Vous êtes sur la page 1sur 65

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 13

Chapter 13

13-1 amount A (mmol) = volume ( mL) cA ( mmol A / mL)

amount A (mole) = volume ( L) cA ( mol A / L)

13-2 (a) The millimole is the amount of an elementary species, such as an atom, an ion, a

molecule, or an electron. A millimole contains

particles mole particles


6.02 10 23 = 6.02 10 20
mole 1000 mmol mmol

(b) A titration involves measuring the quantity of a reagent of known concentration

required to react with a measured quantity of sample of an unknown concentration. The

concentration of the sample is then determined from the quantities of reagent and sample,

the concentration of the reagent, and the stoichiometry of the reaction.

(c) The stoichiometric ratio is the molar ratio of two chemical species that appear in a

balanced chemical equation.

(d) Titration error is the error encountered in titrimetry that arises from the difference

between the amount of reagent required to give a detectable end point and the theoretical

amount for reaching the equivalence point.

13-3 (a) The equivalence point in a titration is that point at which sufficient titrant has been

added so that stoichiometrically equivalent amounts of analyte and titrant are present.

The end point in a titration is the point at which an observable physical change signals the

equivalence point.

(b) A primary standard is a highly purified substance that serves as the basis for a

titrimetric method. It is used either (i) to prepare a standard solution directly by mass or
Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

(ii) to standardize a solution to be used in a titration.

A secondary standard is material or solution whose concentration is determined from the

stoichiometry of its reaction with a primary standard material. Secondary standards are

employed when a reagent is not available in primary standard quality. For example, solid

sodium hydroxide is hygroscopic and cannot be used to prepare a standard solution

directly. A secondary standard solution of the reagent is readily prepared, however, by

standardizing a solution of sodium hydroxide against a primary standard reagent such as

potassium hydrogen phthalate.

13-4 The Fajans method is a direct titration of the chloride ion, while the Volhard approach

requires two standard solutions and a filtration step to eliminate AgCl. The Fajans

method uses a fluorescein dye. At the end point, the fluoresceinate anions are absorbed

into the counter ion layer that surrounds the colloidal silver particles giving the solid an

intense red color. In the Volhard method, the silver chloride is more soluble that silver

thiocyanide such that the reaction AgCl(s ) + SCN



AgSCN( s ) + Cl occurs to a

significant extent as the end point is approached. The released Cl- ions cause the end

point color change to fade resulting in an over consumption of SCN- and a low value for

the chloride analysis.

1 mole H 2 NNH 2
13-5 (a)
2 moles I 2

5 moles H 2 O 2
(b)
2 moles MnO 4
Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

1 mole Na 2 B4 O 7 10 H 2 O
(c)
2 moles H +

2 moles S
(d)
3 moles KIO 3

13-6 In contrast to Ag2CO3 and AgCN, the solubility of AgI is unaffected by the acidity. In

addition, AgI is less soluble than AgSCN. The filtration step is thus unnecessary in the

determination of iodide, whereas it is needed in the determination of carbonate or cyanide.

13-7 The ions that are preferentially absorbed on the surface of an ionic solid are generally

lattice ions. Thus, in a titration, one of the lattice ions is in excess and its charge

determines the sign of the charge of the particles. After the equivalence point, the ion of

the opposite charge is present in excess and determines the sign of the charge on the

particle. Thus, in the equivalence-point region, the charge shift from positive to negative,

or the reverse.

13-8 (a)

0.0750 mole AgNO 3 L


0.0750 M AgNO 3 500 mL = 0.0375 mole
L 1000 mL
169.87 g AgNO 3
0.0375 mole = 6.37 g AgNO 3
mole

Dissolve 6.37 g AgNO3 in water and bring to 500 mL total volume.

(b)

0.325 mole HCl


0.325 M HCl 2.00 L = 0.650 mole
L
L
0.650 mole = 0.108 L reagent
6.00 mole reagent

Dilute 108 mL of the 6.00 M HCl reagent in enough water to yield 2.00 L total volume.
Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

(c)

0.0900 mole K + L
0.0900 M K + 750 mL = 0.0675 mole K +
L 1000 mL
mole K 4 Fe(CN ) 6 368.35 g K 4 Fe(CN ) 6
0.0675 mole K + = 6.22 g K 4 Fe(CN ) 6
4 moles K + mole

Dissolve 6.22 g K4Fe(CN)6 in water and bring to 750 mL total volume.

(d)

2.00 g BaCl 2 mole BaCl 2


2.00% ( w / v ) BaCl 2 600 mL = 0.0576 mole BaCl 2
100 mL solution 208.23 g
L
0.0576 mole BaCl 2 = 0.115 L BaCl 2
0.500 mole BaCl 2

Dilute 115 mL of 0.500M BaCl2 in enough water to yield 600 mL total volume.

(e)

0.120 mole HClO 4


0.120 M HClO 4 2.00 L = 0.240 mole HClO 4
L
1.60 10 3 g reagent 60 g HClO 4 mole HClO 4 9.55 mole HClO 4
=
L reagent 100 g reagent 100.5 g L reagent
L reagent
vol. reagent = 0.240 mole HClO 4 = 0.025 L reagent
9.55 mole HClO 4

Dilute 25 mL HClO4 reagent in enough water to yield 2.00 L total volume.

(f)

60 mg Na +
+
60.0 ppm Na 9.00 L soln = 5.40 10 2 mg Na +
L soln
g mole Na + mole Na 2SO 4 142.0 g Na 2SO 4
5.4 10 2 mg Na + = 1.67 g Na 2SO 4
1000 mg 22.99 g 2 moles Na + mole

Dissolve 1.67 g Na2SO4 in water and bring to 9.00 L total volume.


Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

13-9 (a)

0.150 mole KMnO 4


0.150 M KMnO 4 1.00 L = 0.150 mole KMnO 4
L
158.03 g KMnO 4
0.150 mole KMnO 4 = 23.7 g KMnO 4
mole

Dissolve 23.7 g KMnO4 in water and bring to 1.00 L total volume.

(b)

0.500 mole HClO 4


0.500 M HClO 4 2.50 L = 1.25 mole HClO 4
L
L
1.25 mole HClO 4 = 0.139 L HClO 4 reagent
9.00 mole HClO 4

Dilute 139 mL HClO4 reagent in enough water to yield 2.50 L total volume.

(c)

0.0500 mole I L
0.0500 M I 400 mL = 0.0200 mole I
L 1000 mL
mole MgI 2 278.11 g MgI 2
0.0200 mole I = 2.78 g MgI 2
2 moles I mole

Dissolve 2.78 g MgI2 in water and bring to 400 mL total volume.

(d)

1.00 g CuSO 4 mole CuSO 4


1.00% ( w / v ) CuSO 4 200 mL = 0.0125 mole CuSO 4
100 mL 159.61 g
L
0.0125 mole CuSO 4 = 0.0575 L CuSO 4
0.218 mole CuSO 4

Dilute 57.5 mL of the 0.218 M CuSO4 solution to yield 200 mL total volume.
Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

(e)

0.215 mole NaOH


0.215 M NaOH 1.50 L = 0.3225 mole NaOH
L
1.525 10 3 g reagent 50 g NaOH mole NaOH 1.906 101 mole NaOH
=
L reagent 100 g reagent 40.00 g L reagent
L reagent
vol. reagent = 0.3225 mole NaOH = 0.0169 L reagent
1.906 101 mole NaOH

Dilute 16.9 mL of the concentrated reagent to 1.50 L total volume.

