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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
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.
(c) Neither K+ nor NO3- reacts with H2O. Solution will be neutral
1.00 10 14
HC2O4- + H2O H2C2O4 + OH- Kb2 = 2
1.79 10 13
5.60 10
1.00 10 14
(e) C2O42- + H2O HC2O4- + OH- Kb = 5
1.84 10 10
5.42 10
1.00 10 14
HAsO42- + H2O H2AsO4- + OH- Kb2 = 9.1 10 8
1.1 10 7
1.00 10 14
H2AsO4- + H2O H3AsO4 + OH- Kb3 = 3
1.7 10 12
5.8 10
1.00 10 14
(h) AsO43- + H2O HAsO42- + OH- Kb1 = 12
3.1 10 3
3.2 10
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
pH = -log(2.1210-5) = 4.674
15-4 (Note: In the first printing of the text, the answer in the back of the book was in error.)
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
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
15-6 (a) For this system we should use equation 15-15 since the approximation
pH = -log(2.410-5) = 4.62
pH = -log(4.0910-9) = 8.39
pH = -log(8.4310-5) = 4.07
pH = -log(2.5510-5) = 4.59
[H 3 O ][H 2 AsO -4 ] [H 3 O ] 2
5.8 10 3
[H 3 AsO 4 ] 0.0400 [H 3 O ]
(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
pH = -log(2.3610-5) = 4.63
(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
1.00 10 14
(b) C2O42- + H2O HC2O4- + OH- Kb1 = 5
1.84 10 10
5.42 10
(c) pH = 9.70
(d) pH = 9.89
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,
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,
[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
1.00 10 14
(c) CO32- + H2O HCO3- + OH- Kb1 = 11
2.13 10 4
4.69 10
(b) Recognizing that the first proton of H2SO4 completely dissociates we obtain
1.00 10 14
(d) CH3COO- + H2O CH3COOH + OH- Kb1 = 5
5.7 10 10
1.75 10
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
1/0.066 = 15.2
(b) Substituting [H3O+] = 1.0010-6 into the expressions for K1, K2 and K3 yields
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
Thus, the predominant acid/base system involves [Cit3-] and [HCit2-] and their acid/base
ratio is
(d) (Note: In the first printing of the text, the answer in the back of the book was in error.)
[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
[H2AsO4-]/[HAsO42-] = 9.110-3
[HCO3-]/[CO32-] = 21
[H3O+][HPO42-]/[H2PO4-] = 6.3210-8
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
[H3O+][P2-]/[HP-] = 3.9110-6
(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
[H3O+][CO32-]/[HCO3-] = 4.6910-11
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
0.300 V Na 2 CO 3
- 0.200VHCl = 0.023734 VHCl
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
Let VH 3 PO 4
and VNaOH be the volume in milliliters of the two reagents. Then
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
0.2611 (1000 - VH 3 PO 4
) = 0.4528 VH 3 PO 4
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-.
