = 14.393

14-15 The solution is so dilute that we must take into account the contribution of water to [OH-]

which is equal to [H3O+]. Thus,

1.00  10 14
[OH-] = 2.0010-8 + [H3O+] = 2.0010-8 +
[OH - ]

[OH-]2 – 2.0010-8[OH-] – 1.0010-14 = 0

[OH-] = 1.10510-7

pOH = -log 1.10510-7 = 6.957 and pH = 14.00 – 6.957 = 7.04

14-16 The solution is so dilute that we must take into account the contribution of water to

[H3O+] which is equal to [OH-]. Thus,

Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

+ -8 - 1.00  10 14
-8
[H3O ] = 2.0010 + [OH ] = 2.0010 +
[H 3 O  ]

[H3O+]2 – 2.0010-8[H3O+] – 1.0010-14 = 0

[H3O+] = 1.10510-7 and pH = -log 1.10510-7 = 6.96

0.102 g Mg(OH) 2
14-17 In each part, = 1.749 mmol Mg(OH)2 taken
0.05832 g Mg(OH) 2 / mmol

(a) cHCl = (75.00.0600 – 1.7492)/75.0 = 0.01366 M

[H3O+] = 0.01366 and pH = -log(0.01366) = 1.87

(b) 15.00.0600 = 0.900 mmol HCl added. Solid Mg(OH)2 remains and

1 mmol Mg 2 1
[Mg2+] = 0.900 mmol HCl  = 0.0300 M
2 mmol HCl 15.0 mL soln

Ksp = 7.110-12 = [Mg2+][OH-]2

[OH-] = (7.110-12/0.0300)1/2 = 1.5410-5

pH = 14.00 - (-log(1.5410-5)) = 9.19

(c) 30.000.0600 = 1.80 mmol HCl added, which forms 0.90 mmol Mg2+.

[Mg2+] = 0.90/30.0 = 3.0010-2

[OH-] = (7.110-12/0.0300)1/2 = 1.5410-5

pH = 14.00 - (-log(1.5410-5)) = 9.19

(d) [Mg2+] = 0.0600 M

[OH-] = (7.110-12/0.0600)1/2 = 1.0910-5

pH = 14.00 - (-log(1.0910-5)) = 9.04

Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

14-18 In each part, (20.0 mL HCl  0.200 mmol HCl/mL) = 4.00 mmol HCl is taken

4.00 mmol HCl

(a) cHCl = [H3O+] = = 0.0889 M
20.0  25.0mL soln
pH = -log 0.0899 = 1.05

(b) Same as in part (a); pH = 1.05

(c) cHCl = (4.00 – 25.0  0.132)/(20.0 + 25.0) = 1.55610-2 M

[H3O+] = 1.55610-2 M and pH = -log 1.55610-2 = 1.81

(d) As in part (c), cHCl = 1.55610-2 and pH = 1.81

(The presence of NH4+ will not alter the pH significantly.)

(e) cNaOH = (25.0  0.232 – 4.00)/(45.0) = 4.0010-2 M

pOH = -log 4.0010-2 = 1.398 and pH = 14.00 – 1.398 = 12.60

14-19 (a) [H3O+] = 0.0500 and pH = -log(0.0500) = 1.30

(b)  = ½ {(0.0500)(+1)2 + (0.0500)(-1)2} = 0.0500

 H O = 0.85 (Table 10-2)

3

aH O = 0.860.0500 = 0.0425
3

pH = -log(0.043) = 1.37

14-20 (a) [OH-] = 20.0167 = 0.0334 M

pH = 14 – (-log(0.0334)) = 12.52

(b)  = ½ {(0.0167)(+2)2 + (0.0334)(-1)2} = 0.050

 OH = 0.81 (Table 10-2)

aOH = 0.810.0334 = 0.0271

Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

aOH  aH O = 1.0010-14
3

aH O = 1.0010-14/0.0271 = 3.6910-13
3

pH = -log(3.6910-13) = 12.43

[H 3 O  ][OCl - ]
14-21 HOCl + H2O  H3O+ + OCl- Ka = = 3.010-8
[HOCl]

[H3O+] = [OCl-] and [HOCl] = cHOCl – [H3O+]

[H3O+]2/(cHOCl – [H3O+]) = 3.010-8

rearranging gives the quadratic: 0 = [H3O+]2 + 310-8[H3O+] - cHOCl3.010-8

cHOCl [H3O+] pH

(a) 0.100 5.47610-5 4.26

(b) 0.0100 1.73110-5 4.76

(c) 1.0010-4 1.71710-6 5.76

K w [HOCl][OH - ] 1.00  10 14

14-22 OCl- + H2O  HOCl + OH- Kb =    3.33  10 7
Ka [OCl - ] 3.0  10 8

[HOCl] = [OH-] and [OCl-] = cNaOCl – [OH-]

[OH-]2/(cNaOCl -[OH-]) = 3.3310-7

rearranging gives the quadratic: 0 = [OH-]2 + 3.3310-7[OH-] - cNaOCl3.3310-7

cNaOCl [OH-] pOH pH

(a) 0.100 1.82310-4 3.74 10.26

(b) 0.0100 5.75410-5 4.24 9.76

(c) 1.0010-4 5.60610-6 5.25 8.75

Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

1.00  10 14
14-23 NH3 + H2O  NH4+ + OH- Kb = 10
 1.75  10 5
5.7  10

[NH4+] = [OH-] and [NH3] = cNH3 – [OH-]

[OH-]2/( cNH3 -[OH-]) = 1.7510-5

rearranging gives the quadratic: 0 = [OH-]2 + 1.7510-5[OH-] - cNH3 1.7510-5

cNH3 [OH-] pOH pH

(a) 0.100 1.31410-3 2.88 11.12

(b) 0.0100 4.09710-4 3.39 10.62

(c) 1.0010-4 3.39910-5 4.47 9.53

14-24 NH4+ + H2O  H3O+ + NH3 Ka = 5.710-10

[H3O+] = [NH3] and [NH4+] = c NH – [H3O+]

4

[H3O+]2/( c NH – [H3O+]) = 5.710-10

4

rearranging gives the quadratic: 0 = [H3O+]2 + 5.710-10[H3O+] - c NH 5.710-10

4

c NH [H3O+] pH
4

(a) 0.100 7.55010-6 5.12

(b) 0.0100 2.38710-6 5.62

(c) 1.0010-4 1.38510-7 6.62

1.00  10 14
14-25 C5H11N + H2O  C5H11NH+ + OH- Kb = 12
 1.333  10 3
7.5  10

[C5H11NH+] = [OH-] and [C5H11N] = cC5H11N – [OH-]

Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

[OH-]2/( cC5H11N -[OH-]) = 1.33310-3

rearranging gives the quadratic: 0 = [OH-]2 + 1.33310-3[OH-] - cC5H11N 1.33310-3

cC5H11N [OH-] pOH pH

(a) 0.100 1.09010-2 1.96 12.04

(b) 0.0100 3.04510-3 2.52 11.48

(c) 1.0010-4 9.34510-5 4.03 9.97

14-26 HIO3 + H2O  H3O+ + IO3- Ka = 1.710-1

[H3O+] = [IO3-] and [HIO3] = cHIO3 – [H3O+]

[H3O+]2/( cHIO3 – [H3O+]) = 1.710-1

rearranging gives the quadratic: 0 = [H3O+]2 + 1.710-1[H3O+] - cHIO3 1.710-1

cHIO3 [H3O+] pH

(a) 0.100 7.06410-2 1.15

(b) 0.0100 9.47210-3 2.02

(c) 1.0010-4 9.99410-5 4.00

1 mmol HA 1
14-27 (a) cHA = 43.0 g HA   = 0.9547 M HA
0.090079 g HA 500 mL soln

HA + H2O  H3O+ + A- Ka = 1.3810-4

[H3O+] = [A-] and [HA] = 0.9547 – [H3O+]

[H3O+]2/(0.9547 – [H3O+]) = 1.3810-4

rearranging and solving the quadratic gives: [H3O+] = 0.0114 and pH = 1.94

(b) cHA = 0.954725.0/250.0 = 0.09547 M HA

Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

Proceeding as in part (a) we obtain: [H3O+] = 3.5610-3 and pH = 2.45

(c) cHA = 0.0954710.0/1000.0 = 9.54710-4 M HA

Proceeding as in part (a) we obtain: [H3O+] = 3.0010-4 and pH = 3.52

1 mmol HA 1
14-28 (a) cHA = 1.05 g HA   = 0.04583 M HA
0.22911 g HA 100 mL soln

HA + H2O  H3O+ + A- Ka = 0.43

[H3O+] = [A-] and [HA] = 0.04583 – [H3O+]

[H3O+]2/(0.04583 – [H3O+]) = 0.43

rearranging and solving the quadratic gives: [H3O+] = 0.0418 and pH = 1.38

(b) cHA = 0.0458310.0/100.0 = 0.004583 M HA

Proceeding as in part (a) we obtain: [H3O+] = 4.53510-3 and pH = 2.34

(c) cHA = 0.00458310.0/1000.0 = 4.58310-5 M HA

Proceeding as in part (a) we obtain: [H3O+] = 4.58310-5 and pH = 4.34

0.200 mmol
14-29 Throughout 14-29: amount HA taken = 20.00 mL  = 4.00 mmol
mL

(a) HA + H2O  H3O+ + A- Ka = 1.8010-4

cHA = 4.00/45.0 = 8.8910-2

[H3O+] = [A-] and [HA] = 0.0889 – [H3O+]

[H3O+]2/(0.0889 – [H3O+]) = 1.8010-4

rearranging and solving the quadratic gives: [H3O+] = 3.9110-3 and pH = 2.41

(b) amount NaOH added = 25.0  0.160 = 4.00 mmol

therefore, we have a solution of NaA

Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

A- + H2O  OH- + HA Kb = 1.0010-14/(1.8010-4) = 5.5610-11

cA- = 4.00/45.0 = 8.8910-2

[OH-] = [HA] and [A-] = 0.0889 – [OH-]

[OH-]2/(0.0889 – [OH-]) = 5.5610-11

rearranging and solving the quadratic gives: [OH-] = 2.2210-6 and pH = 8.35

(c) amount NaOH added = 25.0  0.200 = 5.00 mmol

therefore, we have an excess of NaOH and the pH is determined by its concentration

[OH-] = (5.00 - 4.00)/45.0 = 2.2210-2

pH = 14 – pOH = 12.35

(d) amount NaA added = 25.0  0.200 = 5.00 mmol

[HA] = 4.00/45.0 = 0.0889

[A-] = 5.00/45.00 = 0.1111

[H3O+]0.1111/0.0889 = 1.8010-4

[H3O+] = 1.44010-4 and pH = 3.84

14-30 Throughout 14-30 the amount of NH3 taken is 4.00 mmol

1.00  10 14
(a) NH3 + H2O  OH- + NH4+ Kb = 10
 1.75  10 5
5.7  10

cNH3 = 4.00/60.0 = 6.6710-2

[NH4+] = [OH-] and [NH3] = 0.0667 – [OH-]

[OH-]2/(0.0667 – [OH-]) = 1.7510-5

rearranging and solving the quadratic gives: [OH-] = 1.0710-3 and pH = 11.03

(b) amount HCl added = 20.0  0.200 = 4.00 mmol

Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

therefore, we have a solution of NH4Cl

NH4+ + H2O  H3O+ + NH3 Ka = 5.710-10

c NH = 4.00/60.0 = 6.6710-2

4

[H3O+] = [NH3] and [NH4+] = 0.0667 – [H3O+]

[H3O+]2/(0.0667 – [H3O+]) = 5.710-10

rearranging and solving the quadratic gives: [H3O+] = 6.1610-6 and pH = 5.21

(c) amount HCl added = 20.0  0.250 = 5.00 mmol

therefore, we have an excess of HCl and the pH is determined by its concentration

[H3O+] = (5.00 - 4.00)/60.0 = 1.6710-2

pH = 1.78

(d) amount NH4Cl added = 20.0  0.200 = 4.00 mmol

[NH3] = 4.00/60.0 = 0.0667 [NH4+] = 4.00/60.0 = 0.0667

[H3O+]0.0.0667/0.0667 = 5.7010-10

[H3O+] = 5.7010-10 and pH = 9.24

(e) amount HCl added = 20.0  0.100 = 2.00 mmol

[NH3] = (4.00-2.00)/60.0 = 0.0333 [NH4+] = 2.00/60.0 = 0.0333

[H3O+]0.0.0333/0.0333 = 5.7010-10

[H3O+] = 5.7010-10 and pH = 9.24

[H 3 O  ][NH 3 ]
14-31 (a) NH4+ + H2O  H3O+ + NH3 5.7010-5 =
[ NH 4 ]