(f)

12 mg K +
12 ppm K + 1.50 L soln = 1.8 101 mg K +
L soln
g mole K + mole K 4 Fe(CN ) 6 368.3 g K 4 Fe(CN ) 6
1.8 101 mg K +
1000 mg 39.10 g 4 moles K + mole
= 0.0424 g K 4 Fe(CN ) 6

Dissolve 42.4 mg K4Fe(CN)6 in water and bring to 1.50 L total volume.

g
13-10 M HgO = 216.59
mole

2
HgO( s ) + 4 Br + H 2 O

HgBr4 + 2OH

1 mole HgO 2 mole OH 1 mole HClO 4 1000 mmol HClO 4


0.4125 g HgO
216.59 g mole HgO 1 mole OH mole
46.51 mL
= 0.08190 M HClO 4
Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

g
13-11 M Na 2CO3 = 105.99
mole

2
CO 3 + 2H +

H 2 O + CO 2 ( g )

1 mole Na 2 CO 3 2 mole H + 1 mole H 2SO 4 1000 mmol H 2SO 4


0.4512 g Na 2 CO 3
105.99 g mole Na 2 CO 3 2 mole H + mole
36.44 mL
= 0.1168 M H 2SO 4

g
13-12 M Na 2SO4 = 142.04
mole

2
Ba 2+ + SO 4 BaSO 4 ( s )
96.4 g Na 2SO 4 1 mole Na 2SO 4 1 mole BaCl 2 1000 mmol
0.4000 g sample
100 g sample 142.04 g 1 mole Na 2SO 4 mole
41.25 mL
= 0.06581 M BaCl 2

13-13 (Note: In the first printing of the text, the answer in the back of the book was in error.)

VHClO4 27.43 mL HClO 4 mL HClO 4


= = 1.0972
VNaOH 25.00 mL NaOH mL NaOH

The volume of HClO4 required to titrate 0.3125 g Na2CO3 is

1.0972 mL HClO 4
40.00 mL HClO 4 10.12 mL NaOH = 28.896 mL HClO 4
mL NaOH
Thus,
0.3125 g Na 2 CO 3 1 mole Na 2 CO 3 2 mole HClO 4 1000 mmol
= 0.2041 M HClO 4
28.896 mL HClO 4 105.99 g 1 mole Na 2 CO 3 mole
and
VHClO4
c NaOH = c HClO4
VNaOH
0.2041 mole HClO 4 1.0972 mL HClO 4 1 mole NaOH
= 0.2041 M = 0.2239 M NaOH
L mL NaOH mole HClO 4
Fundamentals of Analytical Chemistry: 8th ed. Chapter 13


13-14 2 MnO 4 + 5H 2 C 2 O 4 + 6H +

2 Mn 2+ + 10CO 2 ( g ) + 8H 2 O

0.05251 mole Na 2 C 2 O 4 L 2 mole KMnO 4 1000 mmol


50.00 mL Na 2 C 2 O 4
L 1000 mL 5 mole Na 2 C 2 O 4 mole
36.75 mL
= 0.02858 M KMnO 4

g
13-15 M KIO3 = 214.00
mole


IO 3 + 5I + 6 H + 3I 2 + 3H 2 O

2 2
I 2 + 2S 2 O 3 2I + S 4 O 6

1 mole KIO 3 3 mole I 2 2 mole Na 2S 2 O 3 1000 mmol


0.1045 g KIO 3
214.00 g 1 mole KIO 3 1 mole I 2 mole
30.72 mL
= 0.09537 M Na 2S 2 O 3

13-16

ClCH 2 COOH + Ag + + H 2 O HOCH 2 COOH + H + + AgCl( s )


The unreacted Ag + is titrated with NH 4SCN,
+
Ag + + NH 4SCN NH 4 + AgSCN( s )

0.04521 mole AgNO 3 L 1 mole NH 4SCN 1000 mmol


50.00 mL
L 1000 mL 1 mole AgNO 3 mole
22.98 mL
= 0.098368 M NH 4SCN
Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

0.098368 mmol NH 4SCN


mmol NH 4SCN = 10.43 mL = 1.02598 mmol NH 4SCN
mL
0.04521 mmol
mmol AgCl(s) precipitated = 50.00 mL 1.02598 mmol
mL
= 1.2345 mmol AgCl
1 mole ClCH 2 COOH 94.50 g 1000 mg
1.2345 10 3 mole AgCl
1 mole AgCl mole g
= 116.7 mg ClCH 2 COOH

13-17


BH 4 + 8Ag + + 8OH H 2 BO 3 + 8Ag( s ) + 5H 2 O
Ag + + SCN AgSCN( s )

mmol excess Ag+ equals mmol KSCN,

0.0397 mmol KSCN 1 mmol Ag +


mmol excess Ag + = 3.36 mL = 0.133 mmol Ag +
mL 1 mmol KSCN
0.2221 mmol AgNO 3
mmol AgNO 3 = 50.00 mL = 1.11 101 mmol AgNO 3
mL
reacted mmol Ag = (1.11 101 0.133)mmol = 1.10 101 mmol Ag +
+


1.10 101 mmol Ag + 1 mmol BH 4
+
= 0.0138 M BH 4
100 mL 8 mmol Ag

0.0138 mole BH 4 L 1 mole KBH 4 53.941 g KBH 4
500 mL
= 0.371 g KBH 4
L 1000 mL 1 mole BH 4 mole
0.371 g KBH 4
% purity KBH 4 = 100% = 11.5%
3.213 g material
Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

13-18 H 3 AsO 4 + 3Ag + 3H + + Ag 3 AsO 4 ( s )

mmol excess Ag + equals mmol KSCN,


0.1000 mmol KSCN 1 mmol Ag +
mmol excess Ag + = 10.76 mL = 1.0760 mmol Ag +
mL 1 mmol KSCN
0.06222 mmol AgNO 3
mmol AgNO 3 added = 40.00 mL = 2.4888 mmol AgNO 3
mL

mmol Ag + reacted = ( 2.4888 1.0760) mmol = 1.4128 mmol Ag +


% As 2 O 3 in sample =
1 mmol Ag 3 AsO 4 1 mmol As 2 O 3 197.84 g As 2 O 3
1.4128 mmol Ag +
3 mmol Ag +
2 mmol Ag 3 AsO 4 1000 mmol
100
1.010 g sample
= 4.612% As 2 O 3

g
13-19 M C10 H 5Cl7 = 373.32
mole

The stoichiometry of the titration of heptachlor must be one to one (i.e., one chlorine

reacts with one silver nitrate) for the calculation,

% heptachlor =
(mL Ag cAg mLSCN cSCN ) 37.33
, to be true. The factor 37.33 (with
mass sample

g
unwritten units of ) found in the numerator is derived from the equation below,
mmol

g no.mmol C10 H 5Cl 7 373.32 g C10 H 5Cl 7


37.33 = 100
mmol no.mmol AgNO3 1000 mmol

Thus,

g
37.33 1000 mmol
no.mmol C10 H 5Cl 7 mmol
= = 1.00
no.mmol AgNO3 373.32 g C10 H 5Cl 7 100

confirming that only one of the chlorines in the heptachlor reacts with the AgNO3.
Fundamentals of Analytical Chemistry: 8th ed. Chapter 13


