Fundamentals of Analytical Chemistry: 8th ed.

Chapter 15

Chapter 15

15-1 The HPO42- is such a weak acid (Ka3 = 4.510-13) that the change in pH in the vicinity of the

third equivalence point is too small to be observable.

15-2 (a) NH4+ + H2O NH3 + H3O+ Ka = 5.7010-10

K w 1.00 10 14
OAc- + H2O HOAc + OH- Kb = 5
5.71 10 10
Ka 1.75 10

Since the Ks are essentially identical, the solution should be approximately neutral.

(b) NO2- + H2O HNO2 + OH- Solution will be basic

(c) Neither K+ nor NO3- reacts with H2O. Solution will be neutral

(d) HC2O4- + H2O C2O42- + H3O+ Ka2 = 5.4210-5

1.00 10 14
HC2O4- + H2O H2C2O4 + OH- Kb2 = 2
1.79 10 13
5.60 10

Solution will be acidic

1.00 10 14
(e) C2O42- + H2O HC2O4- + OH- Kb = 5
1.84 10 10
5.42 10

Solution will be basic

(f) HAsO42- + H2O AsO43- + H3O+ Ka3 = 3.210-12

1.00 10 14
HAsO42- + H2O H2AsO4- + OH- Kb2 = 9.1 10 8
1.1 10 7

Solution will be basic

(g) H2AsO4- + H2O HAsO42- + H3O+ Ka2 = 1.110-7

Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

1.00 10 14
H2AsO4- + H2O H3AsO4 + OH- Kb3 = 3
1.7 10 12
5.8 10

Solution will be acidic

1.00 10 14
(h) AsO43- + H2O HAsO42- + OH- Kb1 = 12
3.1 10 3
3.2 10

Solution will basic

15-3 H3PO4 + H2O H2PO4- + H3O+ Ka1 = 7.1110-3

H2PO4- + H2O HPO42- + H3O+ Ka2 = 6.3210-8

Here both Ka2 and Kw/Ka1 are small and we may assume that [H2PO4-] >> [H3PO4] and

[HPO42-] at the first equivalence point. If we further assume that Kw << Ka2[H2PO4-] and

[H2PO4-]/Ka1 >> 1 we may use equation 15-16 to give

[H3O+] = (7.1110-36.3210-8)1/2 = 2.1210-5

pH = -log(2.1210-5) = 4.674

Bromocresol green would be satisfactory

15-4 (Note: In the first printing of the text, the answer in the back of the book was in error.)

H2PO4- + H2O HPO42- + H3O+ Ka2 = 6.3210-8

HPO42- + H2O PO43- + H3O+ Ka3 = 4.510-13

Here again both Ka3 and Kw/Ka2 are small and we may assume that [HPO42-] >> [H2PO4-] and

[PO43-] at the first equivalence point. However, the further approximation Kw <<

Ka3[HPO42-] is likely not valid and we should use equation 15-15. If we assume, for

example, [HPO42-] = 0.01 M we obtain

Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

0.01 4.5 10 13 1.0 10 14

[H3O+] = = 3.010-10

1 0.01 / 6.32 10 8
pH = -log(3.010-10) = 9.52

Phenolphthalein or Thymolphthalein would work.

15-5 Curve A in figure 15-4 is the titration curve for H3PO4. Note that one end point occurs at

about pH 4.5 and a second at about pH 9.5. Thus, H3PO4 would be determined by titration

with bromocresol green as an indicator (pH 3.8 to 5.4). A titration to the second end point

with phenolphthalein would give the number of millimoes of NaH2PO4 plus twice the

number of millimoles of H3PO4. Thus, the concentration of NaH2PO4 is obtained from the

difference in volume for the two titrations.

15-6 (a) For this system we should use equation 15-15 since the approximation

[H2AsO4-]/5.810-3 >> 1 is not valid.

0.05 1.1 10 7 1.0 10 14

[H3O+] = = 2.410-5
1 0.05 /(5.8 10 3 )

pH = -log(2.410-5) = 4.62

Bromocresol green (3.8 to 5.4)

[OH - ][HP - ] 1.00 10 14

(b) P2- + H2O HP- + OH- Kb1 = 6
2.56 10 9
[P ]2-
3.91 10

[OH-] = [HP-] and we assume [P2-] = 0.05 [OH-] 0.05

[OH-] = (0.052.5610-9)1/2 = 1.1310-5

pH = 14.00 (-log(1.1310-5)) = 9.05

Phenolphthalein (8.3 to 10)

Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

(c) As in part (b)

[OH-] = (0.051.0010-14/4.3110-5)1/2 = 3.4110-6

pH = 14.00 (-log(3.4110-6)) = 8.53

Cresol purple (7.6 to9.2)

(d) Here we are able to use equation 15-16

[H3O+] = (1.4210-71.1810-10)1/2 = 4.0910-9

pH = -log(4.0910-9) = 8.39

Cresol purple (7.6 to 9.2)

(e) NH3C2H4NH32+ + H2O NH3C2H4NH2+ + H3O+ Ka1 = 1.4210-7

[H3O+] = (0.051.4210-7)1/2 = 8.4310-5

pH = -log(8.4310-5) = 4.07

Bromocresol green (3.8 to 5.4)

(f) Proceeding as in part (a)

0.05 6.6 10 8 1.0 10 14

[H3O+] = = 2.5510-5
1 0.05 /(1.23 10 2 )

pH = -log(2.5510-5) = 4.59

Bromocresol green (3.8 to 5.4)

(g) Proceeding as in part (b) we obtain pH = 9.94

Phenolphthalein (8.5 to 10.0)

Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

15-7 (a) H3AsO4 + H2O H2AsO4- + H3O+ Ka1 = 5.810-3

[H 3 O ][H 2 AsO -4 ] [H 3 O ] 2

5.8 10 3
[H 3 AsO 4 ] 0.0400 [H 3 O ]

