Student Solution Manual Fundamentals of Analytical Chemistry 10e by Skoog

Student Solution Manual
Student Solution Manual: Skoog et al., Fundamentals of Analytical Chemistry, 10e,

© 2022, 978-0-357-45055-0, Chapter 2: Calculations Used in Analytical Chemistry
Some of the answers below may differ in format but have the same value as your result. Please
check with your instructor if a specific format is desired.
Chapter 2
2-1. Define
Answers:
(a) molar mass.
The molar mass is the mass in grams of one mole of a chemical species.
(c) millimolar mass.

The millimolar mass is the mass in grams of one millimole of a chemical species.
2-3. Give two examples of units derived from the fundamental base SI units.
Solution:
3
1000 mL 1 cm3  m 
The liter: 1 L = × ×  = 10 m
−3 3
1L mL  100 cm 
1 mol L 1 mol
Molar concentration: 1 M = × −3 3 = −3 3
L 10 m 10 m
2-4. Simplify the following quantities using a unit with an appropriate prefix:
Solutions:
(a) 5.8 × 108 Hz.
MHz
5.8 × 108 Hz × = 580 MHz
106 Hz
(c) 9.31 × 107 μmol.

mol
9.31× 10 7 μmol × = 93.1 mol
10 μmol
6
(e) 3.96 × 106 nm.
mm
3.96 × 106 nm × = 3.96 mm
106 nm
© 2022 Cengage. All Rights Reserved. May not be scanned, copied or duplicated, or posted to a
publicly accessible website, in whole or in part.
1
2-5. Why is 1 g no longer exactly 1 mole of unified atomic mass units?
Answer:
The dalton is defined as 1/12 the mass of a neutral 12C atom. With the redefinition of SI
base units in 2019, the definition of the dalton remained the same. However, the
definition of the mole and the kilogram changed in such a way that the molar mass unit
is no longer exactly 1 g/mol.
2-7. Find the number of Na+ ions in 2.75 g of Na3PO4?
Solution:
1 mol Na3PO4 3 mol Na+ 6.022 × 1023 Na+
2.75 g Na3PO4 × × × = 3.03 × 1022 Na+
163.94 g mol Na3PO4 mol Na+
2-9. Find the amount of the indicated element (in moles) in
Solutions:
(a) 5.32 g of B2O3.
2 mol B mol B2O3

5.32 g B2O3 × × = 0.153 mol B
mol B2O3 69.62 g B2O3
(b) 195.7 mg of Na2B4O7 ⋅ 10H2O.
g 7 mol O
195.7 mg Na2B4O7 ⋅ 10H2O × ×
1000 mg mol Na2B4O7 ⋅ 10H2O
mol Na2B4O7 ⋅ 10H2O
× = 3.59 × 10−3 mol O = 3.59 mmol
381.37 g
(c) 4.96 g of Mn3O4.

mol Mn3O4 3 mol Mn
4.96 g Mn3O4 × × = 6.50 × 10 −2 mol Mn
228.81 g Mn3O4 mol Mn3O4
(d) 333 mg of CaC2O4.
g mol CaC2O4 2 mol C

333 mg CaC2O4 × × × = 5.20 × 10−3 mol C
1000 mg 128.10 g CaC2O4 mol CaC2O4
= 5.20 mmol
2-11. Find the number of millimoles of solute in
Solutions:
(a) 2.00 L of 0.0449 MKMnO .
4
0.0449 mol KMnO4 1000 mmol

× × 2.00 L = 89.8 mmol KMnO4
L mol
2
(b) 750 mL of 5 .35 × 1023 M KSCN.
5.35 × 10 −3 M KSCN 1000 mmol L

× × × 750 mL = 4.01 mmol KSCN
L mol 1000 mL
(c) 3.50 L of a solution that contains 6.23 ppm of CuSO4 .
6.23 mg CuSO4 g mol CuSO4 1000 mmol

× × × × 3.50 L = 0.137 mmol CuSO4
L 1000 mg 159.61 g CuSO4 mol
(d) 250 mL of 0.414 mM KCl.

0.414 mmol KCl 1L
× × 250 mL = 0.104 mmol KCl
L 1000 mL
2-13. What is the mass in milligrams of
Solutions:
(a) 0.367 mol of HNO3?
63.01 g HNO3 1000 mg
0.367 mol HNO3 × × = 2.31× 104 mg HNO3
mol HNO3 g
(b) 245 mmol of MgO?

mol 40.30 g MgO 1000 mg
245 mmol MgO × × × = 9.87 × 10 3 mg MgO
1000 mmol mol MgO g
(c) 12.5 mol of NH4NO3 ?
80.04 g NH 4 NO 3 1000 m g
12.5 m ol NH 4 NO 3 × × = 1.00 × 10 6 m g NH 4 NO 3
m ol NH 4 NO 3 g
(d) 4.95 mol of (NH4 )2 e (NO3 )6 ( 548.23 g/mol) ?
548.23 g (NH4 )2 Ce(NO 3 )6 1000 mg

4.95 mol (NH4 ) 2 Ce(NO 3 )6 × ×
mol (NH4 ) 2 Ce(NO 3 )6 g
= 2.71× 10 6 mg (NH4 ) 2 Ce(NO 3 )6
2-15. What is the mass in milligrams of solute in
Solutions:
(a) 16.0 mL of 0.350 M sucrose (342 g/mol)?
0.350 mol sucrose L 342 g sucrose 1000 mg
× × ×
L 1000 mL mol sucrose g
× 16.0 mL = 1.92 × 10 3 mg sucrose
3
(b) 1.92 L of 3.76 × 1023 M H2O2 ?
3.76 × 10 − 3 m ol H 2 O 2 34.02 g H 2 O 2 1000 m g

× × × 1.92 L = 246 m g H 2 O 2
L m ol H 2 O 2 g
2-16. What is the mass in grams of solute in
Solutions:
(a) 250 mL of 0.264 M H2O2 ?
0.264 mol H2 O 2 L 34.02 g H2 O 2

× × × 250 mL = 2.25 g H2 O 2
L 1000 mL mol H2 O 2
(b) 37.0 mL of 5.75 × 10−4 M benzoic acid (122 g/mol)?
5.75 ×10−4 mol benzoicacid L 122 g benzoicacid

× ×
L 1000 mL mol benzoicacid
× 37.0 mL = 2.60 ×10−3 g benzoicacid
2-17. Calculate the p-value for each of the listed ions in the following:
Solutions:
(a) Na1 , Cl , and OH in a solution that is 0.0635 M in NaCl and 0.0403 M in NaOH.
− −
pNa = − log (0.0635 + 0.0403) = −log(0.1038) = 0.9838

pCl = −log(0.0635) = 1.197
pOH = − log (0.0403) = 1.395
(c) H+, Cl−, and Zn21 in a solution that is 0.400 M in HCl and 0.100 M in ZnCl2 .
pH = − log(0.400) = 0.398
pCl = − log(0.400 + 2 × 0.100) = − log(0.600) = 0.222
pZn = − log(0.100) = 1.00
K+, OH−, and Fe ( CN )6

42
(e) in a solution that is 1.62 × 10−7 M in K 4Fe ( CN)6 and 5.12 × 10−7 M
in KOH.
pK = − log(4 × 1.62 × 10−7 + 5.12 × 10−7 ) = − log(1.16 × 10−6 ) = 5.94
pOH = − log(5.12 × 10−7 ) = 6.291

pFe(CN)6 = − log(1.62 × 10−7 ) = 6.790
4
2-18. Calculate the molar H3O+ ion concentration of a solution that has a pH of
Solutions:
(a) 3.73.
pH = 3.73, log[H3O+] = −3.73, [H3O+] = 1.9 × 10−4 M
as in part (a)
(c) 0.59.
[H3O+] = 0.26 M
(e) 7.62.
[H3O+] = 2.4 × 10−8 M
(g) 20.76.
[H3O+] = 5.8 M
2-19. Calculate the p-functions for each ion in a solution that is
Solutions:
(a) 0.0200 M in NaBr.
pNa = pBr = −log(0.0200) = 1.699
(c) 4.5 × 1023 M in Ba ( OH) .

2
pBa = −log(4.5 × 10−3) = 2.35; pOH = −log(2 × 4.5 × 10−3) = 2.05
(e) 7.2 × 1023 M in CaCl and 8.2 × 1023 M in BaCl .

2 2
pCa = −log(7.2 × 10−3) = 2.14; pBa = −log(8.2 × 10−3) = 2.09

pCl = −log(2 × 7.2 × 10−3 + 2 × 8.2 × 10−3) = −log(0.0308) = 1.51
2-20. Convert the following p-functions to molar concentrations:
Solutions:
(a) pH = 1.102.
pH = 1.102; log[H3O+] = −1.102; [H3O+] = 0.0791 M
(c) pBr = 7.77.
pBr = 7.77; log[Br−] = −7.77; [Br−] = 1.70 × 10−8 M
(e) pLi = 12.35.
pLi = 12.35; log[Li+] = −12.35; [Li+] = 4.5 × 10−13 M
5
(g) pMn = 0 .135.
pMn = 0.135; log[Mn2+] = −0.135; [Mn2+] = 0.733 M
2-21. Seawater contains an average of 1.08 × 103 ppm of Na+ and 270 ppm of SO42−. Calculate
Solutions:
(a) the molar concentrations of Na1 and SO4 22 given that the average density of
seawater is 1.02 g/mL.
1 1.02 g 1000 mL mol Na +
1.08 × 10 3 ppm Na + × × × × = 4.79 × 10 −2 M Na +
10 6 ppm mL L 22.99 g
1.02 g 1000 mL mol SO 4

2−
1
270 ppm SO 4 2 − × × × × = 2.87 × 10 −3 M SO 4 2 −
10 6 ppm mL L 96.06 g
(b) the pNa and pSO4 for seawater.
pNa = − log(4.79 × 10−2 ) = 1.320
pSO4 = − log(2.87 × 10−3 ) = 2.543
2-23. A solution was prepared by dissolving 5.76 g of KCl ⋅ MgCl2 ⋅ 6H2O (277.85 g/mol) in
sufficient water to give 2.000 L. Calculate
Solutions:
(a) the molar analytical concentration of KCl ⋅ MgCl2 in this solution.
5.76 g KCl ⋅ MgCl2 ⋅ 6H2 O mol KCl ⋅ MgCl2 ⋅ 6H2 O

× = 1.04 × 10 −2 M KCl ⋅ MgCl2 ⋅ 6H2 O
2.00 L 277.85 g
(b) the molar concentration of Mg21.
There is 1 mole of Mg2+ per mole of KCl ⋅ MgCl2, so the molar concentration of Mg2+
is the same as the molar concentration of KCl ⋅ MgCl2 or 1.04 × 10−2 M.
(c) the molar concentration of Cl2 .

3 m ol Cl−
1.04 × 10 − 2 M KCl ⋅ M gCl2 ⋅ 6H 2 O × = 3.12 × 10 − 2 M Cl−
m ol KCl ⋅ M gCl2 ⋅ 6H 2 O
(d) the weight/volume percentage of KCl ⋅ MgCl2 ⋅ 6H2O.