[NH3] = 0.0300 and [NH4+] = 0.0500

[H3O+] = 5.7010-10  0.0500/0.0300 = 9.5010-10

Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

[OH-] = 1.0010-14/9.5010-10 = 1.0510-5

pH = -log (9.5010-10) = 9.022

(b)  = ½ {(0.0500)(+1)2 + (0.0500)(-1)2} = 0.0500

From Table 10-2  NH = 0.80 and  NH3 = 1.0

4

K a  NH [ NH 4 ] 5.70  10 5  0.80  0.0500

aH O  4
 = 7.6010-10
3
 NH3 [ NH 3 ] 1.00  0.0300

pH = -log (7.6010-10) = 9.12

14-32 In each part of this problem a buffer mixture of a weak acid, HA, and its conjugate base,

NaA, is formed. In each case we will assume initially that [H3O+] and [OH-] are much

smaller than the molar concentration of the acid and conjugate so that [A-]  cNaA and

[HA]  cHA. These assumptions then lead to the following relationship:

[H3O+] = Ka cHA / cNaA

1 mol HA 1
(a) cHA = 9.20 g HA   = 0.1021 M
90.08 g HA 1.00 L soln

1 mol NaA 1
cNaA = 11.15 g HA   = 0.0995 M
112.06 g NaA 1.00 L soln

[H3O+] = 1.3810-40.1021/0.0995 = 1.41610-4

Note that [H3O+] (and [OH-]) << cHA (and cNaA) as assumed. Therefore,

pH = -log (1.41610-4) = 3.85

(b) cHA = 0.0550 M and cNaA = 0.0110 M

[H3O+] = 1.7510-50.0550/0.0110 = 8.7510-5

pH = -log (8.7510-5) = 4.06

Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

mmol HA
(c) Original amount HA = 3.00 g  = 21.72 mmol HA
0.13812 g

0.1130 mmol HA
Original amount NaOH = 50.0 mL  = 5.65 mmol NaOH
mL

cHA = (21.72 – 5.65)/500 = 3.21410-2 M

cNaA = 5.65/500 = 1.13010-2 M

[H3O+] = 1.0610-33.21410-2/(1.13010-2) = 3.01510-3

Note, however, that [H3O+] is not << cHA (and cNaA) as assumed. Therefore,

[A-] = 1.13010-2 + [H3O+] – [OH-]

[HA] = 3.21410-2 – [H3O+] + [OH-]

Certainly, [OH-] will be negligible since the solution is acidic. Substituting into the

dissociation-constant expression gives

 
[H 3 O  ] 1.130  10 2  [H 3 O  ]
= 1.0610-3
3.214  10  2  [H 3 O  ]

Rearranging gives

[H3O+]2 + 1.23610-2 [H3O+] – 3.40710-5 = 0

[H3O+] = 2.32110-3 M and pH = 2.63

(d) Here we must again proceed as in part (c). This leads to

 
[H 3 O  ] 0.100  [H 3 O  ]
= 4.310-1

0.0100  [H 3 O ]

[H3O+]2 + 0.53 [H3O+] – 4.310-3 = 0

[H3O+] = 7.9910-3 M and pH = 2.10

Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

14-33 In each of the parts of this problem, we are dealing with a weak base B and its conjugate

acid BHCl or (BH)2SO4. The pH determining equilibrium can then be written as

BH+ + H2O  H3O+ + B

The equilibrium concentration of BH+ and B are given by

[BH+] = cBHCl + [OH-] – [H3O+] (1)

[B] = cB - [OH-] + [H3O+] (2)

In many cases [OH-] and [H3O+] will be much smaller than cB and cBHCl and [BH+] ≈

cBHCl and [B] ≈ cB so that

cBHCl
[H3O+] = K a  (3)
cB

1 mmol (NH 4 ) 2 SO 4 2 mmol NH 4

(a) Amount NH4+ = 3.30 g (NH4)2SO4   =
0.13214 g (NH 4 ) 2 SO 4 mmol (NH 4 ) 2 SO 4

49.95 mmol

Amount NaOH = 125.0 mL0.1011 mmol/mL = 12.64 mmol

1 mmol NH 3 1
c NH3  12.64 mmol NaOH   = 2.52810-2 M
mmol NaOH 500.0 mL

1
c NH  (49.95  12.64) mmol NH 4  = 7.46210-2 M
4
500.0 mL

Substituting these relationships in equation (3) gives

cBHCl
[H3O+] = K a  = 5.7010-10  7.46210-2 / (2.52810-2) = 1.68210-9 M
cB

pH = -log 1.68210-9 = 8.77

(b) Substituting into equation (3) gives

[H3O+] = 7.510-12  0.080 / 0.120 = 5.0010-12

Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

pH = -log 5.0010-12 = 11.30

(c) cB = 0.050 and cBHCl = 0.167

[H3O+] = 2.3110-11  0.167 / 0.050 = 7.71510-11

pH = -log 7.71510-11 = 10.11

1 mmol B
(d) Original amount B = 2.32 g B = 24.91 mmol
0.09313 g B

Amoung HCl = 100 mL  0.0200 mmol/mL = 2.00 mmol

cB = (24.91 – 2.00)/250.0 = 9.16410-2 M

cBH+ = 2.00/250.0 = 8.0010-3 M

[H3O+] = 2.5110-5  8.0010-3 / 9.16410-2 = 2.19110-6 M

pH = -log 2.19110-6 = 5.66

14-34 (a) pH = 0.00

(b) [H3O+] changes to 0.00500 M from 0.0500 M

pH = -log 0.00500 – (-log0.0500) = 2.301 – 1.301 = 1.000

(c) pH diluted solution = 14.000 – (-log 0.00500) = 11.699

pH undiluted solution = 14.000 – (-log 0.0500) = 12.699

pH = -1.000

(d) In order to get a better picture of the pH change with dilution, we will dispense with

the usual approximations and write

[H 3 O  ][OAc - ]
Ka   1.75  10 5
[HOAc]

[H3O+]2 + 1.7510-5[H3O+] – 0.0500  1.7510-5 = 0

Solving by the quadratic formula or by successive approximations gives

Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

[H3O+] = 9.26710-4 and pH = -log 9.26710-4 = 3.033

For diluted solution, the quadratic becomes

[H3O+]2 + 1.7510-5 – 0.005001.7510-5

[H3O+] = 2.87210-4 and pH = 3.542

pH = 3.033 – 3.542 = -0.509

(e) OAc- + H2O  HOAc + OH-

[HOAc][OH - ] 1.00  10 14

 = 5.7110-10 = Kb
[OAc - ] 1.75  10 5

Here we can use an approximation solution because Kb is so very small. For the

undiluted sample

[OH - ]2
= 5.7110-10
0.0500

[OH-] = (5.7110-10  0.0500)1/2 = 5.34310-6 M

pH = 14.00 – (-log 5.34310-6) = 8.728

For the diluted sample

[OH-] = (5.7110-10  0.00500)1/2 = 1.69010-6 M

pH = 14.00 – (-log 1.69010-6) = 8.228

pH = 8.228 – 8.728 = -0.500

(f) Here we must avoid the approximate solution because it will not reveal the small pH

change resulting from dilution. Thus, we write

[HOAc] = cHOAc + [OH-] – [H3O+] ≈ cHOAc – [H3O+]