0 = [H3O+]2 + 5.810-3[H3O+] 5.810-30.0400

Solving using the quadratic formula gives

[H3O+] = 1.2610-2 and pH = 1.90

Proceeding in the same way we obtain

(b) 2.20

(c) 1.64

(d) 1.77

(e) 4.21

1.00 10 14
(f) NH2C2H4NH2 + H2O NH3C2H4NH2+ + OH- Kb1 = 10
8.47 10 5
1.18 10

[OH - ] 2
8.4710-5
0.0400

[OH-] = (0.04008.4710-5)1/2 = 1.8410-3

pH = 14.00 (-log(1.8410-3)) = 11.26

0.0400 1.1 10 7 1.0 10 14

15-8 (a) [H3O+] = = 2.3610-5
1 0.0400 /(5.8 10 3 )

pH = -log(2.3610-5) = 4.63

Proceeding as in part (a) we obtain

(b) pH = 2.95
Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

(c) pH = 4.28

(d) pH = 4.60

(e) pH = 9.80

(f) pH = 8.39

1.00 10 14
15-9 (a) AsO43- + H2O HAsO42- + OH- Kb1 = 12
3.12 10 3
3.2 10

[OH - ][HAsO 24- ] [OH - ] 2

3.12 10 3
3-
[AsO 4 ] 0.0400 [OH ]-

0 = [OH-]2 + 3.1210-3[OH-] 3.1210-30.0400

Solving using the quadratic formula gives

[OH-] = 9.7210-3 and pH = 14.00 (-log(9.7210-3)) = 11.99

1.00 10 14
(b) C2O42- + H2O HC2O4- + OH- Kb1 = 5
1.84 10 10
5.42 10

[OH-] = (0.04001.8410-10)1/2 = 2.7210-6 and pH = 8.43

Proceeding as in part (b) we obtain

(c) pH = 9.70

(d) pH = 9.89

(e) Proceeding as in part (a) gives pH = 12.58

(f) NH3C2H4NH32+ + H2O NH3C2H4NH2+ + H3O+ Ka1 = 1.4210-7

[H3O+] = (0.04001.4210-7)1/2 = 7.5410-5 and pH = 4.12

Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

15-10 (a) H3PO4 + H2O H2PO4- + H3O+ Ka1 = 7.1110-3

[H 3 O ][H 2 PO -4 ] (0.0200 [H 3 O ])[H 3 O ]

-3
7.1110 =
[H 3 PO 4 ] 0.0500 [H 3 O ]

Rearranging gives 0 = [H3O+]2 +(0.0200+7.1110-3)[H3O+] (7.1110-3)(0.0500)

and solving the quadratic gives [H3O+] = 9.6710-3 and pH = 2.01

(b) H2AsO4- + H2O HAsO42- + H3O+ Ka2 = 1.1110-7

[H 3 O ][HAsO 24- ] (0.0500 [ H 3 O ])[H 3 O ] (0.0500)[H 3 O ]

-7
1.1110 =
[H 2 AsO -4 ] 0.0300 [ H 3 O ] 0.0300

[H3O+] = 6.6610-8 and pH = 7.18

(c) HCO3- + H2O CO32- + H3O+ Ka2 = 4.6910-11

Proceeding as in part (b) we obtain [H3O+] = 2.3410-11 and pH = 10.63

(d) H3PO4 + HPO42- 2H2PO4-

For each milliliter of solution, 0.0200 mmol Na2HPO4 reacts with 0.0200 mmol

H3PO4 to give 0.0400 mmol NaH2PO4 and to leave 0.0200 mmol H3PO4. Thus,

we have a buffer that is 0.0200 M in H3PO4 and 0.0400 M in NaH2PO4.

Proceeding as in part (a) we obtain [H3O+] = 2.8210-3 and pH = 2.55

(e) HSO4- + H2O SO42- + H3O+ Ka2 = 1.0210-2

Proceeding as in part (a) we obtain [H3O+] = 8.6610-3 and pH = 2.06

15-11 (a) Proceeding as in 15-10(a) we obtain [H3O+] = 3.4810-3 and pH = 2.46

(b) Proceeding as in 15-10(b) we obtain [H3O+] = 3.1010-8 and pH = 7.51

(c) HOC2H4NH3+ + H2O HOC2H4NH2 + H3O+ Ka = 3.1810-10

Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

Proceeding as in 15-10(b) we obtain [H3O+] = 3.7310-10 and pH = 9.43

(d) H2C2O4 + C2O42- 2HC2O4-

For each milliliter of solution, 0.0240 mmol H2HPO4 reacts with 0.0240 mmol

C2O42- to give 0.0480 mmol HC2O4- and to leave 0.0120 mmol C2O42-. Thus,

we have a buffer that is 0.0480 M in HC2O4- and 0.0120 M in C2O42-.

Proceeding as in 15-10(a) we obtain [H3O+] = 2.1710-4 and pH = 3.66

(e) Proceeding as in 15-10(b) we obtain [H3O+] = 2.1710-4 and pH = 3.66

15-12 (a) (NO2)3C6H2OH + H2O (NO2)3C6H2O- + H3O+ Ka = 0.43

[H 3 O ][(NO2 ) 3 C 6 H 2 O - ] (0.0100 x) x
0.43 =
[(NO 2 ) 3 C 6 H 2 OH] 0.0200 x

Rearranging gives 0 = x2 +(0.0100+0.43)x (0.43)(0.0200)

and solving the quadratic gives x = 1.8710-2

the total [H3O+] = 0.0100 + x = 0.0287 and pH = 1.54

(b) Proceeding as in part (a) we obtain [H3O+] = 1.01310-2 and pH = 1.99

1.00 10 14
(c) CO32- + H2O HCO3- + OH- Kb1 = 11
2.13 10 4
4.69 10

[OH - ][HCO 3- ] (0.0100 x ) x

-4
2.1310 =
[CO 32- ] 0.100 x

Rearranging gives 0 = x2 +(0.0100+2.1310-4)x (2.1310-4)(0.100)