13-20 Bi 3+ + H 2 PO 4 BiPO 4 ( s ) + 2 H +

0.03369 mmol NaH 2 PO 4


mol NaH 2 PO 4 = 27.36 mL = 0.921758 mol NaH 2 PO 4
mL
1 mmol Bi 3+
mol Bi 3+ = 0.921758 mol NaH 2 PO 4 = 0.921758 mol Bi 3+
1 mmol NaH 2 PO 4
% purity eulytite =
1 mmol 2 Bi 2 O 3 3SiO 2 1112 g 2 Bi 2 O 3 3SiO 2
0.921758 mol Bi 3+
4 mmol Bi 3+ 1000 mmol 100%
0.6423 g sample
= 39.90% eulytite

13-21 (a)

molarity of Ba (OH ) 2 =
1 mole C 6 H 5COOH 1 mole Ba (OH ) 2 1000 mmol
0.1175 g C 6 H 5COOH
122.12 g 2 mole C 6 H 5COOH mole
40.42 mL
= 0.01190 M Ba (OH ) 2

(b)

0.0002 0.03
2 2
2 5
s y = (1.190 10 M ) + = 2.2 10 M
0.1175 40.42

molarity of Ba(OH)2 taking into account the uncertainty of the two measurements can be

written 0.01190(0.00002) M.

(c) Weighing error of -0.0003g results in an absolute error, E, in the molarity calculation,

E=

(0.1175 0.0003) g C 6 H 5COOH
1 mole C 6 H 5COOH 1 mole Ba (OH ) 2 1000 mmol

122.12 g 2 mole C 6 H 5COOH mole
40.42 mL


1.190 10 2 M = (1.187 10 2 M ) (1.190 10 2 M ) = 2.826 10 5 M or 3.0 10 5 M
Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

The relative error, Er, in the molarity calculation resulting from this weighing error is

Er =
( 3.0 10M) 5
= 3.0 10 3 or 3 ppt
2
1.190 10 M

13-22

w / v percentage HOAc =
0.1475 mmol Ba (OH ) 2 2 mmol HOAc 60.05 g HOAc
43.17 mL
mL 1 mmol Ba (OH ) 2 1000 mmol
100%
50.00 mL
= 1.529% HOAc

Similar calculations for samples 2 to 4 yield the results shown in the spreadsheet that

follows,

(a)

x w / v percentage HOAc =
x i
=
6.1134
= 1.528% HOAc
4 4

(b)

( x i ) 2 (6.1134) 2
xi
2

4
9.34351132
4
s= = = 5.71 10 3 % HOAc
3 3

(c)

ts 2.35 (5.63 10 3 )
CI 90% = x = 1.528 = 1.528( 0.007)% HOAc
4 2

(d) The values of 1.5352 and 1.5213 can be considered for rejection. Applying the Q

test we find, that both results are less than Qexpt = 0.765, so neither value should be

rejected.

( w / v )% HOAc V
(e) =
( w / v )% HOAc V
Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

V HOAc 0.05 mL
For sample 1, = = 0.001
V HOAc 50.00 mL

The results for the remaining samples are found in the following spreadsheet.

mean relative systematic error =


x = 0.005 = 0.00125
n 4

For the mean ( w / v ) percent HOAc, ( w / v )% HOAc =


0.00125 1.528 = 1.91 10 3 % or 2 10 3% HOAc

A B C D E F G
1 Problem 13-22
2
3 Conc. Ba(OH)2 0.1475
4 MW HOAc 60.05
5 t 2.35
6
2
7 Sample Sample Vol, mL Ba(OH)2 Vol, mL w/v % HOAc xi xi V/V
8 1 50.00 43.17 1.529 1.52949152 2.33934429 -0.001
9 2 49.50 42.68 1.527 1.52740511 2.33296637 -0.001
10 3 25.00 21.47 1.521 1.52134273 2.31448370 -0.002
11 4 50.00 43.33 1.535 1.53516024 2.35671695 -0.001
12
13 (xi) 6.11339959
(xi )
2
14 9.34351132
15 (a) mean xi 1.528
16 (b) std. dev. % HOAc 5.71E-03
17 (c) CI90%(t=2.35) 6.70E-03
18 (d) Q(expt 1.535-1.521) 0.41
19 Q(expt 1.527-1.521) 0.44
20 (e) (V/V) -0.005
21 mean relative systematic error -1.25E-03
22 mean (w/v) % HOAc -1.91E-03
23 Spreadsheet Documentation
24 D8 = (($B$3*C8*2*$B$4/1000)/B8)*100 C16 = SQRT((B14-(B13)^2/4)/3)
25 E8 = D8 C18 = (D11-D8)/(D11-D10)
26 F8 = E8^2 C19 = (D9-D10)/(D11-D10)
27 G8 = -0.05/B8 C20 = SUM(G8:G11)
28 B13 = SUM(E8:E11) C21 = C20/4
29 B14 = SUM(F8:F11) C22 = C21*C15
30 C15 = B13/4
Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

13-23

0.08181 mmol AgNO 3


no. mmol AgNO 3 consumed by sample = 20.00 mL
mL
0.04124 mmol KSCN 1 mmol AgNO 3
2.81 mL = 1.5204 mmol AgNO 3
mL 1 mmol KSCN

mg saccharin / tablet =
1 mmol saccharin 205.17 g saccharin 1000 mg
1.5204 mmol AgNO 3
1 mmol AgNO 3 1000 mmol g
20 tablets
mg saccharin
= 15.60
tablet

13-24 (a)

1 mole AgNO 3 1 mole Ag + 1000 mmol


0.1752 g AgNO 3
169.87 g 1 mole AgNO 3 mole
weight molarity Ag + =
502.3 mL
= 2.0533 10 3

(b)

2.0533 10 3 mole AgNO 3 1000 mmol


23.765 mL
1000 mL mole
weight molarity KSCN =
25.171 mL
= 1.9386 10 3

g
(c) M BaCl2 2 H 2O = 244.26
mole

2.0533 10 3 mmol AgNO 3


mmol AgNO 3 consumed = 20.102 mL
mL
1.9386 10 3 mmol KSCN 1 mmol AgNO 3
7.543 mL
mL 1 mmol KSCN
= 0.026653 mmol
Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

1 mmol BaCl 2 2 H 2 O 244.26 g


0.026653 mmol AgNO 3
2 mmol AgNO 3 1000 mmol
% BaCl 2 2 H 2 O = 100%
0.7120 g sample
= 0.4572%

13-25 (a)

1 mole KCl MgCl 2 6H 2 O


10.12 g KCl MgCl 2 6H 2 O
277.85 g
= 0.01821 M KCl MgCl 2 6H 2 O
2.000 L
(b) [Mg ] = [KCl MgCl
2+
2 6H 6 O] = 0.01821 M Mg 2+

(c)

3 mole Cl
[Cl ] = 0.01821 mole KCl MgCl

2 6H 2 O
1 mole KCl MgCl 2 6H 2 O
= 0.05463 M Cl

(d)

10.12 g L
( w / v )% KCl MgCl 2 6H 2 O = 100% = 0.506%
2.000 L 1000 mL

(e)