[OAc-] = cNaOAc – [OH-] + [H3O+] ≈ cNaOAc + [H3O+]

Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

Ka = 1.7510 -5
=
 
[H 3 O  ] 0.0500  [H 3 O  ]
0.0500  [H 3 O  ]

Rearranging gives

[H3O+]2 + 5.001810-2[H3O+] – 8.7510-7 = 0

[H3O+] = 1.74910-5 and pH = 4.757

Proceeding in the same way we obtain for the diluted sample

1.7510-5 =

[H 3 O  ] 0.00500  [H 3 O  ] 
0.00500  [H 3 O  ]

[H3O+]2 + 5.017510-3[H3O+] – 8.7510-8 = 0

[H3O+] = 1.73810-5 and pH = 4.760

pH = 4.760 – 4.757 = 0.003

(g) Proceeding as in part (f) a 10-fold dilution of this solution results in a pH change that

is less than 1 in the third decimal place. Thus for all practical purposes,

pH = 0.000

14-35 (a) After addition of acid, [H3O+] = 1 mmol/100 mL = 0.0100 M and pH = 2.00

Since original pH = 7.00

pH = 2.00 – 7.00 = -5.00

(b) After addition of acid

cHCl = (1000.0500 + 1.00)/100 = 0.0600 M

pH = -log 0.0600 – (-log 0.0500) = 1.222 – 1.301 = -0.079

(c) After addition of acid,

cNaOH = (1000.0500 – 1.00)/100 = 0.0400 M

[OH-] = 0.0400 M and pH = 14.00 – (-log 0.0400) = 12.602

Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

From Problem 14-34 (c), original pH = 12.699

pH = -0.097

(d) From Solution 14-34 (d), original pH = 3.033

Upon adding 1 mmol HCl to the 0.0500 M HOAc, we produce a mixture that is

0.0500 M in HOAc and 1.00/100 = 0.0100 M in HCl. The pH of this solution is

approximately that of a 0.0100 M HCl solution, or 2.00. Thus,

pH = 2.000 – 3.033 = -1.033

(If the contribution of dissociation of HOAc to the pH is taken into account, a pH

of 1.996 is obtained and pH = -1.037 is obtained.)

(e) From Solution 14-34 (e), original pH = 8.728

Upon adding 1.00 mmol HCl we form a buffer having the composition

cHOAc = 1.00/100 = 0.0100

cNaOAc = (0.0500  100 – 1.00)/100 = 0.0400

Applying Equation 14-xx gives

[H3O+] = 1.7510-5  0.0100/0.0400 = 4.57510-6 M

pH = -log 4.57510-6 = 5.359

pH = 5.359 – 8.728 = -3.369

(f) From Solution 14-34 (f), original pH = 4.757

With the addition of 1.00 mmol of HCl we have a buffer whose concentrations are

cHOAc = 0.0500 + 1.00/100 = 0.0600 M

cNaOAc = 0.0500 – 1.00/100 = 0.0400 M

Proceeding as in part (e), we obtain

[H3O+] = 2.62510-5 M and pH = 4.581

Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

pH = 4.581 – 4.757 = -0.176

(g) For the original solution

[H3O+] = 1.7510-5  0.500/0.500 = 1.7510-5 M

pH = -log 1.7510-5 = 4.757

After addition of 1.00 mmol HCl

cHOAc = 0.500 + 1.00/100 = 0.510 M

cNaOAc = 0.500 – 1.00/100 = 0.490 M

Proceeding as in part (e), we obtain

[H3O+] = 1.7510-5  0.510/0.490 = 1.82110-5 M

pH = -log 1.82110-5 = 4.740

pH = 4.740 – 4.757 = -0.017

14-36 (a) cNaOH = 1.00/100 = 0.0100 = [OH-]

pH = 14.00 – (-log 0.0100) = 12.00

Original pH = 7.00 and pH = 12.00 – 7.00 = 5.00

(b) Original pH = 1.301 [see Problem 14-34 (b)]

After addition of base, cHCl = (100  0.0500 – 1.00)/100 = 0.0400 M

pH = -log 0.0400 – 1.301 = 1.398 – 1.301 = 0.097

(c) Original pH = 12.699 [see Problem 14.34 (c)]

After addition of base, cNaOH = (100  0.0500 + 1.00)/100 = 0.0600 M

pH = 14.00 – (-log 0.0600) = 12.778

pH = 12.778 – 12.699 = 0.079

(d) Original pH = 3.033 [see Problem 14-34 (d)]

Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

Addition of strong base gives a buffer of HOAc and NaOAc.

cNaOAc = 1.00 mmol/100 = 0.0100 M

cHOAc = 0.0500 – 1.00/100 = 0.0400 M

Proceeding as in Solution 14-35 (e) we obtain

[H3O+] = 1.7510-5  0.0400/0.0100 = 7.0010-5 M

pH = -log 7.0010-5 = 4.155

pH = 4.155 – 3.033 = 1.122

(e) Original pH = 8.728 [see Problem 14.34 (e)]

Here, we have a mixture of NaOAc and NaOH and the pH is determined by the

excess NaOH.

cNaOH = 1.00 mmol/100 = 0.0100 M

pH = 14.00 – (-log 0.0100) = 12.00

pH = 12.00 – 8.728 = 3.272

(f) Original pH = 4.757 [see Problem 14-34 (f)]

cNaOAc = 0.0500 + 1.00/100 = 0.0600 M

cHOAc = 0.0500 – 1.00/100 = 0.0400 M

Proceeding as in Solution 14.35 (e) we obtain

[H3O+] = 1.16710-5 M and pH = 4.933

pH = 4.933 – 4.757 = 0.176

(g) Original pH = 4.757 [see Problem 14-34 (f)]

cHOAc = 0.500 – 1.00/100 = 0.490 M

cNaOAc = 0.500 + 1.00/100 = 0.510 M

Substituting into Equation 9-29 gives

Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

[H3O+] = 1.7510-5  0.400/0.510 = 1.68110-5 M

pH = -log 1.68110-5 = 4.774

pH = 4.774 – 4.757 = 0.017

14-37 For lactic acid, Ka = 1.3810-4 = [H3O+][A-]/[HA]

Throughout this problem we will base calculations on Equations 9-25 and 9-26.