and solving the quadratic gives x = 1.7810-3

Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

the total [OH-] = 0.0100 + x = 0.0118 and pH = 12.07

(d) Proceeding as in part (c) we obtain [OH-] = 1.01710-2 and pH = 12.01

15-13 (a) Proceeding as in 15-12(a) we obtain [H3O+] = 1.28710-2 and pH = 1.89

(b) Recognizing that the first proton of H2SO4 completely dissociates we obtain

HSO4- + H2O SO42- + H3O+ Ka2 = 1.0210-2

[H 3 O ][SO 24- ] (0.0100 0.0150 x) x

1.0210 =-2
[HSO -4 ] 0.0150 x

Rearranging gives 0 = x2 +(0.0250+1.0210-2)x (1.0210-2)(0.0150)

and solving the quadratic gives x = 3.9110-3

the total [H3O+] = 0.0250 + x = 0.0289 and pH = 1.54

(c) Proceeding as in 15-12(c) we obtain [OH-] = 0.0382 and pH = 12.58

1.00 10 14
(d) CH3COO- + H2O CH3COOH + OH- Kb1 = 5
5.7 10 10
1.75 10

CH3COO- is such a weak base that it makes no significant contribution to [OH-].

Therefore, [OH-] = 0.010 and pH = 12.00

15-14 (a) Let us compare the ratio [H2SO3]/[HSO3-] with that of [SO32-]/[HSO3-] at [H3O+]

= 1.0010-6. The larger ratio will contain the predominant acid/base pair.

[ H 2 SO 3 ] [H 3 O ] 1.00 10 6
2
8.1 10 5
-
[ HSO 3 ] K a1 1.23 10
Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

[SO 32- ] K a2 6.6 10 8

0.066
[ HSO 3- ] [H 3 O ] 1.00 10 6

Clearly the predominant pair is SO32-/HSO3- and its acid/base ratio is

1/0.066 = 15.2

(b) Substituting [H3O+] = 1.0010-6 into the expressions for K1, K2 and K3 yields

[H 2 Cit - ] [ HCit 2- ] [Cit 3- ]

= 745 = 17.3 = 0.40
[H 3 Cit] [H 2 Cit - ] [HCit 2- ]

The large size of the first two ratios and the small size of the third indicate the HCit2- is a

predominant species in this solution. To compare [Cit3-] and [H2Cit-] we invert the second

ratio. Then

[H2Cit-]/[HCit2-] = 1/17.3 = 0.058

Thus, the predominant acid/base system involves [Cit3-] and [HCit2-] and their acid/base

ratio is

[HCit2-]/[Cit3-] = 1/0.40 = 2.5

(c) Proceeding as in part (a) we obtain [HM-]/[M2-] = 0.498

(d) (Note: In the first printing of the text, the answer in the back of the book was in error.)

Proceeding as in part (a) we obtain [HT-]/[T2-] = 0.0232

15-15 (a) Proceeding as in Problem 15-14(a) with [H3O+] = 1.0010-9 we obtain

[H2S]/[HS-] = 0.010

(b) Formulating the three species as BH22+, BH+ and B, where B is the symbol for

NH2C2H5NH2.
Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

[ H 3 O ][BH ] [ H 3 O ][ B]
= K1 = 1.4210-7 and = K2 = 1.1810-10
[ BH 22 ] [ BH ]

1.00 10 9
[BH22+]/[BH+] = = 0.0070
1.42 10 7

1.18 10 10
[B]/[BH+] = = 0.118
1.00 10 9

[BH22+] is clearly < [B] and [BH+]/[B] = 1.00/0.118 = 8.5

(c) Proceeding as in Problem 15-14(b) we find

[H2AsO4-]/[HAsO42-] = 9.110-3

(d) Proceeding as in Problem 15-14(a) we find

[HCO3-]/[CO32-] = 21

15-16 pH = 7.30 [H3O+] = antilog (-7.30) = 5.01210-8

[H3O+][HPO42-]/[H2PO4-] = 6.3210-8

[HPO42-]/[H2PO4-] = 6.3210-8 / (5.01210-8) = 1.261

HPO42- + H3PO4 2H2PO4-

no. mmol H3PO4 present = 400 0.200 = 80.0

no. mmol H2PO4- in the buffer = 2 80.0 = 160.0

no. mmol HPO42- needed for the buffer = 1.261 160.0 = 201.8

Thus, we need 80.0 mmol of Na2HPO4 to react with the H3PO4 and an additional 201.8

mmol to provide the needed concentration of HPO42- or 281.8 mmol.

mass Na2HPO42H2O = 281.8 mmol 0.17799 g/mmol = 50.2 g

Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

15-17 pH = 5.75 [H3O+] = antilog (-5.75) = 1.77810-6

[H3O+][P2-]/[HP-] = 3.9110-6

[P2-]/[HP-] = 3.9110-6 / (1.77810-6) = 2.199

P2- + H2P 2HP-

no. mmol H2P present = 750 0.0500 = 37.5

no. mmol HP- in the buffer = 2 37.5 = 75.0

no. mmol P2- needed in the buffer = 2.199 75.0 = 164.9

Thus, we need 37.5 + 164.9 = 202.4 mmol of K2P.