5.76 g KCl ⋅ MgCl2 ⋅ 6H2 O L
× × 100% = 0.288% (w/v)
2.00 L 1000 mL
(e) the number of millimoles of Cl2 in 25.0 mL of this solution.
3.12 × 10 −2 mol Cl− L 1000 mmol

× × × 25 mL = 7.8 × 10 −1 mmol Cl−
L 1000 mL mol
6
(f) ppm K1.
1 mol K + 39.10 g K + 1000 mg

1.04 × 10−2 M KCl ⋅ MgCl2 ⋅ 6H2O × × ×
1mol KCl ⋅ MgCl2 ⋅ 6H2O mol K + g
407 mg
= = 407 ppm K +
L
(g) pMg for the solution.

pMg = −log(1.04 × 10−2) = 1.983
(h) pCl for the solution.

pCl = −log(3.12 × 10−2) = 1.506
2-25. A 5.85% (w/w) Fe(NO3)3 (241.86 g/mol) solution has a density of 1.059 g/mL. Calculate
Solutions:
(a) the molar analytical concentration of Fe (NO3 )3 in this solution.
5.85 g Fe(NO 3 ) 3 1 1.059 g 1000 mL mol Fe(NO 3 ) 3

5.85% Fe(NO 3 )3 = × × × ×
g solution 100 mL L 241.86 g
= 2.56 × 10 −1 M Fe(NO 3 ) 3 = 0.256 M
(b) the molar NO32 concentration in the solution.
2.56 × 10 − 1 m ol Fe(NO 3 ) 3 3 m ol NO 3 −
2.56 × 10 −1 M Fe(NO 3 ) 3 = × = 7.68 × 10 − 1 M NO 3 −
L m ol Fe(NO 3 ) 3
(c) the mass in grams of Fe(NO3 )3 contained in each liter of this solution.
2.56 × 10 −1 mol Fe(NO3 )3 241.86 g Fe(NO3 )3

× × L = 6.20 × 101 g Fe(NO3 )3 = 62.0 g
L mol
2-27. Describe the preparation of
Solutions:
(a) 500 mL of 5.25% (w/v) aqueous ethanol ( C2H5OH, 46.1 g/mol).
5.25 g C2H5OH 1
× × 500 mL soln = 26.3 g C2H5OH
mL soln 100
Weigh 26.3 g ethanol and add enough water to give a final volume of 500 mL.
(b) 500 g of 5.25% (w/w) aqueous ethanol.

5.25 g C 2H5 OH 1
5.25% (w/w) C 2H5 OH = × × 500 g soln = 2.63 × 101 g C 2H5 OH
g soln 100
500 g soln = 26.3 g C2H5OH + x g water
7
x g water = 500 g soln − 26.3 g C2H5OH = 473.7 g water

Mix 26.3 g ethanol with 473.7 g water.
(c) 500 mL of 5.25% (v/v) aqueous ethanol.

5.25 mL C 2H5 OH
5.25% (v/v) C 2H5 OH =
100 mL soln
5.25 mL C 2H5 OH
× 500 mL soln = 26.3 mL C 2H5 OH
100 mL soln
Dilute 26.3 mL ethanol with enough water to give a final volume of 500 mL.
2-29. Describe the preparation of 500 mL of 3.00 M H3PO4 from the commercial reagent that is
86% H3PO4 (w/w) and has a specific gravity of 1.71.
Solution:
3.00 mol H3PO 4 L
× × 500 mL = 1.50 mol H3PO 4
L 1000 mL
86 g H3PO 4 1 1.71 g reagent g water 1000 mL mol H3PO 4 1.50 × 10 mol H3PO 4
1
× × × × × =
g reagent 100 g water mL L 98.0 g L
L
volume 86% (w/w) H3PO 4 required = 1.50 mol H3PO 4 ×
1.50 × 10 mol H3PO 4
1
= 1.00 × 10 −1 L
Dilute 100 mL to 500 mL with water.
Solutions:
(a) 500 mL of 0.1000 M AgNO3 from the solid reagent.
0.1000 mol AgNO3

0.1000 M AgNO3 =
L
0.1000 mol AgNO3 169.87 g AgNO3 L
= × × × 500 mL
L mol 1000 mL
= 8.49 g AgNO3
Dissolve 8.49 g AgNO3 in enough water to give a final volume of 500 mL.
(b) 1.00 L of 0.1000 M HCl, starting with a 6.00 M solution of the reagent.
0.1000 mol HCl
× 1 L = 0.1000 mol HCl
L
L
0.1000 mol HCl × = 1.67 × 10−2 L HCl
6.00 mol HCl
Take 167 mL of the 6.00 M HCl and dilute to 1.00 L using water.
8
(c) 250 mL of a solution that is 0.0810 M in K1 , starting with solid K 4Fe ( CN)6 .
0.0810 mol K + L
× × 250 mL = 2.025 × 10−2 mol K +
L 1000 mL
mol K 4Fe(CN)6 368.35 g K 4Fe(CN)6
2.025 × 10 −2 mol K + × × = 1.86 g K 4Fe(CN)6
4 mol K +
mol
Dissolve 1.86 g K4Fe(CN)6 in enough water to give a final volume of 250 mL.
(d) 500 mL of 3.00% (w/v) aqueous BaCl2 from a 0.400 M BaCl2 solution.
3.00 g BaCl2 1
× × 500 mL = 1.5 × 101 g BaCl2
mL soln 100
mol BaCl2 L
1.5 × 101 g BaCl2 × × = 1.80 × 10 −1 L
208.23 g 0.400 mol BaCl2
Take 180 mL of the 0.400 M BaCl2 solution and dilute to 500 mL using water.
(e) 2.00 L of 0.120 M HClO4 from the commercial reagent [71.0% HClO4 (w/w), sp gr
1.67].
0.120 mol HClO4
× 2.00 L = 0.240 mol HClO4
L
71 g HClO4 1
1.67 g reagent g water 1000 mL mol HClO4 1.18 × 10 mol HClO4
× × × × =
100 g reagent g water mL L 100.46 g L
L
volume 71% (w/w) HClO4 required = 0.240 mol HClO4 =
1.18 × 101 mol HClO4
= 2.03 × 10 −2 L
Take 20.3 mL of the concentrated reagent and dilute to 2.00 L using water.
(f) 1.00 L of a solution that is 60.0 ppm in Na1 , starting with solid Na2 SO4 .
60 mg Na+
60 ppm Na+ =
L soln
60 mg Na+
× 1.00 L = 60 mg Na+
L soln
g mol Na+
60 mg Na+ × × = 2.61× 10 −3 mol Na+
1000 mg 22.99 g
mol Na2 SO 4 142.04 g Na2 SO 4
2.61× 10 −3 mol Na+ × × = 0.19 g Na2 SO4
2 mol Na +
mol
Dissolve 0.19 g Na2SO4 in enough water to give a final volume of 1.00 L.
9
2-33. What mass of solid La(IO3)3 (663.6 g/mol) is formed when 50.0 mL of 0.250 M La3+ is
mixed with 75.0 mL of 0.302 M IO3−?
Solution:
0.250 mol La3+ L
× × 50.0 mL = 1.25 × 10 −2 mol La3+
L 1000 mL
0.302 mol IO3 − L
0.302 M IO3 − = × × 75.0 mL = 2.27 × 10 −2 mol IO3 −
L 1000 mL
Because each mole of La(IO3)3 requires three moles IO3−, IO3− is the limiting reagent.
Thus,
mol La(IO3 )3 663.6 g La(IO3 )3
2.27 × 10 −2 mol IO3 − × × = 5.01 g La(IO3 )3 formed
3 mol IO3 −
mol
2-35. Exactly 0.118 g of pure Na2CO3 is dissolved in 100.0 mL of 0.0731 M HCl.
Solutions:
(a) What mass in grams of CO2 is evolved?
A balanced chemical equation can be written as:

Na2CO3 + 2HCl → 2NaCl + H2O + CO2 (g)
mol Na2 CO3
0.1180 g Na2CO3 × = 1.113 × 10 −3 mol Na2CO3
105.99 g
0.0731 mol HCl L
× × 100.0 mL = 7.31× 10−3 mol HCl
L 1000 mL
Because one mole of CO2 is evolved for every mole Na2CO3 reacted, Na2CO3 is the
limiting reagent. Thus,
mol CO2 44.00 g CO2
1.113 × 10 −3 mol Na2 CO3 × × = 4.897 × 10 −2 g CO2 evolved
mol Na2 CO3 mol
(b) What is the molar concentration of the excess reactant (HCl or Na2CO3 ) ?
amnt HCl left = 7.31× 10−3 mol − (2 × 1.113 × 10−3 mol) = 5.08 × 10−3 mol
5.08 × 10−3 mol HCl 1000 mL
× = 5.08 × 10−2 M HCl
100.0 mL L
2-37. Exactly 75.00 mL of a 0.3132 M solution of Na2SO3 is treated with 150.0 mL of 0.4025 M
HClO4 and boiled to remove the SO2 formed.
Solutions:
(a) What is the mass in grams of SO2 that is evolved?
10

Na2 SO3 + 2HClO4 → 2NaClO4 + H2O + SO2 (g)
0.3132 mol Na2 SO3 L

0.3132 M Na2 SO3 = × × 75 mL = 2.3 ×10 −2 mol Na2 SO3
L 1000 mL
0.4025 mol HClO4 L
0.4025 M HClO4 = × × 150.0 mL
L 1000 mL
= 6.038 × 10−2 mol HClO4
Because one mole SO2 is evolved per mole Na2SO3, Na2SO3 is the limiting reagent.
Thus,
mol SO2 64.06 g SO2
2.3 × 10 −2 mol Na2 SO3 × × = 1.5 g SO2 evolved
mol Na2 SO3 mol
(b) What is the concentration of the unreacted reagent (Na2 SO3 or HClO4 ) after the
reaction is complete?
mol HClO4 unreacted = 6.038 × 10−2 mol − (2 × 2.3 × 10−2 ) = 1.4 × 10−2 mol
1.4 × 10 −2 mol HClO 4 1000 mL
× = 6.4 × 10 −2 M HClO 4 = 0.064 M
225 mL L
2-39. What volume of 0.01000 M AgNO3 is required to precipitate all of the I− in 150 mL of a
solution that contains 22.50 ppt KI?
Solution:
AgNO3 + KI → AgI(s) + KNO3
1 g mol KI
22.50 ppt KI × × × 150 mL × = 2.03 × 10−2 mol KI
10 ppt mL
3
166.0 g
mol AgNO3 L
2.03 × 10 −2 mol KI × × = 2.03 L AgNO3
mol KI 0.0100 mol AgNO3
2.03 L of 0.0100 M AgNO3 would be required to precipitate I− as AgI.
11
© 2022, 978-0-357-45055-0, Chapter 3: Precision and Accuracy of Chemical Analyses
Chapter 3
3-1. Explain the difference between
Answers:
(a) random and systematic error.
Random error causes data to be scattered more or less symmetrically around a
mean value while systematic error causes the mean of a data set to differ from the
accepted value.
(c) absolute and relative error.