[A-] = cNaA + [H3O+] – [OH-]

[HA] = cHA – [H3O+] – [OH-]

 
[H 3 O  ] c NaA  [H 3 O  ]
= 1.3810-4

c HA  [H 3 O ]

This equation rearranges to

[H3O+]2 + (1.3810-4 + 0.0800)[H3O+] – 1.3810-4 cHA = 0

(a) Before addition of acid

[H3O+]2 + (1.3810-4 + 0.0800)[H3O+] – 1.3810-4  0.0200 = 0

[H3O+] = 3.44310-5 and pH = 4.463

Upon adding 0.500 mmol of strong acid

cHA = (100  0.0200 + 0.500)/100 = 0.0250 M

cNaA = (100  0.0800 – 0.500)/100 = 0.0750 M

[H3O+]2 + (1.3810-4 + 0.0750)[H3O+] – 1.3810-4  0.0250 = 0

[H3O+] = 4.58910-5 and pH = 4.338

pH = 4.338 – 4.463 = -0.125

(b) Before addition of acid

[H3O+]2 + (1.3810-4 + 0.0200)[H3O+] – 1.3810-4  0.0800 = 0

Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

[H3O+] = 5.34110-5 and pH = 3.272

After adding acid

cHA = (100  0.0800 + 0.500)/100 = 0.0850 M

cNaA = (100  0.0200 – 0.500)/100 = 0.0150 M

[H3O+]2 + (1.3810-4 + 0.0150)[H3O+] – 1.3810-4  0.0850 = 0

[H3O+] = 7.38810-4 and pH = 3.131

pH = 3.131 – 3.272 = -0.141

(c) Before addition of acid

[H3O+]2 + (1.3810-4 + 0.0500)[H3O+] – 1.3810-4  0.0500 = 0

[H3O+] = 1.37210-4 and pH = 3.863

After adding acid

cHA = (100  0.0500 + 0.500)/100 = 0.0550 M

cNaA = (100  0.0500 – 0.500)/100 = 0.0450 M

[H3O+]2 + (1.3810-4 + 0.0450)[H3O+] – 1.3810-4  0.0550 = 0

[H3O+] = 1.67510-4 and pH = 3.776

pH = 3.776 – 3.863 = -0.087

Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

14-38

A B C D E F G H I
1 Vi, NaOH 50.00
2 ci, NaOH 0.1000 M
3 c, HCl 0.1000 M
4 Veq. pt. 50.00
5 Kw 1.00E-14
6
+
7 Vol. HCl, mL [H3O ] pH
8 0.00 1.00E-13 13.000
9 10.00 1.50E-13 12.824
10 25.00 3.00E-13 12.523
11 40.00 9.00E-13 12.046
12 45.00 1.90E-12 11.721
13 49.00 9.90E-12 11.004
14 50.00 1.00E-07 7.000
15 51.00 9.90E-04 3.004
16 55.00 4.76E-03 2.322
17 60.00 9.09E-03 2.041
18
19 Spreadsheet Documentation
20 B4 = B2*B1/B3
21 B8 = $B$5/(($B$2*$B$1-A8*$B$3)/($B$1+A8))
22 B14 = SQRT(B5)
23 B15 = (A15*$B$3-$B$1*$B$2)/(A15+$B$1)
24 C8 = -LOG(B8)

14-39 Let us calculate pH when 24.95 and 25.05 mL of reagent have been added.

24.95 mL reagent

amount KOH added 24.95  0.1000 mmol KOH 2.495

cA-    = 0.03329 M
total volume soln 74.95 mL soln 74.95

original amount HA - amount KOH added

cHA  [HA] =
total volume soln

(50.00  0.0500 - 24.95  0.1000) mmol HA

=
74.95 mL soln

2.500  2.495 0.005

=  = 6.6710-5 M
74.95 74.95
Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

Substituting into Equation 9-29

[H3O+] = Ka cHA / cA- = 1.80  10-4  6.6710-5 / 0.03329 =3.60710-7 M

pH = -log 3.60710-7 = 6.44

25.05 mL KOH

amount KOH added - initial amount HA

cKOH =
total volume soln

25.05  0.1000 - 50.00  0.05000

= = 6.6610-5 = [OH-]
75.05 mL soln

pH = 14.00 – (-log 6.6610-5) = 9.82

Thus, the indicator should change color in the range of pH 6.5 to 9.8. Cresol purple

(range 7.6 to 9.2, Table 14-1) would be quite suitable.

14-40 (See Solution 14-39) Let us calculate the pH when 49.95 and 50.05 mL of HClO4 have

been added.

49.95 mL HClO4

B = C2H5NH2 BH+ = C2H5NH3+

no. mmol HClO 4 49.95  0.10000 4.995

c BH     = 0.04998 M ≈ [BH+]
total volume soln 99.95 99.95

cB =
50.00  0.1000  49.95  0.1000  0.00500 = 5.0010-5 M ≈ [B]
99.95 99.95

[H3O+] = 2.31  10-11  0.04998 / 5.0010-5 =2.30910-8 M

pH = -log 2.30910-8 = 7.64

50.05 mL HClO4

cHClO4 
50.05  0.1000  50.00  0.1000 = 4.99810-5 = [H3O+]
100.05

pH = -log 4.99810-5 = 4.30

Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

Indicator should change color in the pH range of 7.64 to 4.30. Bromocresol purple would

be suitable.

For Problems 14-41 through 14-43 we set up spreadsheets that will solve a quadratic equation

to determine [H3O+] or [OH-], as needed. While approximate solutions are appropriate for many

of the calculations, the approach taken represents a more general solution and is somewhat easier

to incorporate in a spreadsheet. As an example consider the titration of a weak acid with a strong

base.

Before the equivalence point: [HA] =

ci HAVi HA  ci NaOHVNaOH  - [H3O+]
Vi HA  VNaOH 

and [A-] =
ci NaOHVNaOH  + [H O+]
Vi HA  VNaOH  3

Substituting these expressions into the equilibrium expression for HA and rearranging gives

 c V   K a ci HAVi HA  ci NaOHVNaOH 

0 = [H3O+]2 +  i NaOH NaOH  K a  [H3O+] -
 Vi HA  VNaOH   Vi HA  VNaOH 
From which [H3O+] is directly determined.