0.05463 mmol Cl
25.0 mL = 1.37 mmol Cl
mL

(f)

0.01821 mole KCl MgCl 2 6H 2 O 1 mole K + 39.10 g K + 1000 mg



L 1 mole KCl MgCl 2 6H 2 O 1 mole g
= 712.0 ppm K +
Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

g
13-26 M CH 2O = 30.03
mole

0.121 mmol KCN


mmol CH 2 O = mmol KCN reacted = 30.0 mL
mL
0.100 mmol AgNO 3 0.134 mmol NH 4SCN
40.0 mL 16.1 mL = 1.787 mmol CH 2 O
mL mL
30.03 g CH 2 O
1.787 mmol CH 2 O
1000 mmol
100% = 21.5% CH 2 O
25.0 mL
5.00 g sample
500 mL

g
13-27 M C19 H16O4 = 308.34
mole

0.02979 mmol AgNO 3


mmol AgNO 3 reacted = 25.00 mL
mL
0.05411 mmol KSCN
2.85 mL = 0.5905 mmol AgNO 3
mL
1 mmol CHI 3
mmol C19 H 16 O 4 = 0.5905 mmol AgNO 3
3 mmol AgNO 3
1 mmol C19 H 16 O 4
= 0.1968 mmol C19 H 16 O 4
1 mmol CHI 3
308.34 g C19 H 16 O 4
0.1968 mmol C19 H 16 O 4
1000 mmol 100% = 0.4348% C H O
19 16 4
13.96 g sample
Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

13-28

+
AgNO 3 + 2 NH 3 Ag( NH 3 ) 2 + NO 3
+ +
6Ag( NH 3 ) 2 + 3Se( s ) + 3H 2 O 2Ag 2Se( s ) + Ag 2SeO 3 ( s ) + 6 NH 4

0.0360 mmol AgNO 3


mmol AgNO 3 reacted to form Ag 2Se( s ) = 25.00 mL
mL
0.01370 mmol KSCN
16.74 mL = 0.6707 mmol AgNO 3
mL
+
1 mmol Ag( NH 3 ) 2
mmol Se from Ag 2Se( s ) = 0.6707 mmol AgNO 3
1 mmol AgNO 3
1 mmol Ag 2Se( s ) 3 mmol Se( s )
+
= 0.503 mmol Se
2 mmol Ag( NH 3 ) 2 2 mmol Ag 2Se( s )
78.96 mg Se
0.503 mmol Se
mmol
= 7.94 mg Se / mL sample
5.00 mL

13-29

0.08551 mmol AgNO 3 1 mmol Cl


mmol Cl = 13.97 g = 1.195 mmol Cl
mL 1 mmol AgNO 3

0.08551 mmol AgNO 3 1 mmol ClO 4
mmol ClO 4 = ( 40.12 mL 13.97 mL)
mL 1 mmol AgNO 3

= 2.236 mmol ClO 4
35.453 g Cl
1.195 mmol Cl
%Cl = 100% = 10.60% Cl
1000 mmol
50.00 mL
1.998 g sample
250.0 mL
99.45 g ClO 4
2.236 mmol ClO 4
1000 mmol
%ClO 4 = 100% = 55.65% ClO 4
50.00 mL
1.998 g sample
250.0 mL
Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

13-30 (a) The equivalence point occurs at 50.0 mL,

0.05000 mmol AgNO 3


mmol Ag + = 25.00 mL = 1.250 mmol Ag +
mL
1 mmol NH 4SCN 1 mL
mL SCN = 1.250 mmol Ag + +
= 50.00 mL
1 mmol Ag 0.02500 mmol NH 4SCN

At 30.00 mL,

(1.250 mmol Ag ) 0.0250 mmol



+ SCN
30.00 mL
[ Ag + ] = mL = 9.09 10 3 M Ag +
(25.00 mL + 30.00 mL)
pAg = log(9.09 10 3 ) = 2.04
[SCN ] = K sp / 9.09 10 3 = 1.1 10 12 / 9.09 10 3 = 1.2 10 10 M SCN

Proceeding in the same way, we obtain the data for 40.00 mL and 49.00 mL. The results

are displayed in the spreadsheet at the end of the solution.

At 50.00 mL,

[ Ag + ] = [SCN ] = K sp = 1.1 10 12 = 1.05 10 6 M


pAg = log(1.05 10 6 ) = 5.98

At 51.00 mL,

0.0250 mmol SCN


51.00 mL 1.250 mmol
[SCN ] =
mL
= 3.29 10 4 M
(51.00 mL + 25.00 mL)
[ Ag + ] = 1.1 10 12 / 3.29 10 4 = 3.3 10 9 M
pAg = log(3.3 10 9 ) = 8.48

At 60.00 mL and 70.00 mL, pAg is calculated in the same way and the results are

displayed in the spreadsheet below.


Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

A B C D E F
1 Problem 13-30(a)
2 The equivalence point occurs at 0.05000 mmol/mL X
-
3 Conc. AgNO3 0.05000 25.00 mL X (1 mL/0.02500 mmol) = 50.00 mL SCN

4 Vol. AgNO3 25.00


5 Conc. KSCN 0.02500
6 Ksp 1.10E-12
- + -
7 Vol. SCN [Ag ] [SCN ] pAg
8 30.00 9.09E-03 1.21E-10 2.041
9 40.00 3.85E-03 2.86E-10 2.415
10 49.00 3.38E-04 3.26E-09 3.471
11 50.00 1.05E-06 1.05E-06 5.979
12 51.00 3.34E-09 3.29E-04 8.48
13 60.00 3.74E-10 2.94E-03 9.43
14 70.00 2.09E-10 5.26E-03 9.68
15
16 Spreadsheet Documentation
17 B8=(($B$3*$B$4)-($B$5*A8))/($B$4+A8) C8=$B$6/B8
18 B11=SQRT($B$6) C12=(($B$5*A12)-($B$3*$B$4))/($B$4+A12)
19 B12=$B$6/C12 D8 = -LOG(B8)
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

(b) Proceeding as in part (a), we obtain the results in the spreadsheet below.

A B C D E F
1 Problem 13-30(b)
2 The equivalence point occurs at 0.06000 mmol/mL X
-
3 Conc. AgNO3 0.06000 20.00 mL X (1 mL/0.03000 mmol) = 40.00 mL I

4 Vol. AgNO3 20.00


5 Conc. KI 0.03000
6 Ksp 8.30E-17
- + -
7 Vol. I [Ag ] [I ] pAg
8 20.00 1.50E-02 5.53E-15 1.824
9 30.00 6.00E-03 1.38E-14 2.222
10 39.00 5.08E-04 1.63E-13 3.294
11 40.00 9.11E-09 9.11E-09 8.04
12 41.00 1.69E-13 4.92E-04 12.77
13 50.00 1.94E-14 4.29E-03 13.71
14 60.00 1.11E-14 7.50E-03 13.96
15
16 Spreadsheet Documentation
17 B8=(($B$3*$B$4)-($B$5*A8))/($B$4+A8) C8=$B$6/B8
18 B11=SQRT($B$6) C12=(($B$5*A12)-($B$3*$B$4))/($B$4+A12)
19 B12=$B$6/C12 D8 = -LOG(B8)
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

(c) Proceeding as in part (a), we obtain the results in the spreadsheet below.