The absolute error of a measurement is the difference between the measured value
and the true value while the relative error is the absolute error divided by the true value.
3-2. Suggest two sources of systematic error and two sources of random error in measuring
the length of a 3-m table with a 1-m metal rule.
Answers:
(1) Meter stick slightly longer or shorter than 1.0 m—systematic error.
(2) Markings on the meter stick always read from a given angle—systematic error.
(3) Variability in the sequential movement of the 1-m metal rule to measure the full 3-m
table length—random error.
(4) Variability in interpolation of the finest division of the meter stick—random error.
3-4. Describe at least three systematic errors that might occur while weighing a solid on an
analytical balance.
Answers:
(1) The analytical balance is miscalibrated.
(2) After weighing an empty vial, fingerprints are placed on the vial while adding sample
to the vial.
(3) A hygroscopic sample absorbs water from the atmosphere while placing it in a
weighing vial.
publicly accessible website, in whole or in part. 1
3-5. Describe at least three ways in which a systematic error might occur while using a pipet
to transfer a known volume of liquid.
Answers:
(1) The pipet is miscalibrated and holds a slightly different volume of liquid than the
indicated volume.
(2) The user repetitively reads the meiscus from an angle rather than at eye level.
(3) The temperature differs from the calibration temperature.
3-7. What kind of systematic errors are detected by varying the sample size?
Answer:
Both constant and proportional systematic errors can be detected by varying the sample
size. Constant errors do not change with the sample size while proportional errors
increase or decrease with increases or decreases in the samples size.
3-8. A method of analysis yields masses of gold that are low by 0.4 mg. Calculate the percent
relative error caused by this result if the mass of gold in the sample is
Solutions:
(a) 500 mg.
(−0.4 mg/500 mg) × 100% = −0.08%
As in part (a)
(c) 125 mg.

−0.32%
3-9. The method described in Problem 3-8 is to be used for the analysis of ores that assay
about 1.2% gold. What minimum sample mass should be taken if the relative error
resulting from a 0.4-mg loss is not to exceed
Solutions:
(a) 20.1%?
First determine how much gold is needed to achieve the desired relative error.
(−0.4 mg/−0.1%) × 100% = 400 mg gold
Then determine how much ore is needed to yield the required amount of gold.
(400 mg/1.2%) × 100% = 33,000 mg ore or 33 g ore
(c) 20.8% ?
4.2 g ore
3-10. The color change of a chemical indicator requires an overtitration of 0.03 mL. Calculate
the percent relative error if the total volume of titrant is
Solutions:
(a) 50.00 mL.
(0.03/50.00) × 100% = 0.060%
As in part (a)
(b) 10.0 mL.

0.30%
(c) 25.0 mL.

0.12%
3-11. A loss of 0.4 mg of Zn occurs in the course of an analysis for that element. Calculate the
percent relative error due to this loss if the mass of Zn in the sample is
Solutions:
(a) 30 mg.
(−0.4/30) × 100% = −1.3%
(c) 300 mg.

−0.13%
3-12. Find the mean and median of each of the following sets of data. Determine the deviation
from the mean for each data point within the sets, and find the mean deviation for each
set. Use a spreadsheet if it is convenient.
Solutions:
(a) 0.0110 0.0104 0.0105
 0.0110 + 0.0104 + 0.0105 

mean =   = 0.01063 ≈ 0.0106
 3 
Arranging the numbers in increasing value the median is:
0.0104
0.0105 ← median
0.0110
The deviations from the mean are:

0.0104 − 0.01063 = 0.00023
0.0105 − 0.01063 = 0.00013
0.0110 − 0.01063 = 0.00037
 0.00023 + 0.00013 + 0.00037 
mean deviation =   = 0.00024 ≈ 0.0002
 3 
(c) 188 190 194 187

mean = 190 median = 189 deviation from mean 2, 0, 4, 3 mean deviation = 2
(e) 39.83 39.61 39.25 39.68

mean = 39.59 median = 39.64 deviation from mean 0.24, 0.02, 0.34, 0.09
mean deviation = 0.17
© 2022, 978-0-357-45055-0, Chapter 4: Random Errors in Chemical Analysis
Chapter 4
4-1. Define
Answers:
(a) sample standard deviation.
The sample standard deviation is the standard deviation of a sample of data. It
applies to a small set of data from the population. It uses deviations from the
experimental mean and the number of degrees or freedom N − 1 in place of the
population mean μ and N.
(c) variance.
The variance is the square of the standard deviation.
4-2. Differentiate between
Answers:
(a) parameter and statistic.
The term parameter refers to quantities such as the mean and standard deviation
of a population or distribution of data. The term statistic refers to an estimate of a
parameter that is made from a sample of data.
(c) random and systematic error.

Random errors result from uncontrolled variables in an experiment while systematic
errors are those that can be ascribed to a particular cause and can usually be
determined.
4-3. Distinguish between
Answer:
(a) the sample variance and the population variance.
The sample variance s2 is the variance of a sample drawn from the population. It is
N
(x − x)
2
i
given by s 2 = i =1
, where x is the sample mean.
N −1
1
The population variance σ2 is the variance of an entire population given by

N
(x − μ)
2
i
σ2 = i =1
, where μ is the population mean.
N
4-5. From the Gaussian (normal) error curve, what is the probability that a result from a
population lies between 0 and +1σ of the mean? What is the probability of a result
occurring that is between +1σ and +2σ of the mean?
Answer:
Since the probability that a result lies between −1σ and +1σ is 0.683, the probability that
a result will lie between 0 and +1σ will be half this value or 0.342. The probability that a
result will lie between +1σ and +2σ will be half the difference between the probability of
the result being between −2σ and +2σ, and −1σ and +1σ, or ½ (0.954−0.683) = 0.136.
4-7. Consider the following sets of replicate measurements:
A C E
9.5 0.612 20.63

8.5 0.592 20.65
9.1 0.694 20.64
9.3 0.700 20.51
9.1
For each set, calculate the (a) mean, (b) median, (c) spread or range, (d) standard
deviation, and (e) coefficient of variation.
Solutions:
For set A
xi xi2
9.5 90.25
8.5 72.25
9.1 82.81
9.3 86.49
9.1 82.81
Σxi = 45.5 Σxi2 = 414.61
mean: x = 45.5/5 = 9.1
median = 9.1
spread: w = 9.5 − 8.5 = 1.0
414.61− ( 45.5 ) / 5
2
standard deviation: s = = 0.37

5 −1
coefficient of variation: CV = (0.37/9.1) × 100% = 4.1%
2
Results for Sets A, C, and E, obtained in a similar way, are given in the following table.
A C E
(a) x 9.1 0.650 20.61
(b) median 9.1 0.653 20.64
(c) w 1.0 0.108 0.14
(d) s 0.37 0.056 0.07
(e) CV, % 4.1 8.5 0.32
4-9. Estimate the absolute deviation and the coefficient of variation for the results of the
following calculations. Round each result so that it contains only significant digits. The
numbers in parentheses are absolute standard deviations.
Solutions:
(a) y = 3.95 ( ±0.03) + 0.993 ( ±0.001)
27.025 ( ±0.001) = 22.082
( 0.03) + ( 0.001) + ( 0.001)

2 2 2
sy = = 0.030
CV = (0.03/−2.082) × 100% = −1.4%
y = −2.08(±0.03)
(c) y = 29.2 ( ±0.3 ) × 2.03 ( ±0.02 ) ×10217

= 5.93928 × 10216
2 2
sy  0.3   0.02 × 10 −17 
=   + −17 
= 0.01422
y  29.2   2.034 × 10 
CV = (0.0142) × 100% = 1.42%
sy = (0.0142) × (5.93928 × 10−16) = 0.08446 × 10−16
y = 5.94(±0.08) × 10−16
187 ( ±6 ) − 89 ( ±3 )
(e) y= = 7.5559 × 1022
1240 ( ±1) + 57 ( ±8 )
(6 ) + ( 3)
2 2
snum = = 6.71 ynum = 187 − 89 = 98
(1) + ( 8 )
2 2
sden = = 8.06 yden = 1240 + 57 = 1297
2 2
sy  6.71  8.06 
=   +  = 0.0688
y  98   1297 
CV = (0.0688) × 100% = 6.88%
sy = (0.0688) × (0.075559) = 0.00520
y = 7.6(±0.5) × 10−2
3
4-10. Estimate the absolute standard deviation and the coefficient of variation for the results
of the following calculations. Round each result to include only significant figures. The
Solutions:
(a) y = 1.02 ( ±0.02 ) × 1028 − 3.54 ( ±0.2 ) × 1029
( 0.02 × 10 ) + ( 0.2 × 10 )
2 2
sy = −8 −9
= 2.83 × 10−10
y = 1.02×10−8 − 3.54×10−9 = 6.66×10−9
2.83 × 10−10
CV = × 100% = 4.25%
6.66 × 10−9
y = 6.7 ±0.3 × 10−9
(c) y = 0.0040 ( ±0.0005) × 10.28 ( ±0.02 )

× 347 ( ±1)
2 2
sy  0.0005   0.02   1 
=   +  +  = 0.1250
y  0.0040   10.28   347 
CV = (0.1250) × 100% = 12.5%
y = 0.0040 × 10.28 × 347 = 14.27
sy = (0.125) × (14.27) = 1.78
y = 14(±2)
100 ( ±1)
(e) y=
2 ( ±1)
2 2
sy  1   1
=   +   = 0.500
y  100   2 
CV = (0.500) × 100% = 50.0%
y = 100 / 2 = 50.0
sy = (0.500) × (50.0) = 25
y = 50(±25)
4-11. Calculate the absolute standard deviation and the coefficient of variation for the results
Solutions:
(a) y = log 2.00 ( ±0.03) × 1024 
y = log(2.00 × 10−4) = −3.6989

( 0.434 ) ( 0.03 × 10 )
−4
sy = = 6.51× 10 −3
( 2.00 × 10 )
−4
4
y = −3.699 ±0.006
CV = (0.006/3.699) × 100% = 0.16%
(c) y = antilog 1.200 ( ±0.003) 

sy
y = antilog(1.200) = 15.849 = ( 2.303 )( 0.003 ) = 0.0069
y
sy = (0.0069)(15.849) = 0.11 y = 15.8 ±0.1
CV = (0.11/15.8) × 100% = 0.69%
4-12. Calculate the absolute standard deviation and the coefficient of variation for the results
Solution:
3
(a) y =  4.17 ( ±0.03 ) × 1024 
sy
 0.03 × 10−4 
y = (4.17 × 10−4)3 = 7.251 × 10−11 = 3 −4 
= 0.0216
y  4.17 × 10 
sy = (0.0216)(7.251 × 10−11) = 1.565 × 10−12 y = 7.3(±0.2) × 10−11
CV = (1.565 × 10−12/7.251 × 10−11) × 100% = 2.2%
4-13. The standard deviation in measuring the diameter d of a sphere is ±0.02 cm. What is the
standard deviation in the calculated volume V of the sphere if d = 2.35 cm?
Solution:
From the equation for the volume of a sphere, we have
3 3
4 3 4 d 4  2.35 
V= πr = π   = π   = 6.80 cm
3
3 3 2 3  2 
Hence, we may write

sV s 0.02
= 3× d = 3× = 0.0255
V d 2.35
sV = 6.80 × 0.0255 = 0.173
V = 6.8(±0.2) cm3
4-15. In a volumetric determination of an analyte A, the data obtained and their standard
deviations are as follows:
Initial buret reading 0.19 mL 0.02 mL