At and after the equivalence point: [A-] =

ci HAVHA  - [HA]
Vi HA  VNaOH 

and [OH-] =
ci NaOHVNaOH  ci HAVi HA  + [HA]
Vi HA  VNaOH 
Substituting these expressions into the equilibrium expression for A- and rearranging gives

 c V c V  K  K w ci HAVHA 
0 = [HA]2 +  i NaOH NaOH i HA i HA  w  [HA] -
 Vi HA  VNaOH  Ka  K a Vi HA  VNaOH 

From which [HA] can be determined and [OH-] and [H3O+] subsequently calculated. A similar

approach is taken for the titration of a weak base with a strong acid.
Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

14-41

A B C D E F
1 Part (a)
2 Vi, HNO2 50.00
3 ci, HNO2 0.1000
4 Ka, HNO2 7.10E-04
5 Kw, H2O 1.00E-14
6
7 c, NaOH 0.1000
8 Veq. pt. 50.00
9
+
10 Vol. NaOH, mL b c [OH-] [H3O ] pH
11 0.00 7.1000E-04 -7.1000E-05 8.0786E-03 2.0927
12 5.00 9.8009E-03 -5.8091E-05 4.1607E-03 2.3808
13 15.00 2.3787E-02 -3.8231E-05 1.5112E-03 2.8207
14 25.00 3.4043E-02 -2.3667E-05 6.8155E-04 3.1665
15 40.00 4.5154E-02 -7.8889E-06 1.7404E-04 3.7594
16 45.00 4.8078E-02 -3.7368E-06 7.7599E-05 4.1101
17 49.00 5.0205E-02 -7.1717E-07 1.4281E-05 4.8452
18 50.00 1.4085E-11 -7.0423E-13 8.3917E-07 1.1916E-08 7.9239
19 51.00 9.9010E-04 -6.9725E-13 9.9010E-04 1.0100E-11 10.9957
20 55.00 4.7619E-03 -6.7069E-13 4.7619E-03 2.1000E-12 11.6778
21 60.00 9.0909E-03 -6.4020E-13 9.0909E-03 1.1000E-12 11.9586
22
23 Spreadsheet Documentation
24 C8 = C2*C3/C7
25 B11 = $C$7*A11/($C$2+A11)+$C$4
26 C11 = -$C$4*($C$3*$C$2-$C$7*A11)/($C$2+A11)
27 E11 = (-B11+SQRT(B11^2-4*C11))/2
28 F11 = -LOG(E11)
29 B18 = ($C$7*A18-$C$3*$C$2)/($C$2+A18)+$C$5/$C$4
30 C18 = -($C$5/$C$4)*($C$2*$C$3/($C$2+A18))
31 D18 = (-B18+SQRT(B18^2-4*C18))/2+($C$7*A18-$C$2*$C$3)/($C$2+A18)
32 E18 = $C$5/D18
Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

A B C D E F
1 Part (b)
2 Vi, Lactic Acid 50.00
3 ci, Lactic Acid 0.1000
4 Ka, Lactic Acid 1.38E-04
5 Kw, H2O 1.00E-14
6
7 c, NaOH 0.1000
8 Veq. pt. 50.00
9
+
10 Vol. NaOH, mL b c [OH-] [H3O ] pH
11 0.00 1.3800E-04 -1.3800E-05 3.6465E-03 2.4381
12 5.00 9.2289E-03 -1.1291E-05 1.0938E-03 2.9611
13 15.00 2.3215E-02 -7.4308E-06 3.1579E-04 3.5006
14 25.00 3.3471E-02 -4.6000E-06 1.3687E-04 3.8637
15 40.00 4.4582E-02 -1.5333E-06 3.4367E-05 4.4639
16 45.00 4.7506E-02 -7.2632E-07 1.5284E-05 4.8158
17 49.00 4.9633E-02 -1.3939E-07 2.8083E-06 5.5516
18 50.00 7.2464E-11 -3.6232E-12 1.9034E-06 5.2537E-09 8.2795
19 51.00 9.9010E-04 -3.5873E-12 9.9010E-04 1.0100E-11 10.9957
20 55.00 4.7619E-03 -3.4507E-12 4.7619E-03 2.1000E-12 11.6778
21 60.00 9.0909E-03 -3.2938E-12 9.0909E-03 1.1000E-12 11.9586

A B C D E F
1 Part (c)
+
2 Vi, C5H5NH 50.00
+
3 ci, C5H5NH 0.1000
+
4 Ka, C5H5NH 5.90E-06
5 Kw, H2O 1.00E-14
6
7 c, NaOH 0.1000
8 Veq. pt. 50.00
9
+
10 Vol. NaOH, mL b c [OH-] [H3O ] pH
11 0.00 5.9000E-06 -5.9000E-07 7.6517E-04 3.1162
12 5.00 9.0968E-03 -4.8273E-07 5.2760E-05 4.2777
13 15.00 2.3083E-02 -3.1769E-07 1.3755E-05 4.8615
14 25.00 3.3339E-02 -1.9667E-07 5.8979E-06 5.2293
15 40.00 4.4450E-02 -6.5556E-08 1.4748E-06 5.8313
16 45.00 4.7374E-02 -3.1053E-08 6.5546E-07 6.1835
17 49.00 4.9501E-02 -5.9596E-09 1.2039E-07 6.9194
18 50.00 1.6949E-09 -8.4746E-11 9.2049E-06 1.0864E-09 8.9640
19 51.00 9.9010E-04 -8.3907E-11 9.9018E-04 1.0099E-11 10.9957
20 55.00 4.7619E-03 -8.0710E-11 4.7619E-03 2.1000E-12 11.6778
21 60.00 9.0909E-03 -7.7042E-11 9.0909E-03 1.1000E-12 11.9586
Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