mass K2P = 202.4 mmol 0.24232 g K2P /mmol = 49.0 g K2P

15-18 no. mmol NaH2PO4 = 50.0 0.200 = 10.0

(a) no. mmol H3PO4 formed = no. mmol HCl added = 50.0 0.120 = 6.00

c H 3 PO 4 = 6.00/100 = 0.0600 M

c NaH 2 PO 4 = (10.0 6.00)/100 = 0.0400

Proceeding as in Problem 15-10(a) we obtain pH = 2.11

(b) c Na 2 HPO 4 = 6.00/100 = 0.0600 M

c NaH 2 PO 4 = (10.0 6.00)/100 = 0.0400

Proceeding as in Problem 15-10(b), using K2 gives pH = 7.38

15-19 no. mmol KHP = 100 0.150 = 15.0

(a) no. mmol P2- = 100 0.0800 = 8.00

no. mmol KHP = 15.0 8.00 = 7.00

c HP - = 7.00/200 = 0.0350 M c P 2 - = 8.00/200 = 0.0400

Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

Proceeding as in Problem 15-10(b) we obtain pH = 5.47

(b) c H 2 P = 8.00/200 = 0.0400 M c HP - = (15.00 - 8.00)/200 = 0.0350

Proceeding as in Problem 15-10(a) we obtain pH = 2.92

15-20 pH = 9.60 [H3O+] = antilog (-9.60) = 2.51210-10

[H3O+][CO32-]/[HCO3-] = 4.6910-11

[CO32-]/[HCO3-] = 4.6910-11/2.51210-10 = 0.1867

Let VHCl = mL 0.200 M HCl and V Na 2 CO 3

= mL 0.300 M Na2CO3

Since the solutions are dilute, the volumes will be additive

VHCl + V Na 2 CO 3
= 1000 mL

Assume

[CO32-] c Na 2 CO 3
= ( V Na 2 CO 3
0.300 - VHCl 0.200)/1000

[HCO3-] c HCO 3- = VHCl 0.200/1000

Substituting these relationships into the ratio [CO32-]/[HCO3-] gives

0.300 V Na 2CO 3 0.200VHCl

= 0.1867
0.200VHCl

0.300 V Na 2 CO 3
- 0.200VHCl = 0.023734 VHCl

0.300(1000 VHCl) = 0.23734 VHCl

VHCl = 300/0.5373 = 558 mL

V Na 2 CO3 = 1000 558 = 442 mL

Thus mix 442 mL of 0.300 M Na2CO3 with (1000 442) = 558 mL of 0.200 M HCl.
Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

15-21 [H3O+][HPO42-]/[HPO4-] = 6.3210-8

[ HPO 24- ] 6.32 10 8

= 0.632 (1)
[ H 2 PO -4 ] 1.00 10 7

Let VH 3 PO 4
and VNaOH be the volume in milliliters of the two reagents. Then

VH 3PO 4 + VNaOH = 1000 mL (2)

From mass-balance considerations we may write that in the 1000 mL

no. mmol NaH2PO4 + no. mmol Na2HPO4 = 0.200 VH 3 PO 4 (3)

no. mmol NaH2PO4 + 2 no. mmol Na2HPO4 = 0.160 VNaOH (4)

Equation (1) can be written as

no. mmol Na 2 HPO 4 /1000 no. mmol Na 2 HPO 4

= 0.632 (5)
no. mmol NaH 2 PO 4 /1000 no. mmol NaH 2 PO 4

Thus, we have four equations, (2), (3), (4) and (5), and four unknowns: VH 3 PO 4
, VNaOH, no.

mmol NaH2PO4 and no. mmol Na2HPO4. Subtracting Equation (3) from (4) yields

no. mmol Na2HPO4 = 0.160 VNaOH 0.200 VH 3 PO 4

(6)

Substituting Equation (6) into (3) gives

no. mmo NaH2PO4 + 0.160 VNaOH 0.200 VH 3 PO 4

= 0.200 VH 3 PO 4

no. mmo NaH2PO4 = -0.160 VNaOH + 0.400 VH 3 PO 4

(7)

Substituting Equations (6) and (7) into (5) gives

Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

0.160V NaOH 0.200VH 3PO 4

= 0.632
0.400VH 3PO 4 0.160V NaOH

This equation rearranges to

0.2611 VNaOH = 0.4528 VH 3 PO 4

Substituting Equation (2) gives

0.2611 (1000 - VH 3 PO 4
) = 0.4528 VH 3 PO 4

VH 3PO 4 = 261.1/0.7139 = 366 mLand VNaOH = 1000 366 = 634 mL

Thus, mix 366 mL H3PO4 with 634 mL NaOH

15-22 [H3O+][HAsO42-]/[H2AsO4-] = 1.110-7

[HAsO42-]/[H2AsO4-] = 1.110-7 / (1.0010-6) = 0.11 (1)

As in Problem 15-21 we now develop four independent equations that allow calculation of

VHCl, V Na 3 AsO 4
, no. mmol of HAsO42- and no. mmol of H2AsO4-.

V Na 3AsO4 + VHCl = 1000 mL (2)

no. mmol NaH2AsO4 + no. mmol Na2HAsO4 = 0.500 V Na 3 AsO 4

(3)

2 no. mmol NaH2AsO4 + no. mmol Na2HAsO4 = 0.400 VHCl (4)

no. mmol Na2HAsO4 / no. mmol NaH2AsO4 = 0.11 (5)

Proceeding as in Problem 15-21 we solve equations (2), (3), (4) and (5) and conclude that

704 mL of the HCl should be mixed with 296 mL of the Na3AsO4.

15-23 (a) For Na2M, K1 = 1.310-2 and K2 = 5.910-7. This initial pH is high and two equally

spaced end points will be encountered. Thus, curve C.

Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

(b) Curve A.

(c) Curve C for the reasons given in part (a).

15-24 (a) Titrations with NaOH of a solution containing a mixture of two weak acids HA1 and

HA2. HA1 is present in a greater concentration and has a dissociation constant that is larger

by a factor of about 104.

(b) Titration of a typical monoprotic weak acid.

(c) Titration of a mixture of a weak base, such as Na2CO3, and an acid salt, such as

NaHCO3.

15-25 For the titration of a mixture of H3PO4 and H2PO4- the volume to the first end point would have

to be smaller than one half the total volume to the second point because in the titration from the

first to second end points both analytes are titrated, whereas to the first end point only the H3PO4

is titrated.