Final buret reading 9.26 mL 0.03 mL
Sample mass 45.0 mg 0.2 mg
From the data, find the coefficient of variation of the final result for the %A that is
obtained by using the equation that follows and assuming there is no uncertainty in the
equivalent mass.
5
%A = titrant volume × equivalent mass × 100%/sample mass

Solution:
Since the titrant volume equals the final buret reading minus the initial buret reading, we
can introduce the values given into the equation for %A.
%A = [9.26(±0.03) − 0.19(±0.02)] × equivalent weight × 100/[45.0(±0.2)]
Obtaining the value of the first factor and the error in the first factor
( 0.03 ) + ( 0.02 )
2 2
sy = = 0.0361 y = 9.26 − 0.19 = 9.07
We can now obtain the relative error of the calculation

2 2
s%A  0.036   0.2 
=   +  = 0.00596
%A  9.07   45.0 
The coefficient of variation is then

CV = (0.00596) × 100% = 0.596% or 0.6%
4-17. Chapter 22 shows that quantitative molecular absorption spectrometry is based on

Beer’s law, which can be written as
2logT = ε bcX
where T is the transmittance of a solution of an analyte X, b is the thickness of the

absorbing solution, c X is the molar concentration of X, and ε is an experimentally
determined constant. By measuring a series of standard solutions of X, ε b was found to
have a value of 3312(±12) M−1, where the number in parentheses is the absolute
standard deviation.
An unknown solution of X was measured in a cell identical to the one used to
determine ε b. The replicate results were T = 0.213, 0.216, 0.208, and 0.214. Calculate (a)
the molar concentration of the analyte cX, (b) the absolute standard deviation of the cX,
and (c) the coefficient of variation of cX.
Solutions:
We first calculate the mean transmittance and the standard deviation of the mean.
 0.213 + 0.216 + 0.208 + 0.214 
mean T =   = 0.2128
 4 
sT = 0.0034
 − log T  − log ( 0.2128 )

(a) cX =  = = 2.029 × 10−4 M
 εb  3312
(b) For −logT, sy = (0.434)sT/T = 0.434 × (0.0034/0.2128) = 0.00693

−log(0.2128) = 0.672
− log T 0.672 ± 0.00693
cX = =
εb 3312 ± 12
6
sC 2
 0.00693   12 
2
=   +  = 0.0109
X
cX  0.672   3312 
( )
sC X = ( 0.0109 ) 2.029 × 10 −4 = 2.22 × 10 −6
(c) CV = (2.22 × 10−6/2.029 × 10−4) × 100% = 1.1%
4-19. Six bottles of wine of the same variety were analyzed for residual sugar content with the
following results:
Bottle Percent (w/v) Residual Sugar
1 1.02, 0.84, 0.99

2 1.13, 1.02, 1.17, 1.02
3 1.12, 1.32, 1.13, 1.20, 1.25
4 0.77, 0.58, 0.61, 0.72
5 0.73, 0.92, 0.90
6 0.73, 0.88, 0.72, 0.70
(a) Evaluate the standard deviation s for each set of data.

Solution:
The standard deviations are s1 = 0.096, s2 = 0.077, s3 = 0.084, s4 = 0.090, s5 = 0.104, s6

= 0.083
7
(b) Pool the data to obtain an absolute standard deviation for the method.
Solution:
spooled = 0.088 or 0.09
4-21. Calculate a pooled estimate of σ from the following spectrophotometric analysis for NTA
(nitrilotriacetic acid) in water from the Ohio River:
Sample NTA, ppb
1 13, 19, 12, 7

2 42, 40, 39
3 29, 25, 26, 23, 30
Solution:
8
© 2022, 978-0-357-45055-0, Chapter 5: Statistical Data Treatment and Evaluation
Chapter 5
5-1. Describe in your own words why the confidence interval for the mean of five
measurements is smaller than that for a single result.
Solution:
The distribution of means is narrower than the distribution of single results. Hence, the
standard error of the mean of 5 measurements is smaller than the standard deviation of
a single result. The mean is thus known with more confidence than is a single result.
5-4. Consider the following sets of replicate measurements:
A C E
0.514 70.24 0.812

0.503 70.22 0.792
0.486 70.10 0.794
0.497 0.900
0.472
Calculate the mean and the standard deviation for each of these six data sets. Calculate
the 95% confidence interval for each set of data. What does this interval mean?
Solutions:
For Set A
xi xi2
0.514 0.2642
0.503 0.2530
0.486 0.2362
0.497 0.2470
0.472 0.2228
Σxi = 2.472 Σxi2 = 1.223
mean: x = 2.472/5 = 0.494
1.223 − ( 2.472 ) / 5
2
standard deviation: s = = 0.016

5 −1
1
Since, for a small set of measurements we cannot be certain s is a good approximation

of σ, we should use the t statistic for confidence intervals. From Table 5-3, at 95%
confidence t for 4 degrees of freedom is 2.78, therefore for set A,
CI for μ = 0.494 ±
( 2.78 )( 0.016 ) = 0.494 ± 0.020
5
Similarly, for sets A, C, and E, we obtain the results shown in the following table:
A C E
x 0.494 70.19 0.824
s 0.016 0.08 0.051
95% CI 0.494 ± 0.020 70.19 ± 0.20 0.824 ± 0.081
The 95% confidence interval is the range within which the population mean is expected
to lie with a 95% probability.
5-5. Calculate the 95% confidence interval for each set of data in Problem 5-4 if s is a good
estimate of σ and has a value of set A, 0.015; set C, 0.070; set E, 0.0090.
Solutions:
If s is a good estimate of σ then we can use z = 1.96 for the 95% confidence level. For set
A, at the 95% confidence,
CI for μ = 0.494 ±
(1.96 )( 0.015 ) = 0.494 ± 0.013. Similarly for sets C and E, the limits are:
5
C E
CI 70.19 ± 0.079 0.824 ± 0.009
5-7. An atomic absorption method for the determination of the amount of iron present in
used jet engine oil was found from pooling 30 triplicate analyses to have a standard
deviation s = 2.9 μg Fe/mL. If s is a good estimate of σ , calculate the 95% and 99%
confidence intervals for the result 17.2 μg Fe/mL if it was based on (a) a single analysis,
(b) the mean of two analyses, and (c) the mean of four analyses.
Solutions:
(a) 99% CI = 17.2 ± 2.58 × 2.9 = 17.2 ± 7.5 μg Fe/mL
95% CI = 17.2 ± 1.96 × 2.9 = 17.2 ± 5.7 μg Fe/mL
2.58 × 2.9
(b) 99% CI = 17.2 ± = 17.2 ± 5.3 μg Fe/mL
2
1.96 × 2.9
95% CI = 17.2 ± = 17.2 ± 4.0 μg Fe/mL
2
2
2.58 × 2.9
(c) 99% CI = 17.2 ± = 17.2 ± 3.7 μg Fe/mL
4
1.96 × 2.9
95% CI = 17.2 ± = 17.2 ± 2.8 μg Fe/mL
4
5-9. How many replicate measurements are needed to decrease the 95% and 99%
confidence limits for the analysis described in Problem 5-7 to ±1.9 μg Fe/mL?
Solutions:
1.96 × 2.9
1.9 = For a 95% CI, N = 8.9 ≅ 9
N
2.58 × 2.9
1.9 = For a 99% CI, N = 15.6 ≅ 16
N
5-11. A volumetric calcium analysis on triplicate samples of the blood serum of a patient believed
to be suffering from a hyperparathyroid condition produced the following data: mmol
Ca/L = 3 .15, 3.25, 3.26. What is the 95% confidence interval for the mean of the data,
assuming
Solutions:
(a) no prior information about the precision of the analysis?
For the data set, x = 3.22 and s = 0.06
4.30 × 0.06
95% CI = 3.22 ± = 3.22 ± 0.15 meq Ca/L
3
(b) s → σ = 0.056 mmol Ca/L?
1.96 × 0.056
95% CI = 3.22 ± = 3.22 ± 0.06 meq Ca/L
3
5-13. A standard method for the determination of glucose in serum is reported to have a
standard deviation of 0.36 mg/dL. If s = 0.36 is a good estimate of σ , how many
replicate determinations should be made in order for the mean for the analysis of a
sample to be within
Solution:
(a) 0.3 mg/dL of the true mean 99% of the time?
2.58 × 0.36
0.3 = For the 99% CI, N = 9.6 ≅ 10
N
3
5-15. A prosecuting attorney in a criminal case presented as principal evidence small

fragments of glass found imbedded in the coat of the accused. The attorney claimed that
the fragments were identical in composition to a rare Belgian stained glass window
broken during the crime. The average of triplicate analyses for five elements in the glass
are in the table. On the basis of these data, does the defendant have grounds for
claiming reasonable doubt as to guilt? Use the 99% confidence level as a criterion for
doubt.
Concentration, ppm Standard Deviation
Element From Clothes From Window s→σ
As 129 119 9.5

Co 0.53 0.60 0.025
La 3.92 3.52 0.20
Sb 2.75 2.71 0.25
Th 0.61 0.73 0.043
Solution:
This is a two-tailed test where s → σ and from Table 5-1, zcrit = 2.58 for the 99%
confidence level.
129 − 119
For As: z = = 1.28 ≤ 2.58
3+3
9.5
3×3
No significant difference exists at the 99% confidence level.

Proceeding in a similar fashion for the other elements
Element z Significant Difference?