A B C D E F
1 Problem 13-30(c)
2 The equivalence point occurs at 0.07500 mmol/mL X
-
3 Conc. AgNO3 0.07500 30.00 mL X (1 mL/0.07500 mmol) = 30.00 mL CI

4 Vol. AgNO3 30.00


5 Conc. NaCl 0.07500
6 Ksp 1.82E-10
- + -
7 Vol. CI [Ag ] [CI ] pAg
8 10.00 3.75E-02 4.85E-09 1.426
9 20.00 1.50E-02 1.21E-08 1.824
10 29.00 1.27E-03 1.43E-07 2.896
11 30.00 1.35E-05 1.35E-05 4.87
12 31.00 1.48E-07 1.23E-03 6.83
13 40.00 1.70E-08 1.07E-02 7.77
14 50.00 9.71E-09 1.88E-02 8.01
15
16 Spreadsheet Documentation
17 B8=(($B$3*$B$4)-($B$5*A8))/($B$4+A8) C8=$B$6/B8
18 B11=SQRT($B$6) C12=(($B$5*A12)-($B$3*$B$4))/($B$4+A12)
19 B12=$B$6/C12 D8 = -LOG(B8)
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

(d) The equivalence point occurs at 70.00 mL,

2 0.4000 mmol Na 2SO 4 2


mmol SO 4 = 35.00 mL = 1.400 101 mmol SO 4
mL
2 mL
mL Pb 2+ = 1.400 101 mmol SO 4 = 70.00 mL Pb( NO 3 ) 2
0.2000 mmol Pb( NO 3 ) 2

At 50.00 mL,

(1.400 10 mmol) 0.2000 mmol


1 Pb( NO ) 3 2
50.00 mL
2
[SO 4 ] = mL = 4.706 10 2 M SO 2
(35.00 mL + 50.00 mL)
4

[ Pb 2+ ] = 1.6 10 8 / 4.706 10 2 = 3.4 10 7 M Pb 2+


pPb = log(3.4 10 7 ) = 6.47

At 60.00 mL and 69.00 mL, the calculations are made in the same way and the results

are shown in the following spreadsheet.

At 70.00 mL,

2
[ Pb 2+ ] = [SO 4 ] = K sp = 1.6 10 8 = 1.3 10 4 M Pb 2+
pPb = log(1.3 10 4 ) = 3.90

At 71.00 mL,

0.2000 mmol Pb( NO 3 ) 2 2


71.00 mL 1.400 101 mmol SO 4
[ Pb 2+ ] =
mL
= 1.887 10 3 M Pb 2+
(35.00 mL + 71.00 mL)
2 2
[SO 4 ] = 1.6 10 8 / 1.887 10 3 = 8.5 10 6 M SO 4
pPb = log(1.887 10 3 ) = 2.7243

At 80.00 mL and 90.00 mL, the calculations are made in the same way and the results

are shown in spreadsheet below.


Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

A B C D E F
1 Problem 13-30(d)
2 The equivalence point occurs at 0.4000 mmol/mL X
2+
3 Conc. Na2SO4 0.4000 35.00 mL X (1 mL/0.2000 mmol) = 70.00 mL Pb

4 Vol. Na2SO4 35.00


5 Conc. Pb(NO3)2 0.2000
6 Ksp 1.60E-08
2+ 2- 2+
7 Vol. Pb [SO4 ] [Pb ] pPb
8 50.00 4.71E-02 3.40E-07 6.469
9 60.00 2.11E-02 7.60E-07 6.119
10 69.00 1.92E-03 8.32E-06 5.080
11 70.00 1.26E-04 1.26E-04 3.898
12 71.00 8.48E-06 1.89E-03 2.724
13 80.00 9.20E-07 1.74E-02 1.760
14 90.00 5.00E-07 3.20E-02 1.495
15
16 Spreadsheet Documentation
17 B8=(($B$3*$B$4)-($B$5*A8))/($B$4+A8) C8=$B$6/B8
18 B11=SQRT($B$6) C12=(($B$5*A12)-($B$3*$B$4))/($B$4+A12)
19 B12=$B$6/C12 D8 = -LOG(D8)
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

(e) Proceeding as in part (a), we obtain the results in the spreadsheet below.

A B C D E F
1 Problem 13-30(e)
2 The equivalence point occurs at 0.02500 mmol/mL X
2-
3 Conc. BaCl2 0.0250 40.00 mL X (1 mL/0.05000 mmol) = 20.00 mL SO4

4 Vol. BaCl2 40.00


5 Conc. Na2SO4 0.0500
6 Ksp 1.10E-10
2- 2+ 2-
7 Vol. SO4 [Ba ] [SO4 ] pBa
8 0.00 2.50E-02 1.602
9 10.00 1.00E-02 1.10E-08 2.000
10 19.00 8.47E-04 1.30E-07 3.072
11 20.00 1.05E-05 1.05E-05 4.979
12 21.00 1.34E-07 8.20E-04 6.872
13 30.00 1.54E-08 7.14E-03 7.812
14 40.00 8.80E-09 1.25E-02 8.056
15
16 Spreadsheet Documentation
17 B8=(($B$3*$B$4)-($B$5*A8))/($B$4+A8) C8=$B$6/B8
18 B11=SQRT($B$6) C12=(($B$5*A12)-($B$3*$B$4))/($B$4+A12)
19 B12=$B$6/C12 D8 = -LOG(B8)
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

(f) Proceeding as in part (d), we obtain the results in the spreadsheet below.

A B C D E F
1 Problem 13-30(f)
2 The equivalence point occurs at 0.2000 mmol/mL X
-
3 Conc. NaI 0.2000 50.00 mL X (1 mL/0.4000 mmol) = 25.00 mL Tl
4 Vol. NaI 50.00
5 Conc. TlNO3 0.4000
6 Ksp 6.50E-08
+ - +
7 Vol. Tl [I ] [Tl ] pTl
8 5.00 1.45E-01 4.47E-07 6.350
9 15.00 6.15E-02 1.06E-06 5.976
10 24.00 5.41E-03 1.20E-05 4.920
11 25.00 2.55E-04 2.55E-04 3.594
12 26.00 1.24E-05 5.26E-03 2.279
13 35.00 1.38E-06 4.71E-02 1.327
14 45.00 7.72E-07 8.42E-02 1.075
15
16 Spreadsheet Documentation
17 B8=(($B$3*$B$4)-($B$5*A8))/($B$4+A8) C8=$B$6/B8
18 B11=SQRT($B$6) C12=(($B$5*A12)-($B$3*$B$4))/($B$4+A12)
19 B12=$B$6/C12 D8 = -LOG(C8)
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36

13-31 (Note: In the first printing of the text, the last answer for pAg in the back of the book was

in error.)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

0.0400 mmol KBr


mmol KBr = 50.0 mL = 2.00 mmol KBr
mL

At 5.00 mL,

0.0500 mmol AgNO 3


2.00 mmol 5.00 mL
[ Br ] = mL = 3.18 10 2 M
(50.0 mL + 5.00 mL)
[ Ag + ] = K sp /[ Br ] = 5.0 10 13 / 3.18 10 2 = 1.6 10 11 M Ag +
pAg = log(1.6 10 11 ) = 10.80

At 15.00 mL, 25.00 mL, 30.00 mL, 35.00 mL and 39.00 mL, the calculations are

performed in the same way and the results are shown in the spreadsheet at the end of this

solution.