Proceeding as in Problem 15-21 we solve equations (2), (3), (4) and (5) and conclude that
15-23 (a) For Na2M, K1 = 1.310-2 and K2 = 5.910-7. This initial pH is high and two equally
(b) Curve 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
(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
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
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
c i H2A VH 2 A
At and after the 2nd equivalence point: [A2-] =
V i H2A 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
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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
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
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
ci BVB ciSAViMix
and [A-] = + [H3O+]
Vi Mix VB
Substituting these expressions into the equilibrium expression for HA- and rearranging gives
ci HAViMix
At and after the 2nd equivalence point: [A-] = - [HA]
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
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25
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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$1+A14)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 15
15-28
A B C D E F
1 Vi, Mixture 50.00 Kw, H2O 1.00E-14
2 ci, HClO4 0.1000 c, KOH 0.2000
3 ci, HCOOH 8.00E-02
4 Ka, HCOOH 1.80E-04
5 Vol. KOH, mL b c [OH-] [H3O+] pH
6 0.00 1.0018E-01 -1.4400E-05 1.0014E-01 1.00
7 10.00 5.0180E-02 -1.2000E-05 5.0238E-02 1.30
8 20.00 1.4466E-02 -1.0286E-05 1.4965E-02 1.83
9 24.00 2.8827E-03 -9.7297E-06 4.6975E-03 2.33
10 25.00 1.8000E-04 -9.6000E-06 3.0097E-03 2.52
11 26.00 2.8116E-03 -9.0000E-06 1.9073E-03 2.72
12 35.00 2.3709E-02 -4.2353E-06 1.7731E-04 3.75
13 44.00 4.0606E-02 -3.8298E-07 9.4295E-06 5.03
14 45.00 5.5556E-11 -2.3392E-12 1.5294E-06 6.5385E-09 8.19
15 46.00 2.0833E-03 -2.3148E-12 2.0833E-03 4.8000E-12 11.32
16 50.00 1.0000E-02 -2.2222E-12 1.0000E-02 1.0000E-12 12.00
17
18
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24
25
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29
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31
32 Spreadsheet Documentation
33 B6 = ($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$1/D14
Fundamentals of Analytical Chemistry: 8th ed. Chapter 15
[ H 3 O ][H 2 AsO -4 ]
K1 = = 5.810-3 (1)
[ H 3 AsO 4 ]
[ H 3 O ][HAsO 24- ]
K2 = = 1.110-7 (2)
[ H 2 AsO -4 ]
[H 3 O ][AsO 34- ]
K3 = 2- = 3.210-12 (3)
[ HAsO 4 ]
Subtracting the first reaction from the second and rearranging give
Fundamentals of Analytical Chemistry: 8th ed. Chapter 15
[ NH 3 ][HOAc] 5.70 10 10
= 3.2610-5
[ NH 4 ][OAc - ] 1.75 10 5
Fundamentals of Analytical Chemistry: 8th ed. Chapter 15
15-31
A B C D E F G H I J
1 pH [H3O ]+
K1 K2 K3 0 1 2 3
2 (a) 2.00 1.00E-02 1.12E-03 3.91E-06 0.899 0.101 3.94E-05
3 6.00 1.00E-06 1.82E-04 0.204 7.96E-01
4 10.00 1.00E-10 2.28E-12 2.56E-05 1.00E+00
5 (b) 2.00 1.00E-02 7.11E-03 6.32E-08 4.5E-13 0.584 0.416 2.63E-06 1.18E-16
6 6.00 1.00E-06 1.32E-04 0.940 5.94E-02 2.67E-08
7 10.00 1.00E-10 2.21E-11 1.57E-03 9.94E-01 4.47E-03
8 (c) 2.00 1.00E-02 7.45E-04 1.73E-05 4.02E-07 0.931 0.069 1.20E-04 4.82E-09
9 6.00 1.00E-06 5.31E-05 3.96E-02 6.85E-01 2.75E-01
10 10.00 1.00E-10 1.93E-16 1.44E-09 2.49E-04 1.00E+00
11 (d) 2.00 1.00E-02 5.8E-03 1.1E-07 3.2E-12 0.633 0.367 4.04E-06 1.29E-15
12 6.00 1.00E-06 1.55E-04 0.901 9.91E-02 3.17E-07
13 10.00 1.00E-10 1.52E-11 8.80E-04 9.68E-01 3.10E-02
14 (e) 2.00 1.00E-02 3E-02 1.62E-07 0.250 0.750 1.21E-05
15 6.00 1.00E-06 2.87E-05 0.861 1.39E-01
16 10.00 1.00E-10 2.06E-12 6.17E-04 9.99E-01
17 (f) 2.00 1.00E-02 5.60E-02 5.42E-05 0.151 0.845 4.58E-03
18 6.00 1.00E-06 3.23E-07 0.018 9.82E-01
19 10.00 1.00E-10 3.29E-15 1.85E-06 1.00E+00
20
21 Spreadsheet Documentation
22 C2 = 10^(-C2)
23 G2 = C2^2/(C2^2+$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
[ 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
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
gives
cT D
=
[ H 3 A] [ H 3 O ]3
[ H 3 A] [ H 3 O ]3
= = 0 (6)
cT D
[ 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
[ A 3- ] K1 K 2 K 3
= = 3
cT D