As 1.28 No
Co −3.43 Yes
La 2.45 No
Sb 0.20 No
Th −3.42 Yes
For two of the elements there is a significant difference, but for three there are not.
Thus, the defendant might have grounds for claiming reasonable doubt. It would be
prudent, however, to analyze other windows and show that these elements are good
diagnostics for the rare window.
4
5-17. The week 3 measurement in the data set of Problem 5-16 is suspected of being an
outlier. Use the Q test to determine if the value can be rejected at the 95% confidence
level.
Solution:
5.6 − 5.1
Q= = 0.385 and Qcrit for 8 observations at 95% confidence = 0.526.
5.6 − 4.3
Since Q < Qcrit the outlier value 5.6 cannot be rejected at the 95% confidence level.
5-19. The level of a pollutant in a river adjacent to a chemical plant is regularly monitored.
Over a period of years, the normal level of the pollutant has been established by
chemical analyses. Recently, the company has made several changes to the plant that
appear to have increased the level of the pollutant. The Environmental Protection
Agency (EPA) wants conclusive proof that the pollutant level has not increased. State the
relevant null and alternative hypotheses, and describe the type I and type II errors that
might occur in this situation.
Solution:
The null hypothesis is that for the pollutant the current level = the previous level
(H0: μcurrent = μprevious). The alternative hypothesis is Ha: μcurrent > μprevious. This would
be a one-tailed test. The type I error for this situation would be that we reject the null
hypothesis when, in fact, it is true, i.e. we decide the level of the pollutant is > the
previous level at some level of confidence when, in fact, it is not. The type II error would
be that we accept the null hypothesis when, in fact, it is false, i.e. we decide the level of
the pollutant = the previous level when, in fact, it is > than the previous level.
5-20. State quantitatively the null hypothesis H0 and the alternative hypothesis Ha for the
following situations, and describe the type I and type II errors. If these hypotheses were
to be tested statistically, comment on whether a one- or two-tailed test would be
involved for each case.
Solutions:
(a) The mean values for Ca determinations by an ion-selective electrode method and
by an EDTA titration differ substantially.
H0: μISE = μEDTA, Ha: μISE ≠ μEDTA. This would be a two-tailed test. The type I error for
this situation would be that we decide the methods do not agree when they do The
type II error would be that we decide the methods agree when they do not.
(c) Results show that the batch-to-batch variation in the impurity content of Brand X
acetonitrile is lower than Brand Y acetonitrile.
H0: σ X2 = σ Y2 ; Ha: σ X2 < σ Y2 . This is a one-tailed test. The type I error would be that we
decide that σ X2 < σ Y2 when it is not. The type II error would be that we decide that
σ X2 = σ Y2 when actually σ X2 < σ Y2 .
5
5-21. The homogeneity of the chloride level in a water sample from a lake was tested by
analyzing portions drawn from the top and from near the bottom of the lake, with the
following results in ppm Cl:
Top Bottom
26.30 26.22
26.43 26.32
26.28 26.20
26.19 26.11
26.49 26.42
Solutions:
(a) Apply the t test at the 95% confidence level to determine if the chloride level from
the top of the lake is different from that at the bottom.
For the Top data set, x = 26.338
For the bottom data set, x = 26.254
spooled = 0.1199
degrees of freedom = 5 + 5 − 2 = 8
For 8 degrees of freedom at 95% confidence tcrit = 2.31
26.338 − 26.254
t= = 1.11
5+5
0.1199
5×5
Since t < tcrit, we conclude that no significant difference exists at 95% confidence
level.
(b) If each row in the table were samples analyzed in top-bottom pairs, use the paired t
test and determine whether there is a significant difference between the top and
bottom values at the 95% confidence level.
From the data, N = 5, d = 0.084 and sd = 0.015166

For 4 degrees of freedom at 95% confidence t = 2.78
0.084 − 0
t= = 12.52
0.015 / 5
Since 12.52 > 2.78, a significant difference does exist at 95% confidence level.
(c) Why is a different conclusion drawn from using the paired t test than from just
pooling the data and using the normal t test for differences in means?
The large sample to sample variability causes sTop and sBottom to be large and masks
the differences between the samples taken from the top and the bottom.
6
5-23. Sir William Ramsey (Lord Rayleigh) prepared nitrogen samples by several different methods.
The density of each sample was measured as the mass of gas required to fill a particular flask
at a certain temperature and pressure. Masses of nitrogen samples prepared by
decomposition of various nitrogen compounds were 2.29280, 2.29940, 2.29849, and 2.30054 g.
Masses of “nitrogen” prepared by removing oxygen from air in various ways were 2.31001,
2.31163, and 2.31028 g. Is the density of nitrogen prepared from nitrogen compounds
significantly different from that prepared from air? What are the chances of the conclusion
being in error? (Study of this difference led to the discovery of the inert gases by Lord Rayleigh).
Solution:
For the first data set: x = 2.2978
For the second data set: x = 2.3106
spooled = 0.0027
Degrees of freedom = 4 + 3 − 2 = 5
2.2978 − 2.3106
t= = −6.207
4+3
0.0027
4×3
For 5 degrees of freedom at the 99% confidence level, t = 4.03 and at the 99.9% confidence
level, t = 6.87. Thus, we can be between 99% and 99.9% confident that the nitrogen prepared
in the two ways is different. The Excel TDIST(x,df,tails) function can be used to calculate the
probability of getting a t value of −6.207. In this case we find TDIST(6.207,5,2) = 0.0016.
Therefore, we can be 99.84% confident that the nitrogen prepared in the two ways is
different. There is a 0.16% probability of this conclusion being in error.
5-25. The ascorbic acid concentration in mmol/L of five different brands of orange juice was
measured. Six replicate samples of each brand were analyzed. The following partial
ANOVA table was obtained.
Variation Source SS df MS F
Between juices ______ ______ ______ 8.45
Within juices ______ ______ 0.913

Total ______ ______
Solutions:
(a) Fill in the missing entries in the table.
Source SS df MS F
Between juices 4 × 7.715 = 30.86 5−1=4 0.913 × 8.45 = 7.715 8.45
Within juices 25 × 0.913 = 22.825 30 − 5 = 25 0.913
Total 30.86 + 22.82 = 53.68 30 − 1 = 29
7
(b) State the null and alternative hypotheses.

H0: μbrand1 = μbrand2 = μbrand3 = μbrand4 = μbrand5; Ha: at least two of the means differ.
(c) Is there a difference in the ascorbic acid content of the five juices at the 95%
confidence level?
The Excel FINV(prob,df1,df2) function can be used to calculate the F value for the above
problem. In this case we find FINV(0.05,4,25) = 2.76. Since F calculated exceeds F critical,
we reject the null hypothesis and conclude that the average ascorbic acid contents of
the 5 brands of orange juice differ at the 95% confidence level.
5-27. Four analysts perform replicate sets of Hg determinations on the same analytical
sample. The results in ppb Hg are shown in the following table:
Determination Analyst 1 Analyst 2 Analyst 3 Analyst 4
1 10.19 10.19 10.14 10.24

2 10.15 10.11 10.12 10.26
3 10.16 10.15 10.04 10.29
4 10.10 10.12 10.07 10.23
Solutions:
(a) State the appropriate hypotheses.
H0: μAnalyst1 = μAnalyst2 = μAnalyst3 = μAnalyst4; Ha: at least two of the means differ.
(b) Do the analysts differ at the 95% confidence level? At the 99% confidence level
( Fcrit = 5.95 ) ? At the 99.9% confidence level ( Fcrit = 10.80 ) ?
See spreadsheet next page. From Table 5-4 the F value for 3 degrees of freedom in
the numerator and 12 degrees of freedom in the denominator at 95% is 3.49. Since
F calculated exceeds F critical, we reject the null hypothesis and conclude that the
analysts differ at 95% confidence. The F value calculated of 13.60 also exceeds the
critical values at the 99% and 99.9% confidence levels so that we can be certain that
the analysts differ at these confidence levels.
(c) Which analysts differ from each other at the 95% confidence level?
Based on the calculated LSD value of 0.0573, there are significant differences
between analysts 1 and 4, analysts 1 and 3, analysts 2 and 4, and analysts 3 and 4.
There is no significant difference between analysts 1 and 2 and 2 and 3.
8
Spreadsheet for Problem 5-27.
5-29. Three different analytical methods are compared for determining Ca in a biological
sample. The laboratory is interested in knowing whether the methods differ. The results
shown next represent Ca results in ppm determined by an ion-selective electrode (ISE)
method, by EDTA titration, and by atomic absorption spectrometry:
Repetition No. ISE EDTA Titration Atomic Absorption
1 39.2 29.9 44.0

2 32.8 28.7 49.2
3 41.8 21.7 35.1
4 35.3 34.0 39.7
5 33.5 39.1 45.9
Solutions:
(a) State the null and alternative hypotheses.
H0: μISE = μEDTA = μAA; Ha: at least two of the means differ.
9
(b) Determine whether there are differences in the three methods at the 95%
confidence levels.
See spreadsheet.
From Table 5-4 the F value for 2 degrees of freedom in the numerator and 12
degrees of freedom in the denominator at 95% is 3.89. Since F calculated is greater
than F critical, we reject the null hypothesis and conclude that the 3 methods give
different results at the 95% confidence level.
(c) If a difference was found at the 95% confidence level, determine which methods
differ from each other.
Based on the calculated LSD value there is a significant difference between the
atomic absorption method and the EDTA titration. There is no significant difference
between the EDTA titration method and the ion-selective electrode method and
there is no significant difference between the atomic absorption method and the
ion-selective electrode method.
10
5-31. Apply the Q test to the following data sets to determine whether the outlying result
should be retained or rejected at the 95% confidence level.
Solutions:
(a) 95.10, 94.62, 94.70
95.10 − 94.70
95.10 − 94.62
Since Q < Qcrit the outlier value 95.10 cannot be rejected with 95% confidence.
(b) 95.10, 94.62, 94.65, 94.70
95.10 − 94.70
95.10 − 94.62
Since Q > Qcrit the outlier value 95.10 can be rejected with 95% confidence.
11
© 2022, 978-0-357-45055-0, Chapter 6: Sampling, Standardization, and Calibration
Chapter 6
6-1. A 0.005-g sample of a rock is to be analyzed, and iron is to be determined at the ppm
level. Determine the type of analysis and type of constituent.
Answer:
The sample size is in the micro range and the analyte level is in the trace range. Hence,
the analysis is a micro analysis of a trace constituent.
6-3. Describe the steps in a sampling operation.
Answer:
Step 1: Identify the population from which the sample is to be drawn.
Step 2: Collect the gross sample.
Step 3: Reduce the gross sample to a laboratory sample, which is a small quantity of
homogeneous material.
6-5. The following results were obtained for the determination of calcium in a NIST limestone
sample: %CaO = 51.33, 51.22, 51.36, 51.21, and 51.44. Five gross samples were then
obtained for a carload of limestone. The average percent CaO values for the gross
samples were found to be 48.53, 50.75, 48.60, 48.87, and 50.29. Calculate the relative
standard deviation associated with the sampling step.
Solution:
so2 = ss2 + sm2
From the NIST sample: sm2 = 0.00947
From the gross sample: so2 = 1.073
ss = 1.07302 − 0.00947 = 1.0313
s   1.0313 
The relative standard deviation =  s  × 100% =   × 100% = 2.01%
x  51.312 
6-7. Changes in the method used to coat the tablets in Problem 6-6 lowered the percentage
of rejects from 8.0% to 3.0%. How many tablets should be taken for inspection if the
permissible relative standard deviation in the measurement is to be
1
Solutions:
(a) 15%?
N=
(1− p) = (1− 0.03) =
32.333
= 1437
pσ 2
r
0.03(0.15) 2
(0.15)2
(b) 10%?
N = 32.333/(0.10)2 = 3233
(c) 5%?
N = 32.333/(0.05)2 = 12,933
(d) 2%?
N = 32.333/(0.02)2 = 80,833
6-9. Approximately 15% of the particles in a shipment of silver-bearing ore are judged to be
argentite, Ag2S (d = 7.3 g cm−3, 87% Ag); the remainder are siliceous (d = 2.6 g cm−3) and
contain essentially no silver.
Solutions:
(a) Calculate the number of particles that should be taken for the gross sample if the
relative standard deviation due to sampling is to be 2% or less.
2 2
d d  P −P 
N = p(1− p)  A 2 B   A B 
 d   σrP 
d = 7.3 × 0.15 + 2.6 × 0.85 = 3.3
P = 0.15 × 7.3 × 0.87 × 100 / 3.3 = 29%
2 2
 7.3 × 2.6   87 − 0 
N = 0.15(1 − 0.15)     = 8714 particles
 (3.3)   0.020 × 29 
2
(b) Estimate the mass of the gross sample, assuming that the particles are spherical
and have an average diameter of 3.5 mm.
mass = (4/3)π(r)3 × d × N = (4/3) π (0.175 cm)3 × 3.3(g/cm3) × 8.714 × 103
= 650 g
(c) The sample taken for analysis is to weigh 0.500 g and contain the same number of
particles as the gross sample. To what diameter must the particles be ground to
satisfy these criteria?
0.500 = (4/3)π(r)3 × 3.3(g/cm3) × 8.714 × 103
r = 0.016 cm (diameter = 0.32 mm)
2
6-11. The data in the accompanying table represent the concentration of glucose in the blood
serum of an adult patient. On four consecutive days, a blood sample was drawn from
the patient and analyzed in triplicate. The variance for a given sample is an estimate of
the measurement variance while the day-to-day variance reflects both the measurement
variance and the sampling variance.
Day Glucose Concentration, mg/100 mL
1 62 60 63
2 58 57 57
3 51 47 48
4 54 59 57
Solutions:
(a) Perform an analysis of variance, and see whether the mean concentrations vary
significantly from day to day.
The following single-factor ANOVA table was generated using Excel’s Data Analysis Tools:
The Between Groups SS value of 264.25, the large F value, and the small P value all
indicate that the mean concentrations vary significantly from day to day.
(b) Estimate the sum of squares due to sampling.