At 40.00 mL,

[ Ag + ] = [ Br ] = K sp = 5.0 10 13 = 7.1 10 7 M Ag +
pAg = log(7.1 10 7 ) = 6.15

At 41.00 mL,

0.0500 mmol AgNO 3


41.00 mL 2.00 mmol Br
[ Ag + ] =
mL
= 5.49 10 4 M Ag +
(50.0 mL + 41.00 mL)
pAg = log(5.49 10 4 ) = 3.260

At 45.00 mL and 50.00 mL, the calculations are performed in the same way and the

results are shown in the spreadsheet that follows.


Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

A B C D E F
1 Problem 13-31
2 The equivalence point occurs at 0.04000 mmol/mL X
+
3 Conc. AgNO3 0.05000 50.00 mL X (1 mL/0.05000 mmol) = 40.00 mL Ag

4 Vol. KBr 50.00


5 Conc. KBr 0.04000
6 Ksp 5.00E-13
+ - +
7 Vol. Ag [Br ] [Ag ] pAg
8 5.00 3.18E-02 1.57E-11 10.804
9 15.00 1.92E-02 2.60E-11 10.585
10 25.00 1.00E-02 5.00E-11 10.301
11 30.00 6.25E-03 8.00E-11 10.097
12 35.00 2.94E-03 1.70E-10 9.770
13 39.00 5.62E-04 8.90E-10 9.051
14 40.00 7.07E-07 7.07E-07 6.151
15 41.00 7.28E+01 5.49E-04 3.260
16 45.00 1.52E+01 2.63E-03 2.580
17 50.00 8.00E+00 5.00E-03 2.301
18
19 Spreadsheet Documentation
20 B8=(($B$5*$B$4)-($B$3*A8))/($B$4+A8) C8=$B$6/B8
21 B14=SQRT($B$6) C15=(($B$3*A15)-($B$4*$B$5))/($B$4+A15)
22 B15=$B$6/C15 D8 = -LOG(C8)
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

Challenge Problem

[ Fe(SCN ) 2+ ]
Fe 3+ + SCN
Fe(SCN ) 2+ K f = 1.05 10 3 =

[ Fe 3+ ][SCN ]

For part (a) we find,

0.250 g
mass Ag = 0.250% 50.00 mL = 0.125 g Ag
100 mL
1 mol Ag
mol Ag = 0.125 g Ag = 1.1588 10 3 mol Ag
107.8682 g
1 mol SCN L
L SCN = 1.1588 10 3 mol Ag = 4.6353 10 2 L SCN
mol Ag 0.025 mol
1 10 5
cFe ( SCN )2+ = = 9.759 10 5
1.05 10 3

9.759 10 5 mol Fe(SCN ) 2+ L


mol Fe(SCN ) 2+ = 50.00 mL + 4.6353 10 2 L
L 1000 mL
6 2+
= 9.4030 10 mol Fe(SCN )
6 1 mol SCN
2+ 1 mol Ag
9.4030 10 mol Fe(SCN ) 2+

mol Fe(SCN ) mol SCN
% Error = = 100% = 0.81%
1.1588 10 3 mol Ag

Proceeding the same way for parts (b) and (c), we find the results in the following spreadsheet.
Fundamentals of Analytical Chemistry: 8th ed. Chapter 13

A B C D E F G
1 Problem 13-32
2
3 mL taken 50
4 Kf 1.05E+03
5 conc SCN 0.025
6 AW Ag 107.8682
7 min complx 1.00E-05
-
8 %Ag g Ag moles Ag L SCN c SCN cmplx mol SCN cmplx %Error
9 (a) 0.25 0.125 0.0011588 0.046353 9.759E-05 9.40308E-06 0.811434
10 (b) 0.1 0.05 0.0004635 0.018541 9.759E-05 6.68893E-06 1.443046
11 (c) 0.05 0.025 0.0002318 0.009271 9.759E-05 5.78422E-06 2.495732
12
13 Spreadsheet Documentation
14 B9=$B$3*(A9/100) E9=SQRT($B$7/$B$4)
15 C9=B9/$B$6 F9=E9*(($B$3/1000)+D9)
16 D9=C9/$B$5 G9=F9/C9*100
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 = = 9.1 10 9 Thus, NaOCl
1.1 10 6

1.00 10 14
(b) For NH3, Kb = 10
= 1.75 10 5
5.7 10

1.00 10 14
For sodium phenolate, K b = = 1.00 10 4 Thus, sodium phenolate
1.00 10 10

(c) For hydroxyl amine Kb = 9.110-9 (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 = = 1.6 10 3 Thus, NaCN
6.2 10 10

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

(a) For nitrous acid Ka = 7.110-4

For iodic acid Ka = 1.710-1 Thus, iodic acid

(b) For anilinium Ka = 2.5110-5

For benzoic acid Ka = 6.2810-5 Thus, benzoic acid

(c) For hypochlorous acid Ka = 3.010-8

For pyruvic acid Ka = 3.210-3 Thus, pyruvic acid

(d) For salicylic acid Ka = 1.0610-3

For acetic acid Ka = 1.7510-5 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) = 7.9410-8

[HIn]/[In-] = 1.43

Substituting these values into the equilibrium expression and rearranging gives

[H3O+] = 7.9410-81.43 = 1.1310-7

pH = -log(1.1310-7) = 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) = 3.4710-4

[InH+]/[In] = 1.64

Substituting these values into the equilibrium expression and rearranging gives

[H3O+] = 3.4710-41.64 = 5.6910-4

pH = -log(5.6910-4) = 3.24

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

At 0oC, pH = - log(1.1410-15) = 7.47

At 50oC, pH = - log(5.4710-14) = 6.63

At 100oC, pH = - log(4.910-13) = 6.16


Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

14-11 At 0oC, pKw = -log(1.1410-15) = 14.94

At 50oC, pKw = -log(5.4710-14) = 13.26

At 100oC, pKw = -log(4.910-13) = 12.31

14-12 pH + pOH = pKw and pOH = -log[OH-] = -log(1.0010-2) = 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-] = 2.0010-8 + [H3O+] = 2.0010-8 +
[OH - ]

[OH-]2 2.0010-8[OH-] 1.0010-14 = 0

[OH-] = 1.10510-7

pOH = -log 1.10510-7 = 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

1.00 10 14
[H3O+] = 2.0010-8 + [OH-] = 2.0010-8 +
[H 3 O + ]

[H3O+]2 2.0010-8[H3O+] 1.0010-14 = 0

[H3O+] = 1.10510-7 and pH = -log 1.10510-7 = 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 = (75.00.0600 1.7492)/75.0 = 0.01366 M

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

(b) 15.00.0600 = 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 = 7.110-12 = [Mg2+][OH-]2

[OH-] = (7.110-12/0.0300)1/2 = 1.5410-5

pH = 14.00 - (-log(1.5410-5)) = 9.19

(c) 30.000.0600 = 1.80 mmol HCl added, which forms 0.90 mmol Mg2+.