For Problem 15-26 we set up spreadsheets that will solve a quadratic equation to determine [H3O+]

or [OH-], as needed (See approach taken for Problems 14-41 through 43). 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 diprotic acid with a strong base.

c i H2A Vi H 2A ci NaOHVNaOH
Before the 1st equivalence point: [H2A] =
Vi H2A VNaOH - [H3O+]

ci NaOHVNaOH
and [HA-] =
V i H2A V NaOH + [H3O+]
Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

Substituting these expressions into the equilibrium expression for H2A and rearranging gives

ci NaOHV NaOH




K a1 ci H 2 AVi H 2 A ci NaOHVNaOH

K

+ 2 +
0 = [H3O ] + a1 [H3O ] -

Vi H 2 A V NaOH Vi H 2 A V NaOH

From which [H3O+] is directly determined.

At the 1st equivalence point we use Equation 15-13

K a2 ciH 2 AViH 2 A /(ViH 2 A V NaOH ) K w

[H3O+] =
1 ciH 2 AViH 2 A /( K a1 (ViH 2 A V NaOH ))

After the 1st and before the 2nd equivalence point:

2 c i H2A Vi H 2 A ci NaOHV NaOH

V
-
[HA ] = - [H3O+]
i H 2A VNaOH

c VNaOH ciH 2 AViH 2 A

i NaOH
V
2-
and [A ] = + [H3O+]
i H 2A VNaOH

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

ci NaOHVNaOH ciH 2 AViH 2 A
0 = [H3O+]2 + K a2 [H3O+] -


Vi H 2 A VNaOH

K a2 2 ci H 2 AVi H 2 A ci NaOHV NaOH
V i H 2A VNaOH
Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

From which [H3O+] is directly determined.

c i H2A VH 2 A
At and after the 2nd equivalence point: [A2-] =
V i H2A V NaOH - [HA-]

c i NaOH VNaOH 2 ci H 2 AVi H 2 A

and [OH-] =
V i H 2A V NaOH + [HA-]

Substituting these expressions into the equilibrium expression for A2- and rearranging gives

ci NaOHVNaOH 2 ci H 2 AVi H 2 A K K w ci H 2AViH 2 A
0 = [HA-]2 + w [HA-] -


Vi H 2 A VNaOH K a2 K a2 Vi H 2 A V NaOH
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 15

15-26
A B C D E F
1 Part (a) Vi, H2SO3 50.00 Kw, H2O 1.00E-14
2 ci, H2SO3 0.1000 c, NaOH 0.2000
3 Ka1, H2SO3 1.23E-02 Veq. pt. 25.00
4 Ka2, H2SO3 6.60E-08
5 Vol. NaOH, mL b c [OH-] [H3O+] pH
6 0.00 1.2300E-02 -1.2300E-03 2.9456E-02 1.53
7 12.50 5.2300E-02 -4.9200E-04 8.1403E-03 2.09
8 20.00 6.9443E-02 -1.7571E-04 2.4443E-03 2.61
9 24.00 7.7165E-02 -3.3243E-05 4.2843E-04 3.37
10 25.00 2.6179E-05 4.58
11 26.00 2.6316E-03 -4.1684E-09 1.5830E-06 5.80
12 37.50 2.8571E-02 -1.8857E-09 6.6000E-08 7.18
13 45.00 4.2105E-02 -6.9474E-10 1.6500E-08 7.78
14 49.00 4.8485E-02 -1.3333E-10 2.7500E-09 8.56
15 50.00 1.5152E-07 -7.5758E-09 8.6963E-05 1.1499E-10 9.94
16 51.00 1.9803E-03 -7.5008E-09 1.9840E-03 5.0404E-12 11.30
17 60.00 1.8182E-02 -6.8871E-09 1.8182E-02 5.4999E-13 12.26
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33 Spreadsheet Documentation
34 F3 = C1*C2/F2
35 B6 = $F$2*A6/($C$1+A6)+$C$3
36 C6 = -$C$3*($C$2*$C$1-$F$2*A6)/($C$1+A6)
37 E6 = (-B6+SQRT(B6^2-4*C6))/2
38 F6 = -LOG(E6)
39 E10 = SQRT(($C$4*$C$1*$C$2/($C$1+A10)+$F$1)/(1+$C$1*$C$2/($C$1+A10)/$C$3))
40 B11 = ($F$2*A11-$C$1*$C$2)/($C$1+A11)+$C$4
41 C11 = -$C$4*(2*$C$2*$C$1-$F$2*A11)/($C$1+A11)
42 B15 = ($F$2*A15-2*$C$1*$C$2)/($C$1+A15)+$F$1/$C$4
43 C15 = -($F$1/$C$4)*($C$2*$C$1)/($C$1+A15)
44 D15 = (-B15+SQRT(B15^2-4*C15))/2+($F$2*A15-2*$C$1*$C$2)/($C$1+A15)
45 E15 = $F$1/D15