14-42

A B C D E F
1 Part (a)
2 Vi, NH3 50.00
3 ci, NH3 0.1000
+
4 Ka, NH4 5.70E-10
5 Kw, H2O 1.00E-14
6
7 c, HCl 0.1000
8 Veq. pt. 50.00
9
+
10 Vol. HCl, mL b c [OH-] [H3O ] pH
11 0.00 1.7544E-05 -1.7544E-06 1.3158E-03 7.6000E-12 11.1192
12 5.00 9.1085E-03 -1.4354E-06 1.5495E-04 6.4535E-11 10.1902
13 15.00 2.3094E-02 -9.4467E-07 4.0832E-05 2.4490E-10 9.6110
14 25.00 3.3351E-02 -5.8480E-07 1.7525E-05 5.7060E-10 9.2437
15 40.00 4.4462E-02 -1.9493E-07 4.3838E-06 2.2811E-09 8.6419
16 45.00 4.7386E-02 -9.2336E-08 1.9485E-06 5.1321E-09 8.2897
17 49.00 4.9512E-02 -1.7721E-08 3.5791E-07 2.7940E-08 7.5538
18 50.00 5.7000E-10 -2.8500E-11 5.3383E-06 5.2726
19 51.00 9.9010E-04 -2.8218E-11 9.9013E-04 3.0043
20 55.00 4.7619E-03 -2.7143E-11 4.7619E-03 2.3222
21 60.00 9.0909E-03 -2.5909E-11 9.0909E-03 2.0414
22
23 Spreadsheet Documentation
24 C8 = C2*C3/C7
25 B11 = $C$7*A11/($C$2+A11)+$C$5/$C$4
26 C11 = -$C$5/$C$4*($C$3*$C$2-$C$7*A11)/($C$2+A11)
27 D11 = (-B11+SQRT(B11^2-4*C11))/2
28 E11 = $C$5/D11
29 F11 = -LOG(E11)
30 B18 = ($C$7*A18-$C$3*$C$2)/($C$2+A18)+$C$4
31 C18 = -($C$4)*($C$2*$C$3/($C$2+A18))
32 E18 = (-B18+SQRT(B18^2-4*C18))/2+($C$7*A18-$C$2*$C$3)/($C$2+A18)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

A B C D E F
1 Part (b)
2 Vi, H2NNH2 50.00
3 ci, H2NNH2 0.1000
+
4 Ka, H2NNH3 1.05E-08
5 Kw, H2O 1.00E-14
6
7 c, HCl 0.1000
8 Veq. pt. 50.00
9
+
10 Vol. HCl, mL b c [OH-] [H3O ] pH
11 0.00 9.5238E-07 -9.5238E-08 3.0813E-04 3.2454E-11 10.4887
12 5.00 9.0919E-03 -7.7922E-08 8.5625E-06 1.1679E-09 8.9326
13 15.00 2.3078E-02 -5.1282E-08 2.2219E-06 4.5006E-09 8.3467
14 25.00 3.3334E-02 -3.1746E-08 9.5233E-07 1.0501E-08 7.9788
15 40.00 4.4445E-02 -1.0582E-08 2.3809E-07 4.2001E-08 7.3767
16 45.00 4.7369E-02 -5.0125E-09 1.0582E-07 9.4502E-08 7.0246
17 49.00 4.9496E-02 -9.6200E-10 1.9436E-08 5.1451E-07 6.2886
18 50.00 1.0500E-08 -5.2500E-10 2.2908E-05 4.6400
19 51.00 9.9011E-04 -5.1980E-10 9.9062E-04 3.0041
20 55.00 4.7619E-03 -5.0000E-10 4.7620E-03 2.3222
21 60.00 9.0909E-03 -4.7727E-10 9.0910E-03 2.0414

A B C D E F
1 Part (c)
2 Vi, NaCN 50.00
3 ci, NaCN 0.1000
4 Ka, HCN 6.20E-10
5 Kw, H2O 1.00E-14
6
7 c, HCl 0.1000
8 Veq. pt. 50.00
9
+
10 Vol. HCl, mL b c [OH-] [H3O ] pH
11 0.00 1.6129E-05 -1.6129E-06 1.2620E-03 7.9242E-12 11.1010
12 5.00 9.1070E-03 -1.3196E-06 1.4267E-04 7.0092E-11 10.1543
13 15.00 2.3093E-02 -8.6849E-07 3.7547E-05 2.6633E-10 9.5746
14 25.00 3.3349E-02 -5.3763E-07 1.6113E-05 6.2060E-10 9.2072
15 40.00 4.4461E-02 -1.7921E-07 4.0304E-06 2.4811E-09 8.6054
16 45.00 4.7385E-02 -8.4890E-08 1.7914E-06 5.5821E-09 8.2532
17 49.00 4.9511E-02 -1.6292E-08 3.2905E-07 3.0390E-08 7.5173
18 50.00 6.2000E-10 -3.1000E-11 5.5675E-06 5.2543
19 51.00 9.9010E-04 -3.0693E-11 9.9013E-04 3.0043
20 55.00 4.7619E-03 -2.9524E-11 4.7619E-03 2.3222
21 60.00 9.0909E-03 -2.8182E-11 9.0909E-03 2.0414
Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

14-43

A B C D E F
1 Part (a)
+
2 Vi, C6H5NH3 50.00
+
3 ci, C6H5NH3 0.1000
+
4 Ka, C6H5NH3 2.51E-05
5 Kw, H2O 1.00E-14
6
7 c, NaOH 0.1000
8 Veq. pt. 50.00
9
+
10 Vol. NaOH, mL b c [OH-] [H3O ] pH
11 0.00 2.5100E-05 -2.5100E-06 1.5718E-03 2.8036
12 5.00 9.1160E-03 -2.0536E-06 2.1997E-04 3.6576
13 15.00 2.3102E-02 -1.3515E-06 5.8356E-05 4.2339
14 25.00 3.3358E-02 -8.3667E-07 2.5062E-05 4.6010
15 40.00 4.4470E-02 -2.7889E-07 6.2706E-06 5.2027
16 45.00 4.7394E-02 -1.3211E-07 2.7872E-06 5.5548
17 49.00 4.9520E-02 -2.5354E-08 5.1198E-07 6.2907
18 50.00 3.9841E-10 -1.9920E-11 4.4630E-06 2.2406E-09 8.6496
19 51.00 9.9010E-04 -1.9723E-11 9.9012E-04 1.0100E-11 10.9957
20 55.00 4.7619E-03 -1.8972E-11 4.7619E-03 2.1000E-12 11.6778
21 60.00 9.0909E-03 -1.8109E-11 9.0909E-03 1.1000E-12 11.9586
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Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