SST is the total variance and is the sum of the within day variance, SSE, and the day-
to-day variance, SSF; SST = SSE + SSF. The within day variance, SSE, reflects the
method variance, SSM. The day-to-day variance, SSF, reflects the sum of the
method variance, SSM, and the sampling variance, SSS; SSF = SSM + SSS. Thus,
SST = SSM + SSM + SSS and SSS = SST – 2×SSM
SSS = 290.92 – 2×26.67 = 237.58. The SSS could be used to extract the sampling
variance (see D. C. Montgomery, Design and Analysis of Experiments 10th ed., Chap. 3,
Hoboken, NJ, Wiley, 2020).
3
(c) What is the best way to lower the overall variance?

The best approach to lowering the overall variance would be to reduce the
sampling variance, since this is the major component of the total variance ( σ t2 =
88.08333).
6-13. A method for the determination of the corticosteroid methylprednisolone acetate in

solutions obtained from pharmaceutical preparations yielded a mean value of 3.7 mg
mL−1 with a standard deviation of 0.3 mg mL−1. For quality control purposes, the relative
uncertainty in the concentration should be no more than 3%. How many samples of
each batch should be analyzed to ensure that the relative standard deviation does not
exceed 7% at the 95% confidence level?
Solution:
See Example 6-3
(1.96)2 × (0.3)2
Using t = 1.96 for infinite samples N= = 5.16
(3.7)2 × (0.07)2
(2.78)2 × (0.3)2
Using t = 2.78 for 5 samples (4 df) N= = 10.36
(3.7)2 × (0.07)2
(2.26)2 × (0.3)2
Using t = 2.26 for 10 samples N= = 6.85
(3.7)2 × (0.07)2
(2.45)2 × (0.3)2
(3.7)2 × (0.07)2
(2.36)2 × (0.3)2
(3.7)2 × (0.07)2
The iterations converge at between 7 and 8 samples, so 8 should be taken for safety.
6-15. The following data were obtained in calibrating a calcium ion electrode for the determination
of pCa. A linear relationship between the potential and pCa is known to exist.
pCa = −log [Ca2+] E, mV
5.00 −53.8
4.00 −27.7
3.00 +2.7
2.00 +31.9
1.00 +65.1
Solutions:
(b) Find the least-squares expression for the best straight line among the points. Plot
this line.
Equation of the line: y = –29.74x + 92.86
4
(d) Calculate the pCa of a serum solution in which the electrode potential was 15.3 mV.
Find the absolute and relative standard deviations for pCa if the result was from a
single voltage measurement.
pCaUnk = 2.608; SD in pCa = 0.079; RSD = 0.030 (CV = 3.0%)
6-17. The data in the following table were obtained during a colorimetric determination of
glucose in blood serum.
Glucose Concentration, mM Absorbance, A
0.0 0.002
2.0 0.150
4.0 0.294
6.0 0.434
8.0 0.570
10.0 0.704
Solutions:
(a) Assuming a linear relationship between the variables, find the least-squares
estimates of the slope and intercept.
m = 0.07014 and b = 0.008286
5
(b) What are the standard deviations of the slope and intercept? What is the standard
error of the estimate?
sm = 0.00067; sb = 0.004039; SE = 0.00558
(c) Determine the 95% confidence intervals for the slope and intercept.
95% CIm = m ± t × sm = 0.07014 ± 0.0019
95% CIb = b ± t × sb = 0.0083 ± 0.0112
(d) A serum sample gave an absorbance of 0.413. Find the 95% confidence interval for
glucose in the sample.
cunk = 5.77 mM; sunk = 0.09; 95% CIunk = cunk ± t × sUnk = 5.77 ± 0.24 mM
6-19. A study was made to determine the activation energy EA for a chemical reaction. The rate
constant k was determined as a function of temperature T, and the data in the following
table were obtained.
T, K k, s−1
599 0.00054
629 0.0025
647 0.0052
666 0.014
683 0.025
700 0.064
Solutions:
The data should fit a linear model of the form log k = log A − EA/(2.303RT ), where A is the
preexponential factor, and R is the gas constant.
(b) Find the slope, intercept, and standard error of the estimate.
m = –8.456; b = 10.83 and SE = 0.0459
(c) Noting that EA = −b × 2.303R × 1000, find the activation energy and its standard
deviation (Use R = 1.987 cal mol−1 K−1).
EA = –m × 2.303 × R × 1000 (Note: m has units of mK) =
–(–8.456 mK)×(2.303)×(1.987 cal mol–1 K–1)×(1000 K/mK)
= 38697 cal/mol
sEA = sm × 2.303 × R × 1000
= 1069 cal/mol
Thus, EA = 38,697 ± 1069 cal/mol or 38.7 ± 1.1 kcal/mol
6
(d) A theoretical prediction gave EA = 41.00 kcal mol−1 K−1. Test the null hypothesis that
EA is this value at the 95% confidence level.
H0: EA = 41.00 kcal/mol; HA: EA ≠ 41.00 kcal/mol.
t = (38.697 – 41.00)/1.069 = –2.15
t(0.025, 4) = 2.776
Since t > –tcrit we retain H0. There is no reason to doubt that EA is not 41.00 kcal/mol
at the 95% confidence level.
6-21. Potassium can be determined by flame emission spectrometry (flame photometry) using a
lithium internal standard. The following data were obtained for standard solutions of KCl and
an unknown containing a constant, known amount of LiCl as the internal standard. All the
intensities were corrected for background by subtracting the intensity of a blank.
cK, ppm Intensity of K Emission Intensity of Li Emission
1.0 10.0 10.0

2.0 15.3 7.5
5.0 34.7 6.8
7.5 65.2 8.5
10.0 95.8 10.0
20.0 110.2 5.8
Unknown 47.3 9.1
Solution:
(c) Calculate the concentration of K in the unknown.

5.247 ppm rounded to 5.2 ppm
6-23. The method of standard additions was used to determine nitrite in a soil sample. A 1.00-
mL portion of the sample was mixed with 24.00 mL of a colorimetric reagent, and the
nitrite was converted to a colored product that produced a blank-corrected absorbance
of 0.300. To 50.00 mL of the original sample, 1.00 mL of a standard solution of 1.00 ×
10−3 M nitrite was added. The same color-forming procedure was followed, and the new
absorbance was 0.530. What was the concentration of nitrite in the original undiluted
sample?
7
Solution:
See Example 6-8.
(0.300)(1.00 × 10 −3 )(1.00)
cu = = 2.4938 × 10–5 M
(0.530)(51.00) − (0.300)(50.00)
To obtain the concentration of the original sample, we need to multiply by 25.00/1.00.
cu = (2.4938×10–5 M)(25.00)/(1.00) = 6.23 × 10–4 M
6-25. Atomic emission measurements were made to determine sodium in a blood serum
sample. The following emission intensities were obtained for standards of 5.0 and 10.0
ng/mL and for the serum sample. All emission intensities were corrected for any blank
emission. The mean value for the blank intensity (cNa = 0.0) was 0.000 with a standard
deviation of 0.0071 (arbitrary units).
cNa, ng/mL Emission Intensity
5.0 0.51
5.0 0.49
5.0 0.48
10.0 1.02
10.0 1.00
10.0 0.99
Serum 0.71
Serum 0.77
Serum 0.78
Solution:
(c) Find the detection limit for k values of 2 and 3. To what level of confidence do these
correspond?
For k = 2, DL = 0.14 ng/mL (92.1% confidence level)
for k = 3, DL = 0.21 ng/mL (98.3% confidence level)
6-27. The following table gives the sample means and standard deviations for six
measurements each day of the purity of a polymer in a process. The purity is monitored
for 24 days. Determine the overall mean and standard deviation of the measurements,
and construct a control chart with upper and lower control limits. Do any of the means
indicate a loss of statistical control?
8
Day Mean SD Day Mean SD
1 96.50 0.80 13 96.64 1.59

2 97.38 0.88 14 96.87 1.52
3 96.85 1.43 15 95.52 1.27
4 96.64 1.59 16 96.08 1.16
5 96.87 1.52 17 96.48 0.79
6 95.52 1.27 18 96.63 1.48
7 96.08 1.16 19 95.47 1.30
8 96.48 0.79 20 96.43 0.75
9 96.63 1.48 21 97.06 1.34
10 95.47 1.30 22 98.34 1.60
11 97.38 0.88 23 96.42 1.22
12 96.85 1.43 24 95.99 1.18
Solution:
The process went out of control on Day 22.
9
© 2022, 978-0-357-45055-0, Chapter 7: Aqueous Solutions and Chemical Equilibria
Chapter 7
7-1. Briefly describe or define and give an example of
Solutions:
(a) a strong electrolyte.
A strong electrolyte totally ionizes when dissolved in water. HCl is an example of a
strong electrolyte.
(c) the conjugate acid of a Brønsted-Lowry base.

The conjugate acid of a Brønsted-Lowry base is the potential proton donor formed
when a Brønsted-Lowry base accepts a proton. For example, the NH4+ is a
conjugate acid in the reaction, NH3 + proton  NH4 + .
(e) an amphiprotic solute.

An amphiprotic solute can act either as an acid or a base depending on the situation
An amino acid is an amphiprotic solute.
(g) autoprotolysis.
Autoprotolysis is the act of self-ionization to produce both a conjugate acid and a
conjugate base.
(i) Le Châtelier’s principle.

The Le Châtelier principle states that the position of an equilibrium always shifts in
such a direction that it relieves the stress. A common ion like sulfate added to a
solution containing sparingly soluble BaSO4 is an example.
7-2. Briefly describe or define and give an example of
Solutions:
(a) an amphiprotic solvent.
An amphiprotic solvent can act either as an acid or a base depending on the solute.
Water is an example of an amphiprotic solvent since it can act as a proton donor or
a proton acceptor.
1
(c) a leveling solvent.