A B C D E F
Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

1 Part (b) Vi, H2NC2H4NH2 50.00 Kw, H2O 1.00E-14

2 ci, H2NC2H4NH2 0.1000 c, NaOH 0.2000
2+
3 Ka1, H3NC2H4NH 3 1.42E-07 Veq. pt. 25.00
+
4 Ka2, H2NC2H4NH 3 1.18E-10
5 Vol. HCl, mL b c [OH-] [H3O+] pH
6 0.00 8.4746E-05 -8.4746E-06 2.8690E-03 3.4855E-12 11.46
7 12.50 4.0085E-02 -3.3898E-06 8.4389E-05 1.1850E-10 9.93
8 20.00 5.7228E-02 -1.2107E-06 2.1147E-05 4.7287E-10 9.33
9 24.00 6.4950E-02 -2.2904E-07 3.5263E-06 2.8359E-09 8.55
10 25.00 4.0960E-09 8.39
11 26.00 2.6316E-03 -4.4477E-09 1.6890E-06 5.9206E-09 8.23
12 37.50 2.8571E-02 -2.0121E-09 7.0422E-08 1.4200E-07 6.85
13 45.00 4.2105E-02 -7.4129E-10 1.7606E-08 5.6800E-07 6.25
14 49.00 4.8485E-02 -1.4227E-10 2.9343E-09 3.4080E-06 5.47
15 50.00 1.4200E-07 -7.1000E-09 8.4191E-05 4.07
16 51.00 1.9803E-03 -7.0297E-09 1.9837E-03 2.70
17 60.00 1.8182E-02 -6.4545E-09 1.8182E-02 1.74
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33 Spreadsheet Documentation
34 F3 = C1*C2/F2
35 B6 = $F$2*A6/($C$1+A6)+$F$1/$C$4
36 C6 = -$F$1/$C$4*($C$2*$C$1-$F$2*A6)/($C$1+A6)
37 D6 = (-B6+SQRT(B6^2-4*C6))/2
38 E6 = $F$1/D6
39 F6 = -LOG(E6)
40 E10 = SQRT(($C$4*$C$1*$C$2/($C$1+A10)+$F$1)/(1+$C$1*$C$2/($C$1+A10)/$C$3))
41 B11 = ($F$2*A11-$C$1*$C$2)/($C$1+A11)+$F$1/$C$3
42 C11 = -($F$1/$C$3)*(2*$C$2*$C$1-$F$2*A11)/($C$1+A11)
43 B15 = ($F$2*A15-2*$C$2*$C$1)/($C$1+A15)+$C$3
44 C15 = -($C$3)*($C$1*$C$2/($C$1+A15))
45 E15 = (-B15+SQRT(B15^2-4*C15))/2+(A15*$F$2-2*$C$1*$C$2)/(A15+$C$1)

A B C D E F
1 Part (c) Vi, H2SO4 50.00 Kw, H2O 1.00E-14
Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

2 ci, H2SO4 0.1000 c, NaOH 0.2000

3 Ka1, H2SO4 Veq. pt. 25.00
4 Ka2, H2SO4 1.02E-02
5 Vol. NaOH, mL b c [OH-] [H3O+] pH
6 0.00 1.1020E-01 -1.0200E-03 1.0859E-01 0.96
7 12.50 5.0200E-02 -8.1600E-04 5.2926E-02 1.28
8 20.00 2.4486E-02 -7.2857E-04 3.1682E-02 1.50
9 24.00 1.2903E-02 -6.8919E-04 2.3285E-02 1.63
10 25.00 1.0200E-02 -6.8000E-04 2.1471E-02 1.67
11 26.00 1.2832E-02 -6.4421E-04 1.9764E-02 1.70
12 37.50 3.8771E-02 -2.9143E-04 6.4452E-03 2.19
13 45.00 5.2305E-02 -1.0737E-04 1.9779E-03 2.70
14 49.00 5.8685E-02 -2.0606E-05 3.4905E-04 3.46
15 50.00 9.8039E-13 -4.9020E-14 2.2140E-07 4.5166E-08 7.35
16 51.00 1.9802E-03 -4.8534E-14 1.9802E-03 5.0500E-12 11.30
17 60.00 1.8182E-02 -4.4563E-14 1.8182E-02 5.5000E-13 12.26
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33 Spreadsheet Documentation
34 F3 = C1*C2/F2
35 B6 = ($C$1*$C$2-$F$2*A6)/($C$1+A6)+$C$4
36 C6 = -$C$4*($C$2*$C$1)/($C$1+A6)
37 E6 = (-B6+SQRT(B6^2-4*C6))/2+($C$1*$C$2-$F$2*A6)/($C$1+A6)
38 F6 = -LOG(E6)
39 B10 = ($F$2*A10-$C$1*$C$2)/($C$1+A10)+$C$4
40 C10 = -$C$4*(2*$C$2*$C$1-$F$2*A10)/($C$1+A10)
41 E10 = (-B10+SQRT(B10^2-4*C10))/2
42 B15 = ($F$2*A15-2*$C$1*$C$2)/($C$1+A15)+$F$1/$C$4
43 C15 = -($F$1/$C$4)*($C$2*$C$1)/($C$1+A15)
44 D15 = (-B15+SQRT(B15^2-4*C15))/2+($F$2*A15-2*$C$1*$C$2)/($C$1+A15)
45 E15 = $F$1/D15

For Problems 15-27 and 15-28 we set up spreadsheets that will solve a quadratic equation to determine

[H3O+] or [OH-], as needed (See approach taken for Problems 14-41 through 43). While approximate
Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

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 volume of a mixture (ViMix) of a strong (SA) and weak (HA) acid with a strong base (B).

ci HAViMix
Before the 1st equivalence point: [HA] = - [A-]
Vi Mix VB

ViMix cSA ciBVB

and [H3O+] = + [A-]
ViMix VB
Substituting these expressions into the equilibrium expression for HA and rearranging gives

ViMix cSA ciBVB K a ci HAViMix

0 = [A-]2 + K a [A-] +
ViMix VB Vi Mix VB
From which [A-] is determined and [H3O+] may be calculated.

From the 1st equivalence to before the 2nd equivalence point:

ci HAVi Mix (ciBVB ViMix ciSA )

[HA] = - [H3O+]
Vi Mix VB

ci BVB ciSAViMix
and [A-] = + [H3O+]
Vi Mix VB
Substituting these expressions into the equilibrium expression for HA- and rearranging gives

ci BVB ciSAViMix K a ci HAVi Mix (ciBVB ViMix ciSA )

0 = [H3O+]2 + K a [H3O+] +
Vi Mix VB Vi Mix VB
Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

From which [H3O+] is directly determined.

ci HAViMix
At and after the 2nd equivalence point: [A-] = - [HA]
Vi Mix VB

ci BVB ci HAViMix ciSAViMix

and [OH-] = + [HA]
Vi Mix VB
Substituting these expressions into the equilibrium expression for A- and rearranging gives

ci BVB ci HAViMix ciSAViMix K w K w ci HAViMix

0 = [HA]2 + [HA] +
Vi Mix VB Ka K a Vi Mix VB

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

is taken for the titration of a mixture of a strong and weak base with a strong acid.
Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