A B C D E F
1 Part (b)
2 Vi, ClCH2COOH 50.00
3 ci, ClCH2COOH 0.0100
4 Ka, ClCH2COOH 1.36E-03
5 Kw, H2O 1.00E-14
6
7 c, NaOH 0.0100
8 Veq. pt. 50.00
9
+
10 Vol. NaOH, mL b c [OH-] [H3O ] pH
11 0.00 1.3600E-03 -1.3600E-05 3.0700E-03 2.5129
12 5.00 2.2691E-03 -1.1127E-05 2.3889E-03 2.6218
13 15.00 3.6677E-03 -7.3231E-06 1.4351E-03 2.8431
14 25.00 4.6933E-03 -4.5333E-06 8.2196E-04 3.0852
15 40.00 5.8044E-03 -1.5111E-06 2.4960E-04 3.6027
16 45.00 6.0968E-03 -7.1579E-07 1.1523E-04 3.9385
17 49.00 6.3095E-03 -1.3737E-07 2.1698E-05 4.6636
18 50.00 7.3529E-12 -3.6765E-14 1.9174E-07 5.2155E-08 7.2827
19 51.00 9.9010E-05 -3.6401E-14 9.9010E-05 1.0100E-10 9.9957
20 55.00 4.7619E-04 -3.5014E-14 4.7619E-04 2.1000E-11 10.6778
21 60.00 9.0909E-04 -3.3422E-14 9.0909E-04 1.1000E-11 10.9586
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Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

A B C D E F
1 Part (c)
2 Vi, HOCl 50.00
3 ci, HOCl 0.1000
4 Ka, HOCl 3.00E-08
5 Kw, H2O 1.00E-14
6
7 c, NaOH 0.1000
8 Veq. pt. 50.00
9
+
10 Vol. NaOH, mL b c [OH-] [H3O ] pH
11 0.00 3.0000E-08 -3.0000E-09 5.4757E-05 4.2616
12 5.00 9.0909E-03 -2.4545E-09 2.6999E-07 6.5687
13 15.00 2.3077E-02 -1.6154E-09 7.0000E-08 7.1549
14 25.00 3.3333E-02 -1.0000E-09 3.0000E-08 7.5229
15 40.00 4.4444E-02 -3.3333E-10 7.5000E-09 8.1249
16 45.00 4.7368E-02 -1.5789E-10 3.3333E-09 8.4771
17 49.00 4.9495E-02 -3.0303E-11 6.1224E-10 9.2131
18 50.00 3.3333E-07 -1.6667E-08 1.2893E-04 7.7560E-11 10.1104
19 51.00 9.9043E-04 -1.6502E-08 1.0065E-03 9.9355E-12 11.0028
20 55.00 4.7622E-03 -1.5873E-08 4.7652E-03 2.0985E-12 11.6781
21 60.00 9.0912E-03 -1.5152E-08 9.0926E-03 1.0998E-12 11.9587
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Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

A B C D E F
1 Part (d)
+
2 Vi, HONH3 50.00
+
3 ci, HONH3 0.1000
+
4 Ka, HONH3 1.10E-06
5 Kw, H2O 1.00E-14
6
7 c, HCl 0.1000
8 Veq. pt. 50.00
9
+
10 Vol. HCl, mL b c [OH-] [H3O ] pH
11 0.00 9.0909E-09 -9.0909E-10 3.0147E-05 3.3171E-10 9.4792
12 5.00 9.0909E-03 -7.4380E-10 8.1817E-08 1.2222E-07 6.9128
13 15.00 2.3077E-02 -4.8951E-10 2.1212E-08 4.7143E-07 6.3266
14 25.00 3.3333E-02 -3.0303E-10 9.0909E-09 1.1000E-06 5.9586
15 40.00 4.4444E-02 -1.0101E-10 2.2727E-09 4.4000E-06 5.3565
16 45.00 4.7368E-02 -4.7847E-11 1.0101E-09 9.9000E-06 5.0044
17 49.00 4.9495E-02 -9.1827E-12 1.8553E-10 5.3900E-05 4.2684
18 50.00 1.1000E-06 -5.5000E-08 2.3397E-04 3.6308
19 51.00 9.9120E-04 -5.4455E-08 1.0423E-03 2.9820
20 55.00 4.7630E-03 -5.2381E-08 4.7729E-03 2.3212
21 60.00 9.0920E-03 -5.0000E-08 9.0964E-03 2.0411

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Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

14-44

A B C D E F G
+
1 Species pH [H3O ] Ka 0 1
2 (a) Acetic Acid 5.320 4.7863E-06 1.75E-05 0.215 0.785
3 (b) Picric Acid 1.250 5.6234E-02 4.3E-01 0.116 0.884
4 (c) HOCl 7.000 1.0000E-07 3.0E-08 0.769 0.231
+
5 (d) HONH3 5.120 7.5858E-06 1.10E-06 0.873 0.127
6 (e) Piperidine 10.080 8.3176E-11 7.50E-12 0.917 0.083
7
8 Spreadsheet Documentation
9 D2 = 10^(-C2)
10 F2 = D2/(D2+E2)
11 G2 = E2/(D2+E2)

14-45 [H3O+] = 6.31010-4 M. Substituting into Equation 9-35 gives,

6.310  10 4
0 = = 0.778
6.310  10 4  1.80  10 4

HCOOH  HCOOH = 0
cT 0.0850

[HCOOH] = 0.778  0.0850 = 6.6110-2 M

14-46 [H3O+] = 3.3810-12 M. For CH3NH3+, Equation 9-36 takes the form,

[CH 3 NH 2 ] Ka 2.3  10 11

1 =  
cT [H 3 O  ]  K a 3.38  10 12  2.3  10 11

[CH 3 NH 2 ]
= 0.872 =
0.120

[CH3NH2] = 0.872  0.120 = 0.105 M

14-47 For lactic acid, Ka = 1.38  10-4

[H 3 O  ] [H 3 O  ]
0 = 
K a  [H 3 O  ] 1.38  10 4  [H 3 O  ]
Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

= 0.640 =
HA  HA
cT 0.120

[HA] = 0.640  0.120 = 0.0768 M

1 = 1.000 – 0.640 = 0.360

[A-] = 1  0.120 = (1.000 – 0.640)  0.120 = 0.0432 M

[H3O+] = Ka cHA / cA- = 1.38  10-4  0.640 / (1 – 0.640) = 2.45310-4 M

pH = -log 2.45310-4 = 3.61

The remaining data are obtained in the same way.

Acid cT pH [HA] [A-] 0 1

Lactic 0.120 3.61 0.0768 0.0432 0.640 0.360

Iodic 0.200 1.28 0.0470 0.153 0.235 0.765

Butanoic 0.162 5.00 0.0644 0.0979 0.397 0.604

Nitrous 0.179 3.30 0.0739 0.105 0.413 0.587

HCN 0.366 9.39 0.145 0.221 0.396 0.604

Sulfamic 0.250 1.20 0.095 0.155 0.380 0.620