A leveling solvent shows no difference between strong acids. Perchloric acid and
hydrochloric acid ionize completely in water; thus, water is a leveling solvent.
7-3. Briefly explain why there is no term in an equilibrium-constant expression for water or
for a pure solid, even though one (or both) appears in the balanced net ionic equation
for the equilibrium.
Solution:
For dilute aqueous solutions, the concentration of water remains constant and is
assumed to be independent of the equilibrium. Thus, its concentration is included within
the equilibrium constant. For a pure solid, the concentration of the chemical species in
the solid phase is constant. As long as some solid exists as a second phase, its effect on
the equilibrium is constant and is included within the equilibrium constant.
7-4. Identify the acid on the left and its conjugate base on the right in the following
equations:
(a) PO4 3 − + H2PO4 −  2HPO4 2 −
(b) NH+4 + H2O  NH3 + H3O+
(e) HOCl + H2O  H3O+ + OCl−
Solutions:
Acid Conjugate Base
(a) H2PO4 −
HPO42−
(b) NH+4 NH3
(e) HOCl OCl−
7-6. Write expressions for the autoprotolysis of
Solutions:
(a) H2 O.
2H2O  H3O+ + OH−
(c) CH3NH2 .
2CH3NH2  CH3NH3+ + CH3NH−
2
7-7. Write the equilibrium-constant expressions and obtain numerical values for each
constant in
Solutions:
(a) the basic dissociation of aniline, C 6H5NH2 .
C6H5NH2 +H2O  C6H5NH3+ +OH−
1.00×10−14 [C6H5NH3 ][OH ]

+
Kw −
Kb = = = = 3.98 × 10−4
Ka 2.51×10−11 [C6H5NH2 ]
(c) the acidic dissociation of methyl ammonium hydrochloride, CH3NH3 Cl.
CH3NH3 + + H2O  CH3NH2 + H3O+

K w [CH3NH2 ][H3 O+ ]
Ka = = = 2.3 × 10 −11
Kb [CH3NH3 ]+
(e) the dissociation of H3 AsO3 to H3O+ and AsO33 − .
H3 AsO4 + H2O  H3O+ + H2 AsO4 −

H2 AsO4 − + H2O  H3O+ + HAsO4 2 −
HAsO4 2 − + H2O  H3O+ + AsO4 3 −
H3 AsO4 + 3H2O  3H3O+ + AsO4 3
[H3O+ ][H2 AsO4 − ] [H3O+ ][HAsO4 2 − ] [H3O+ ][AsO4 3− ]

K a1 = K a2 = K a3 =
[H3 AsO4 ] [H2 AsO4 − ] [HAsO4 2 − ]
[H3O+ ]3 [AsO4 3− ]
K overall = = K a1K a2 K a3 = 5.8 × 10−3 × 1.1× 10−7 × 3.2 × 10−12 = 2.0 × 10−21
[H3 AsO4 ]
7-8. Generate the solubility-product expression for
Solutions:
(a) CuBr.
CuBr( s )  Cu+ + Br − K sp = [Cu+ ][Br − ]
(b) MgCO3.
MgCO3 ( s)  Mg2 + + CO32 − K sp = [Mg2 + ][CO32 − ]
(c) PbCl2.
PbCl2 ( s )  Pb2 + + 2Cl− K sp = [Pb2 + ][Cl− ]2
3
7-10. Calculate the solubility-product constant for each of the following substances, given that
the molar concentrations of their saturated solutions are as indicated:
Solutions:
(b) RaSO4 (6.6 × 10−6 M).
RaSO4  Ra2− + SO42−

[Ra2+] = [SO42−] = 6.6 × 10−6 M
Ksp = [Ra2+][SO42−] = (6.6 × 10−6 M)2 = 4.4 × 10−11
(d) Ce(IO3)3 (1.9 × 10–3 M).
Ce(IO3)3  Ce3+ + 3IO3−

[Ce3+] = 1.9 × 10−3 M [IO3−] = 3 × 1.9 × 10−3 M = 5.7 × 10−3 M
Ksp = [Ce3+][IO3−]3 = 1.9 × 10−3 × (5.7 × 10−3)3 = 3.5 × 10−10
7-13. What CrO4 2 − concentration is required to
Ag2CrO4(s)  2Ag+ + CrO42−
Solutions:
(a) initiate precipitation of Ag2CrO4 from a solution that is 5.24 × 10 − 3 M in Ag + ?
1.2 × 10 −12
[CrO4 2 − ] = = 4.37 × 10−8 M
(5.24 × 10 −3 )2
(b) lower the concentration of Ag+ in a solution to 7.82 × 10−7 M?
1.2 × 10 −12
[CrO4 2 − ] = = 1.96 M
(7.82 × 10 −7 )2
7-15. The solubility-product constant for Ce(IO3)3 is 3.2 × 10−10. What is the Ce3+ concentration
in a solution prepared by mixing 50.00 mL of 0.0500 M Ce3+ with 50.00 mL of
Ce3+ + 3IO3−  Ce(IO3)3(s)

Ksp = [Ce3+][IO3−]3 = 3.2 × 10−10
Solutions:
(a) water?
50.00 mL × 0.0500 mmol/ml = 2.50 mmol Ce3+
2.50 mmol
[Ce 3 + ] = = 0.0250 M
(50.00 + 50.00) mL
4
(b) 0.0500 M IO3−?

We mix 2.50 mmol Ce3+ with 50.00 mL × 0.050 mmol/mL = 2.50 mmol IO3−.
Each mole of IO3− reacts with 1/3 mole of Ce3+ so 2.50 mmol would consume 1/3 ×
2.50 mmol Ce3+ or the amount of unreacted Ce3+ = 2.50 − 2.50/3 = 1.666 mmol
1.666 mmol
cCe3+ = = 0.0166 M
100 mL
[Ce3+] = 0.0166 + S (where S is the solubility). Assume S is small so [Ce3+] = 0.0166
[IO3−] = 3S
Ksp = [Ce3+][IO3−]3 = 0.0166 × (3S)3 = 3.2 × 10−10
1/3
 3.2 × 10−10 
S = −2 
= 8.9 × 10−4
 27 × 1.66 × 10 
[Ce3+] = 1.66 × 10−2 + 8.9 × 10−4 = 1.7 × 10−2 M
(c) 0.250 M IO3−?

Now we have 0.250 mmol IO3− × 50.00 mL = 12.5 mmol. Since 3 × 2.50 mmol = 7.50
mmol would be required to completely react with the Ce3+, we have excess IO3−.
12.5 mmol − 7.50 mmol
[IO3 − ] = + 3S = 0.0500 + 3S
100 mL
[Ce3+] = S
Ksp = S(0.0500 + 3S)3 = 3.2 × 1010
Lets assume 3S << 0.0500
S = [Ce3+] = 3.2 × 10−10/(0.0500)3 = 2.6 × 10−6 M
Checking the assumption 3 × 2.6 × 10−6 M = 7.8 × 10−6 which is much smaller than
0.0500.
(d) 0.0450 M IO3−?

Now we are mixing 2.50 mmol Ce3+ with 50.00 mL × 0.045 mmol/mL = 2.25 mmol
IO3. The Ce3+ is now in excess so that amount of Ce3+ = 2.50 mmol − 2.25/3 mmol =
1.75 mmol
1.75 mmol
cCe3+ = = 0.0175 M
100 mL
[Ce3+] = 1.75 × 10−2 + S
Ksp = [Ce3+][IO3−]3 = 0.0175 × (3S)3 = 3.2 × 10−10
1/3
 3.2 × 10−10 
S = −2 
= 8.78 × 10−4
 27 × 1.75 × 10 
[Ce3+] = 1.75 × 10−2 + 8.78 × 10−4 = 1.8 × 10−2 M
5
7-17. The solubility products for a series of iodides are
CuI K sp = 1× 10 −12
AgI K sp = 8.3 × 10 −17
PbI2 K sp = 7.1× 10−9
BiI3 K sp = 8.1× 10 −19
List these four compounds in order of decreasing molar solubility in

Solutions:
CuI(s)  Cu+ + I− Ksp = [Cu+][I−] = 1 × 10−12
AgI(s)  Ag+ + I− Ksp = [Ag+][I−] = 8.3 × 10−17
PbI2(s)  Pb2+ + 2I− Ksp = [Pb2+][I−]2 = 7.1 × 10−9 = S(2S)2 = 4S3
BiI3(s)  Bi3+ + 3I− Ksp = [Bi3+][I−]3 = 8.1 × 10−19 = S(3S)3 = 27S4
(a) water.
For CuI, S = [Cu+] = [I−] = 1× 10 −12 = 1× 10 −6 M
For AgI, S = [Ag+] = [I−] = 8.3 × 10 −17 = 9.1× 10 −9 M
7.1× 10−9
For PbI2, S = 3 = 1.2 × 10−3 M
4
8.1× 10−19
For BiI3 S = 4 = 1.3 × 10−5 M
27
So, solubilities are in the order PbI2 > BiI3 > CuI > AgI
(b) 0.20 M NaI.

For CuI, S = 1 × 10−12/0.20 = 5 × 10−12 M
For AgI, S = 8.3 × 10−17/0.20 = 4.2 × 10−16 M
For PbI2, S = 7.1 × 10−9/(0.20)2 = 1.8 × 10−7 M
For BiI3, S = 8.1 × 10−19/(0.20)3 = 1.0 × 10−16 M
So, solubilities are in the order PbI2 > CuI > AgI > BiI3
(c) a 0.020 M solution of the solute cation.