[Mg2+] = 0.90/30.0 = 3.0010-2

[OH-] = (7.110-12/0.0300)1/2 = 1.5410-5

pH = 14.00 - (-log(1.5410-5)) = 9.19

(d) [Mg2+] = 0.0600 M

[OH-] = (7.110-12/0.0600)1/2 = 1.0910-5

pH = 14.00 - (-log(1.0910-5)) = 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) = 1.55610-2 M

[H3O+] = 1.55610-2 M and pH = -log 1.55610-2 = 1.81

(d) As in part (c), cHCl = 1.55610-2 and pH = 1.81

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

(e) cNaOH = (25.0 0.232 4.00)/(45.0) = 4.0010-2 M

pOH = -log 4.0010-2 = 1.398 and pH = 14.00 1.398 = 12.60

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

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

H O + = 0.85 (Table 10-2)


3

a H O + = 0.860.0500 = 0.0425
3

pH = -log(0.043) = 1.37

14-20 (a) [OH-] = 20.0167 = 0.0334 M

pH = 14 (-log(0.0334)) = 12.52

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

OH = 0.81 (Table 10-2)

a OH = 0.810.0334 = 0.0271
Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

a OH a H O + = 1.0010-14
3

a H O + = 1.0010-14/0.0271 = 3.6910-13
3

pH = -log(3.6910-13) = 12.43

[H 3 O + ][OCl - ]
14-21 HOCl + H2O ' H3O+ + OCl- Ka = = 3.010-8
[HOCl]

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

[H3O+]2/(cHOCl [H3O+]) = 3.010-8

rearranging gives the quadratic: 0 = [H3O+]2 + 310-8[H3O+] - cHOCl3.010-8

cHOCl [H3O+] pH

(a) 0.100 5.47610-5 4.26

(b) 0.0100 1.73110-5 4.76

(c) 1.0010-4 1.71710-6 5.76

K w [HOCl][OH - ] 1.00 10 14
14-22 OCl- + H2O ' HOCl + OH- Kb = = = 8
= 3.33 10 7
Ka -
[OCl ] 3.0 10

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

[OH-]2/(cNaOCl -[OH-]) = 3.3310-7

rearranging gives the quadratic: 0 = [OH-]2 + 3.3310-7[OH-] - cNaOCl3.3310-7

cNaOCl [OH-] pOH pH

(a) 0.100 1.82310-4 3.74 10.26

(b) 0.0100 5.75410-5 4.24 9.76

(c) 1.0010-4 5.60610-6 5.25 8.75


Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

1.00 10 14
14-23 NH3 + H2O ' NH4+ + OH- Kb = = 1.75 10 5
5.7 10 10

[NH4+] = [OH-] and [NH3] = c NH 3 [OH-]

[OH-]2/( c NH3 -[OH-]) = 1.7510-5

rearranging gives the quadratic: 0 = [OH-]2 + 1.7510-5[OH-] - c NH3 1.7510-5

c NH3 [OH-] pOH pH

(a) 0.100 1.31410-3 2.88 11.12

(b) 0.0100 4.09710-4 3.39 10.62

(c) 1.0010-4 3.39910-5 4.47 9.53

14-24 NH4+ + H2O ' H3O+ + NH3 Ka = 5.710-10

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


4

[H3O+]2/( c NH + [H3O+]) = 5.710-10


4

rearranging gives the quadratic: 0 = [H3O+]2 + 5.710-10[H3O+] - c NH + 5.710-10


4

c NH + [H3O+] pH
4

(a) 0.100 7.55010-6 5.12

(b) 0.0100 2.38710-6 5.62

(c) 1.0010-4 1.38510-7 6.62

1.00 10 14
14-25 C5H11N + H2O ' C5H11NH+ + OH- Kb = = 1.333 10 3
7.5 10 12

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


Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

[OH-]2/( cC5H11N -[OH-]) = 1.33310-3

rearranging gives the quadratic: 0 = [OH-]2 + 1.33310-3[OH-] - cC5H11N 1.33310-3

cC5H11N [OH-] pOH pH

(a) 0.100 1.09010-2 1.96 12.04

(b) 0.0100 3.04510-3 2.52 11.48

(c) 1.0010-4 9.34510-5 4.03 9.97

14-26 HIO3 + H2O ' H3O+ + IO3- Ka = 1.710-1

[H3O+] = [IO3-] and [HIO3] = c HIO3 [H3O+]

[H3O+]2/( c HIO3 [H3O+]) = 1.710-1

rearranging gives the quadratic: 0 = [H3O+]2 + 1.710-1[H3O+] - c HIO3 1.710-1

c HIO3 [H3O+] pH

(a) 0.100 7.06410-2 1.15

(b) 0.0100 9.47210-3 2.02

(c) 1.0010-4 9.99410-5 4.00

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

HA + H2O ' H3O+ + A- Ka = 1.3810-4

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

[H3O+]2/(0.9547 [H3O+]) = 1.3810-4

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

(b) c HA = 0.954725.0/250.0 = 0.09547 M HA


Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

Proceeding as in part (a) we obtain: [H3O+] = 3.5610-3 and pH = 2.45

(c) c HA = 0.0954710.0/1000.0 = 9.54710-4 M HA

Proceeding as in part (a) we obtain: [H3O+] = 3.0010-4 and pH = 3.52

1 mmol HA 1
14-28 (a) c HA = 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) c HA = 0.0458310.0/100.0 = 0.004583 M HA

Proceeding as in part (a) we obtain: [H3O+] = 4.53510-3 and pH = 2.34

(c) c HA = 0.00458310.0/1000.0 = 4.58310-5 M HA

Proceeding as in part (a) we obtain: [H3O+] = 4.58310-5 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 = 1.8010-4

c HA = 4.00/45.0 = 8.8910-2

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

[H3O+]2/(0.0889 [H3O+]) = 1.8010-4

rearranging and solving the quadratic gives: [H3O+] = 3.9110-3 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 = 1.0010-14/(1.8010-4) = 5.5610-11

c A - = 4.00/45.0 = 8.8910-2

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

[OH-]2/(0.0889 [OH-]) = 5.5610-11

rearranging and solving the quadratic gives: [OH-] = 2.2210-6 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 = 2.2210-2

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 = 1.8010-4

[H3O+] = 1.44010-4 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

c NH3 = 4.00/60.0 = 6.6710-2

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

[OH-]2/(0.0667 [OH-]) = 1.7510-5

rearranging and solving the quadratic gives: [OH-] = 1.0710-3 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 = 5.710-10

c NH + = 4.00/60.0 = 6.6710-2
4

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

[H3O+]2/(0.0667 [H3O+]) = 5.710-10

rearranging and solving the quadratic gives: [H3O+] = 6.1610-6 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 = 1.6710-2

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 = 5.7010-10

[H3O+] = 5.7010-10 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 = 5.7010-10

[H3O+] = 5.7010-10 and pH = 9.24

+ + -5 [H 3 O + ][NH 3 ]
14-31 (a) NH4 + H2O ' H3O + NH3 5.7010 =
[ NH +4 ]

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

[H3O+] = 5.7010-10 0.0500/0.0300 = 9.5010-10


Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

[OH-] = 1.0010-14/9.5010-10 = 1.0510-5

pH = -log (9.5010-10) = 9.022

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

From Table 10-2 NH + = 0.80 and NH 3 = 1.0


4

K a NH + [ NH 4+ ] 5.70 10 5 0.80 0.0500


aH O+ = 4
= = 7.6010-10
3
NH 3 [ NH 3 ] 1.00 0.0300

pH = -log (7.6010-10) = 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+] = 1.3810-40.1021/0.0995 = 1.41610-4