15-27

A B C D E F
1 Vi, Mixture 50.00 Kw, H2O 1.00E-14
2 ci, NaOH 0.1000 c, HClO4 0.2000
3 ci, H2NNH2 8.00E-02
+
4 Ka, H2NNH 3 1.05E-08
5 Vol. HClO4, mL b c [OH-] [H3O+] pH
6 0.00 1.0000E-01 -7.6190E-08 1.0000E-01 9.9999E-14 13.00
7 10.00 5.0001E-02 -6.3492E-08 5.0001E-02 1.9999E-13 12.70
8 20.00 1.4287E-02 -5.4422E-08 1.4290E-02 6.9981E-13 12.15
9 24.00 2.7037E-03 -5.1480E-08 2.7216E-03 3.6743E-12 11.43
10 25.00 9.5238E-07 -5.0794E-08 2.2490E-04 4.4464E-11 10.35
11 26.00 2.6325E-03 -4.7619E-08 1.7966E-05 5.5660E-10 9.26
12 35.00 2.3530E-02 -2.2409E-08 9.5230E-07 1.0501E-08 7.98
13 44.00 4.0426E-02 -2.0263E-09 5.0124E-08 1.9950E-07 6.70
14 45.00 1.0500E-08 -4.4211E-10 2.1021E-05 4.68
15 46.00 2.0833E-03 -4.3750E-10 2.0835E-03 2.68
16 50.00 1.0000E-02 -4.2000E-10 1.0000E-02 2.00
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32 Spreadsheet Documentation
33 B6 = ($C$1*$C$2-$F$2*A6)/($C$1+A6)+$F$1/$C$4
34 C6 = -($F$1/$C$4)*($C$3*$C$1)/($C$1+A6)
35 D6 = (-B6+SQRT(B6^2-4*C6))/2+($C$1*$C$2-$F$2*A6)/($C$1+A6)
36 E6 = $F$1/D6
37 F6 = -LOG(E6)
38 B10 = ($F$2*A10-$C$1*$C$2)/($C$1+A10)+($F$1/$C$4)
39 C10 = -($F$1/$C$4)*($C$3*$C$1-($F$2*A10-$C$1*$C$2))/($C$1+A10)
40 D10 = (-B10+SQRT(B10^2-4*C10))/2
41 C14 = ($F$2*A14-$C$1*$C$2-$C$1*$C$3)/($C$1+A14)+$C$4
42 D14 = -($C$4)*($C$3*$C$1)/($C$1+A14)
43 E14 = (-B14+SQRT(B14^2-4*C14))/2+($F$2*A14-$C$1*$C$2-$C$1*$C$3)/($C$1+A14)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

15-28

A B C D E F
1 Vi, Mixture 50.00 Kw, H2O 1.00E-14
2 ci, HClO4 0.1000 c, KOH 0.2000
3 ci, HCOOH 8.00E-02
4 Ka, HCOOH 1.80E-04
5 Vol. KOH, mL b c [OH-] [H3O+] pH
6 0.00 1.0018E-01 -1.4400E-05 1.0014E-01 1.00
7 10.00 5.0180E-02 -1.2000E-05 5.0238E-02 1.30
8 20.00 1.4466E-02 -1.0286E-05 1.4965E-02 1.83
9 24.00 2.8827E-03 -9.7297E-06 4.6975E-03 2.33
10 25.00 1.8000E-04 -9.6000E-06 3.0097E-03 2.52
11 26.00 2.8116E-03 -9.0000E-06 1.9073E-03 2.72
12 35.00 2.3709E-02 -4.2353E-06 1.7731E-04 3.75
13 44.00 4.0606E-02 -3.8298E-07 9.4295E-06 5.03
14 45.00 5.5556E-11 -2.3392E-12 1.5294E-06 6.5385E-09 8.19
15 46.00 2.0833E-03 -2.3148E-12 2.0833E-03 4.8000E-12 11.32
16 50.00 1.0000E-02 -2.2222E-12 1.0000E-02 1.0000E-12 12.00
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32 Spreadsheet Documentation
33 B6 = ($C$1*$C$2-$F$2*A6)/($C$1+A6)+$C$4
34 C6 = -$C$4*($C$3*$C$1)/($C$1+A6)
35 E6 = (-B6+SQRT(B6^2-4*C6))/2+($C$1*$C$2-$F$2*A6)/($C$1+A6)
36 F6 = -LOG(E6)
37 B10 = ($F$2*A10-$C$1*$C$2)/($C$1+A10)+$C$4
38 C10 = -$C$4*($C$3*$C$1-($F$2*A10-$C$1*$C$2))/($C$1+A10)
39 E10 = (-B10+SQRT(B10^2-4*C10))/2
40 B14 = ($F$2*A14-$C$1*$C$2-$C$1*$C$3)/($C$1+A14)+$F$1/$C$4
41 C14 = -($F$1/$C$4)*($C$3*$C$1)/($C$1+A14)
42 D14 = (-B14+SQRT(B14^2-4*C14))/2+($F$2*A14-$C$1*$C$2-$C$1*$C$3)/($C$1+A14)
43 E14 = $F$1/D14
Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

15-29 (a) 2H2AsO4- H3AsO4 + HAsO42-

[ H 3 O ][H 2 AsO -4 ]
K1 = = 5.810-3 (1)
[ H 3 AsO 4 ]

[ H 3 O ][HAsO 24- ]
K2 = = 1.110-7 (2)
[ H 2 AsO -4 ]

[H 3 O ][AsO 34- ]
K3 = 2- = 3.210-12 (3)
[ HAsO 4 ]

Dividing Equation (2) by Equation (1) leads to

K 2 [H 3 AsO 4 ][HAsO 24- ]

= 1.910-5
K1 [H 2 AsO -4 ]2

which is the desired equilibrium constant expression.