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

pH = -log (1.41610-4) = 3.85

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

[H3O+] = 1.7510-50.0550/0.0110 = 8.7510-5

pH = -log (8.7510-5) = 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 = 3.21410-2 M

cNaA = 5.65/500 = 1.13010-2 M

[H3O+] = 1.0610-33.21410-2/(1.13010-2) = 3.01510-3

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

[A-] = 1.13010-2 + [H3O+] [OH-]

[HA] = 3.21410-2 [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 + ]
= 1.0610-3
2 +
3.214 10 [H 3 O ]

Rearranging gives

[H3O+]2 + 1.23610-2 [H3O+] 3.40710-5 = 0

[H3O+] = 2.32110-3 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 + ]
= 4.310-1
+
0.0100 [H 3 O ]

[H3O+]2 + 0.53 [H3O+] 4.310-3 = 0

[H3O+] = 7.9910-3 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

c BHCl
[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 mL0.1011 mmol/mL = 12.64 mmol

1 mmol NH 3 1
c NH 3 = 12.64 mmol NaOH = 2.52810-2 M
mmol NaOH 500.0 mL

1
c NH + = (49.95 12.64) mmol NH +4 = 7.46210-2 M
4
500.0 mL

Substituting these relationships in equation (3) gives

c BHCl
[H3O+] = K a = 5.7010-10 7.46210-2 / (2.52810-2) = 1.68210-9 M
cB

pH = -log 1.68210-9 = 8.77

(b) Substituting into equation (3) gives

[H3O+] = 7.510-12 0.080 / 0.120 = 5.0010-12


Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

pH = -log 5.0010-12 = 11.30

(c) cB = 0.050 and cBHCl = 0.167

[H3O+] = 2.3110-11 0.167 / 0.050 = 7.71510-11

pH = -log 7.71510-11 = 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 = 9.16410-2 M

cBH+ = 2.00/250.0 = 8.0010-3 M

[H3O+] = 2.5110-5 8.0010-3 / 9.16410-2 = 2.19110-6 M

pH = -log 2.19110-6 = 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 + 1.7510-5[H3O+] 0.0500 1.7510-5 = 0

Solving by the quadratic formula or by successive approximations gives


Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

[H3O+] = 9.26710-4 and pH = -log 9.26710-4 = 3.033

For diluted solution, the quadratic becomes

[H3O+]2 + 1.7510-5 0.005001.7510-5

[H3O+] = 2.87210-4 and pH = 3.542

pH = 3.033 3.542 = -0.509

(e) OAc- + H2O ' HOAc + OH-

[HOAc][OH - ] 1.00 10 14
= = 5.7110-10 = 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
= 5.7110-10
0.0500

[OH-] = (5.7110-10 0.0500)1/2 = 5.34310-6 M

pH = 14.00 (-log 5.34310-6) = 8.728

For the diluted sample

[OH-] = (5.7110-10 0.00500)1/2 = 1.69010-6 M

pH = 14.00 (-log 1.69010-6) = 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 = 1.7510-5 =
( )
[H 3 O + ] 0.0500 + [H 3 O + ]
0.0500 [H 3 O + ]

Rearranging gives

[H3O+]2 + 5.001810-2[H3O+] 8.7510-7 = 0

[H3O+] = 1.74910-5 and pH = 4.757

Proceeding in the same way we obtain for the diluted sample

1.7510-5 =
(
[H 3 O + ] 0.00500 + [H 3 O + ])
0.00500 [H 3 O + ]

[H3O+]2 + 5.017510-3[H3O+] 8.7510-8 = 0

[H3O+] = 1.73810-5 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 = (1000.0500 + 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 = (1000.0500 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+] = 1.7510-5 0.0100/0.0400 = 4.57510-6 M

pH = -log 4.57510-6 = 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+] = 2.62510-5 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+] = 1.7510-5 0.500/0.500 = 1.7510-5 M

pH = -log 1.7510-5 = 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+] = 1.7510-5 0.510/0.490 = 1.82110-5 M

pH = -log 1.82110-5 = 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+] = 1.7510-5 0.0400/0.0100 = 7.0010-5 M

pH = -log 7.0010-5 = 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+] = 1.16710-5 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+] = 1.7510-5 0.400/0.510 = 1.68110-5 M

pH = -log 1.68110-5 = 4.774

pH = 4.774 4.757 = 0.017

14-37 For lactic acid, Ka = 1.3810-4 = [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 + ]
= 1.3810-4
+
c HA [H 3 O ]

This equation rearranges to

[H3O+]2 + (1.3810-4 + 0.0800)[H3O+] 1.3810-4 cHA = 0

(a) Before addition of acid

[H3O+]2 + (1.3810-4 + 0.0800)[H3O+] 1.3810-4 0.0200 = 0

[H3O+] = 3.44310-5 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 + (1.3810-4 + 0.0750)[H3O+] 1.3810-4 0.0250 = 0

[H3O+] = 4.58910-5 and pH = 4.338

pH = 4.338 4.463 = -0.125

(b) Before addition of acid

[H3O+]2 + (1.3810-4 + 0.0200)[H3O+] 1.3810-4 0.0800 = 0


Fundamentals of Analytical Chemistry: 8th ed. Chapter 14

[H3O+] = 5.34110-5 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 + (1.3810-4 + 0.0150)[H3O+] 1.3810-4 0.0850 = 0

[H3O+] = 7.38810-4 and pH = 3.131

pH = 3.131 3.272 = -0.141

(c) Before addition of acid

[H3O+]2 + (1.3810-4 + 0.0500)[H3O+] 1.3810-4 0.0500 = 0

[H3O+] = 1.37210-4 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 + (1.3810-4 + 0.0450)[H3O+] 1.3810-4 0.0550 = 0

[H3O+] = 1.67510-4 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 0.1000M
3 c, HCl 0.1000M
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


= = = 6.6710-5 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 6.6710-5 / 0.03329 =3.60710-7 M

pH = -log 3.60710-7 = 6.44

25.05 mL KOH

amount KOH added - initial amount HA


cKOH =
total volume soln

25.05 0.1000 - 50.00 0.05000


= = 6.6610-5 = [OH-]
75.05 mL soln

pH = 14.00 (-log 6.6610-5) = 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 = 5.0010-5 M [B]
99.95 99.95

[H3O+] = 2.31 10-11 0.04998 / 5.0010-5 =2.30910-8 M

pH = -log 2.30910-8 = 7.64

50.05 mL HClO4

c HClO4 =
(50.05 0.1000 50.00 0.1000) = 4.99810-5 = [H3O+]
100.05

pH = -log 4.99810-5 = 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.

(ci HAVi HA ci NaOHVNaOH )


Before the equivalence point: [HA] = - [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 + V NaOH ) (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 ci HAVi HA ) K w K w (ci HAVHA )


0 = [HA]2 + i NaOH NaOH + [HA] -
(Vi HA + VNaOH ) Ka K a (Vi HA + 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 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
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
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
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
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
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
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

22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
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+] = 6.31010-4 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 = 6.6110-2 M

14-46 [H3O+] = 3.3810-12 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) = 2.45310-4 M

pH = -log 2.45310-4 = 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