(b) 2HAsO42- AsO43- + H2AsO4-

Here we divide Equation (3) by Equation (2)

K 3 [AsO 34- ][H 2 AsO -4 ]

= 2.910-5
K2 [HAsO 24- ]2

15-30 HOAc + H2O H3O+ + OAc- KHOAc = 1.7510-5

NH4+ + H2O H3O+ + NH3 K NH = 5.7010-10

4

Subtracting the first reaction from the second and rearranging give
Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

NH4+ + OAc- NH3 + HOAc K = K NH 4 / KHOAc

[ NH 3 ][HOAc] 5.70 10 10
= 3.2610-5
[ NH 4 ][OAc - ] 1.75 10 5
Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

15-31

A B C D E F G H I J
1 pH [H3O ]+
K1 K2 K3 0 1 2 3
2 (a) 2.00 1.00E-02 1.12E-03 3.91E-06 0.899 0.101 3.94E-05
3 6.00 1.00E-06 1.82E-04 0.204 7.96E-01
4 10.00 1.00E-10 2.28E-12 2.56E-05 1.00E+00
5 (b) 2.00 1.00E-02 7.11E-03 6.32E-08 4.5E-13 0.584 0.416 2.63E-06 1.18E-16
6 6.00 1.00E-06 1.32E-04 0.940 5.94E-02 2.67E-08
7 10.00 1.00E-10 2.21E-11 1.57E-03 9.94E-01 4.47E-03
8 (c) 2.00 1.00E-02 7.45E-04 1.73E-05 4.02E-07 0.931 0.069 1.20E-04 4.82E-09
9 6.00 1.00E-06 5.31E-05 3.96E-02 6.85E-01 2.75E-01
10 10.00 1.00E-10 1.93E-16 1.44E-09 2.49E-04 1.00E+00
11 (d) 2.00 1.00E-02 5.8E-03 1.1E-07 3.2E-12 0.633 0.367 4.04E-06 1.29E-15
12 6.00 1.00E-06 1.55E-04 0.901 9.91E-02 3.17E-07
13 10.00 1.00E-10 1.52E-11 8.80E-04 9.68E-01 3.10E-02
14 (e) 2.00 1.00E-02 3E-02 1.62E-07 0.250 0.750 1.21E-05
15 6.00 1.00E-06 2.87E-05 0.861 1.39E-01
16 10.00 1.00E-10 2.06E-12 6.17E-04 9.99E-01
17 (f) 2.00 1.00E-02 5.60E-02 5.42E-05 0.151 0.845 4.58E-03
18 6.00 1.00E-06 3.23E-07 0.018 9.82E-01
19 10.00 1.00E-10 3.29E-15 1.85E-06 1.00E+00
20
21 Spreadsheet Documentation
22 C2 = 10^(-C2)
23 G2 = C2^2/(C2^2+$D$2*C2+$D$2*$E$2)
24 H2 = C2*$D$2/(C2^2+$D$2*C2+$D$2*$E$2)
25 I2 = $D$2*$E$2/(C2^2+$D$2*C2+$D$2*$E$2)
26 G5 = C5^3/(C5^3+$D$5*C5^2+$D$5*$E$5*C5+$D$5*$E$5*$F$5)
27 H5 = C5^2*$D$5/(C5^3+$D$5*C5^2+$D$5*$E$5*C5+$D$5*$E$5*$F$5)
2 I5 = C5*$D$5*$E$5/(C5^3+$D$5*C5^2+$D$5*$E$5*C5+$D$5*$E$5*$F$5)
29 J5 = $D$5*$E$5*$F$5/(C5^3+$D$5*C5^2+$D$5*$E$5*C5+$D$5*$E$5*$F$5)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

15-32 Letting H3A = H3AsO4 we write

[ H 3 O ][ H 2 A - ] [ H 3 O ][HA 2- ]
K1 = (1) K2 = K3 =
[H 3 A] [H 2 A - ]

[ H 3 O ][A 3- ]
[ HA 2- ]

[ H 3 O ] 2 [HA 2- ] [H 3 O ]3 [A 3- ]
K1K2 = (2) K1K2K3 = (3)
[ H 3 A] [H 3 A]

By definition

[ H 3 A] [H 2 A - ] [HA 2- ]
0 = 1 = 2 =
cT cT cT

[ A 3- ]
3 =
cT

where

cT = [H3A] + [H2A-] + [HA2-] + [A3-] (4)

Substituting Equations (1), (2) and (3) into (4) yields

K 1 [H 3 A] K 1 K 2 [H 3 A] K 1 K 2 K 3 [H 3 A]
cT = [H3A] +
[H 3 O ] [H 3 O ] 2 [ H 3 O ]3

cT K1 K1 K 2 K K K
= 1+
2
1 2 33
[ H 3 A] [H 3O ] [H 3O ] [H 3 O ]
Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

Multiplying the numerator and denominator of the right side of this equation by [H3O+]3

gives

cT [ H 3 O ]3 K 1 [ H 3 O ] 2 K 1 K 2 [ H 3 O ] K 1 K 2 K 3
=
[ H 3 A] [ H 3 O ]3

Letting D = [H3O+]3 + K1[H3O+]2 + K1K2[H3O+] + K1K2K3 (5)

gives

cT D
=
[ H 3 A] [ H 3 O ]3

and inverting the two terms leads to 0

[ H 3 A] [ H 3 O ]3
= = 0 (6)
cT D

Substituting Equation (1) into (6) gives

[ H 3 O ][H 2 A - ] [ H 3 O ]3
=
K 1c T D

[H 2 A - ] K1[H 3 O ]2
= = 1
cT D

In the same way substituting Equation (2) into (6) gives upon rearrangement

[HA 2- ] K1 K 2 [H 3 O ]
= = 2
cT D
Fundamentals of Analytical Chemistry: 8th ed. Chapter 15

Similarly, substituting Equation (3) into (6) yields

[ A 3- ] K1 K 2 K 3
= = 3
cT D