For CuI, S = 1 × 10−12/0.020 = 5 × 10−11 M
For AgI, S = 8.3 × 10−17/0.020 = 4.2 × 10−15 M
1 7.1× 10 −9
For PbI2, S = = 3.0 × 10 −4 M
2 0.020
1 3 8.1× 10 −19
For BiI3, S = = 1.1× 10 −6 M
3 0.020
So, solubilities are in the order, PbI2 > BiI3 > CuI > AgI
6
7-20. At 25ºC, what are the molar H3O+ and OH− concentrations in
Solutions:
(a) 0.0300 M HCOOH?
For formic acid, Ka = 180 × 10−5. Call formic acid HFm and the formate anion Fm−
HFm + H2O  Fm− + H3O+
[Fm− ][H3O+ ]
Ka = = 1.80 × 10 −4 Mass balance cHFm = [HFm] + [Fm−] = 0.0300
[HFm]
[Fm−] = [H3O+] Thus, [HFm] = 0.0300 [Fm−] = 0.0300 − [H3O+]
[H3O+ ]2
= 1.80 × 10−4
0.0300 − [H3O ] +
Solving the quadratic or solving by iterations gives,

[H3O+] = 2.24 × 10−3 M so [OH−] = 1.00 × 10−14/2.24 × 10−3 = 4.5 × 10−12 M
(c) 0.200 M ethylamine?
C2H5NH2 +H2O  C2H5NH3+ +OH−

[C2H5NH3+ ][OH− ] K w 1.0 × 10−14
Kb = = = = 4.33 × 10 −4
[C2H5NH2 ] K a 2.31× 10 −11
[OH ]=[C2H5NH3+ ]
−
[C2H5NH2 ] = 0.200 − [OH− ]
[OH− ]2
= 4.33 × 10−4 [OH− ]2 = 4.33 × 10−4 (0.200 − [OH− ])
(0.200 − [OH ])
−
[OH− ]2 + 4.33 × 10 −4 [OH− ] − 8.66 × 10 −5 = 0

−4.33 × 10 −4 + (4.33 × 10 −4 )2 + 4(8.66 × 10 −5 )
[OH− ] = = 9.09 × 10 −3 M
2
1.0 × 10 −14
[H3O+ ] = = 1.1× 10 −12 M
9.09 × 10 −3
(e) 0.250 M C6H5COONa (sodium benzoate)?
Bz + H2O  HBz + OH− Kb = Kw/Ka = 1.00 × 10−14/6.28 × 10−5 = 1.60 × 10−10

[OH−] = [HBz] [Bz] = 0.250 − [OH−]
[OH− ]2
= 1.60 × 10 −10
0.250 − [OH− ]
[OH−] = 6.32 × 10−6 M [H3O+] = 1.00 × 10−14/6.32 × 10−6 = 1.58 × 10−9 M
7
(g) 0.250 M hydroxylamine hydrochloride?
HONH3+ + H2O  HONH2 +H3O+ Ka = 1.1 × 10−6
[H3O+ ]2
As in part (b) = 1.1 × 10−6
0.250 − [H3O+ ]
[H3O+] = 5.24 × 10−4 M [OH−] = 1.91 × 10−11 M
7-21. At 25°C, what is the hydronium ion concentration in
Solutions:
(a) 0.100 M chloroacetic acid?
[ClCH2COO− ][H3O+ ]
ClCH2 COOH+H2 O  ClCH2 COO− + H3O+ Ka = = 1.36 × 10 −3
[ClCH2COOH]
[H3O+ ] = [ClCH2COO− ] [ClCH2COOH] = 0.100 − [H3O+ ]
[H3O+ ]2
= 1.36 × 10 −3 [H3O+ ]2 =1.36×10 −3 (0.100 − [H3O+ ])
(0.100 − [H3O+ ])
[H3O+ ]2 + 1.36 × 10 −3 [H3O+ ] − 1.36 × 10 −4 = 0
−1.36 × 10 −3 + (1.36 × 10 −3 )2 + 4(1.36 × 10 −4 )
[H3O+ ] = = 1.10 × 10 −2 M
2
(b) 0.100 M sodium chloroacetate?
ClCH2COO− + H2O  ClCH2COOH + OH−

[ClCH2COOH][OH− ] Kw 1.0 × 10−14
Kb = = = = 7.35 × 10−12
[ClCH2COO− ] Ka 1.36 × 10 −3
[OH− ] = [ClCH2COOH] [ClCH2COO− ] = 0.100 M − [OH− ]

[OH− ]2
= 7.35 × 10−12 [OH− ]2 = 7.35 × 10−12 (0.100 − [OH− ])
(0.100 − [OH− ])
[OH− ]2 + 7.35 × 10 −12 [OH− ] − 7.35 × 10−13 = 0
[OH− ] = 8.57 × 10−7 M
1.0 × 10−14
[H3O+ ] = = 1.17 × 10−8 M
8.57 × 10−7
(e) 1.50 × 103 M aniline hydrochloride?
[C6H5NH2 ][H3O+ ]
C6H5NH3+ + H2O  C6H5NH2 + H3O+ Ka = = 2.51 × 10−5
[C6H5NH3 ]
+
+
[H3O ] = [C6H5NH2 ] [C6H5NH3+ ] = 0.0015 M − [H3O+ ]
[H3O+ ]2
= 2.51× 10 −5
(0.0015 − [H3O+ ])
Proceeding as in part (d), we find [H3O+] = 1.82 × 10−4 M
8
7-23. Define buffer capacity.
Answer:
Buffer capacity of a solution is defined as the number of moles of a strong acid (or a
strong base) that causes 1.00 L of a buffer to undergo a 1.00-unit change in pH.
7-25. Consider solutions prepared by
HOAc + H2O  OAc− + H3O+ OAc− + H2O  HOAc + OH−
Solutions:
(a) dissolving 8.00 mmol of NaOAc in 200 mL of 0.100 M HOAc.
8.00 mmol
[OAc − ] = = 4 × 10 −2 M
200 mL
[HOAc] = 0.100 M
4 × 102
pH = −log(1.75 × 10 −5 ) + log = 4.359
0.100
(b) adding 100 mL of 0.0500 M NaOH to 100 mL of 0.175 M HOAc.

0.175 mmol
0.175 M HOAc = × 100 mL = 17.5 mmol
mL
0.0500 mmol
0.0500 M NaOH = × 100 mL = 5.00 mmol
mL
(17.5 − 5.00) mmol
[HOAc] = = 6.25 × 10−2 M
200 mL
5 mmol
[OAc− ] = = 2.50 × 10−2 M
200 mL
2.50 × 10−2
pH = −log(1.75 × 10 −5 ) + log = 4.359
6.25 × 10−2
(c) adding 40.0 mL of 0.1200 M HCl to 160.0 mL of 0.0420 M NaOAc.

In what respects do these solutions resemble one another? How do they differ?
0.042 mmol
0.0420 M OAc − = × 160 mL = 6.72 mmol
mL
0.1200 mmol
0.1200 M HCl = × 40.0 mL = 4.80 mmol
mL
(6.72 − 4.80) mmol
[OAc − ] = = 9.6 × 10 −3 M
200 mL
4.8 mmol
[HOAc] = = 2.4 × 10 −2 M
200 mL
9.6 × 10 −3
pH = − log(1.75 × 10 −5 ) + log = 4.359
2.4 × 10 −2
The solutions all are buffers with the same pH, but they differ in buffer capacity
with (a) having the greatest and (c) the least.
9
7-26. Consult Appendix 3, and pick out a suitable acid-base pair to prepare a buffer with a pH of
Solutions:
(a) 10.3.
The closest are C2H5NH3+/ C2H5NH2 (pKa = 10.64) and CH3NH3+/CH3NH2 (pKa = 10.64)
(c) 4.5.
C6H5NH3+/C6H5NH2 (pKa = 4.60)
7-27. What mass of sodium formate must be added to 500.0 mL of 1.00 M formic acid to
produce a buffer solution that has a pH of 3.75?
Solution:
[HCOO− ] [HCOO− ]
pH = 3.75 = pK a + log = − log(1.8 × 10−4 ) + log
[HCOOH] [HCOOH]
[HCOO− ] [HCOO− ]
3.75 = 3.74 + log = 100.01 = 1.02
[HCOOH] [HCOOH]
mmol HCOOH
500 mL × 1.00 = 500 mmol HCOOH
mL
So amount of HCOO− needed = 1.02 × 500 mmol = 511.6 mmol
511.6 mmol × 10−3 mol/mmol = 0.5116 mol HCOO−
Mass HCOONa = 0.5116 mol × 67.997 g/mol = 34.79 g
7-29. What volume of 0.200 M HCl must be added to 500.0 mL of 0.300 M sodium mandelate
to produce a buffer solution with a pH of 3.25?
Solution:
Let HMn = mandelic acid, Mn− = mandelate anion.
500 mL × 0.300 M NaMn = 150 mmol Mn.
For a pH of 3.25 need the ratio of Mn− to HMn to be
[Mn− ] [Mn− ] [Mn− ]
pH = 3.25 = pK a + log = 3.398 + log log = 3.25 − 3.398 = −0.148
[HMn] [HMn] [HMn]
[Mn− ]
= 0.711
[HMn]
mmol Mn− − x mmol HCl
= 0.711
x mmol HCl
0.711 × x mmol HCl = mmol Mn− x mmol HCl
x = mmol Mn−/1.711 = 150 mmol Mn−/1.711 = 87.66 mmol HCl
Volume HCl = 87.66 mmol/(0.200 mmol/mL) = 438 mL
10
© 2022, 978-0-357-45055-0, Chapter 8: Effect of Electrolytes on Chemical Equilibria
Chapter 8
8-1. Make a distinction between
Answers:
(a) activity and activity coefficient.
Activity, aA, is the effective concentration of a chemical species A in solution. The
activity coefficient, γA, is the numerical factor necessary to convert the molar
concentration of the chemical species A to activity as shown below:
aA=γA[A]
(b) thermodynamic and concentration equilibrium constants.

The thermodynamic equilibrium constant refers to an ideal system within which each
chemical species is unaffected by any others. A concentration equilibrium constant
takes into account the influence exerted by solute species upon one another. The
thermodynamic equilibrium constant is numerically constant and independent of
ionic strength; the concentration equilibrium constant depends on molar
concentrations of reactants and products as well as other chemical species that
may not participate in the equilibrium.
8-3. Neglecting any effects caused by volume changes, would you expect the ionic strength to
(1) increase, (2) decrease, or (3) remain essentially unchanged when NaOH is added to a
dilute solution of
Answers:
(a) magnesium chloride [ Mg ( OH)2 ( s ) ] forms?
MgCl2 + 2NaOH  Mg(OH)2 (s) + 2NaCl

Replacing divalent Mg2+ with Na+ causes the ionic strength to decrease.
(b) hydrochloric acid?

HCl + NaOH  H2O + NaCl
There is no change in the charge states of the ions present in the solution
equilibria. The ionic strength is unchanged.
1
(c) acetic acid?

HOAc + NaOH  H2O + NaOAc
The ionic strength will increase because NaOH and NaOAc are totally ionized
wheras acetic acid is only partially ionized.
8-5. Explain why the activity coefficient for dissolved ions in water is usually less than that for
water itself.
Answer:
Water is a neutral molecule and its activity equals its concentration at all low to
moderate ionic strengths. That is, its activity coefficient is unity. In solutions of low to
moderate ionic strength, activity coefficients of ions decrease with increasing ionic
strength because the ionic atmosphere surrounding the ion causes it to lose some of its
chemical effectiveness and its activity is less than its concentration.
8-7. Explain why the initial slope for Ca2+ in Figure 8-3 is steeper than that for K+?
Answer:
Multiply charged ions deviate from ideality more than singly charged ions because of the
effect of the surrounding ionic atmosphere. The initial slope of the activity coefficient vs
square root of ionic strength for Ca2+ is steeper than that for K+ because the activity
coefficient of Ca2+ is more influenced by ionic strength than that for K+.
8-9. Calculate the ionic strength of a solution that is
Solutions:
(a) 0.025 M in FeSO4 .
μ = ½[0.025 × 22 + 0.025 × 22] = 0.10
(c) 0.25 M in FeCl3 and 0.15 M in FeCl2 .
μ = ½[0.25 × 32 + 0.75 × 12 + 0.15 × 22 + 0.30 × 12] = 1.95
8-10. Use Equation 8-5 to calculate the activity coefficient of
0.51Z X2 μ
− log γ X = This problem is easiest to work with a spreadsheet.
1 + 3.3α X μ
2
Rounding these results, gives for the γ X

Solutions:
(a) Fe31 at μ = 0.057.
0.23
(c) Ce41 at μ = 0.065.
0.08
8-12. For a solution in which μ = 6.5 × 10−2 , calculate K sp

′ for
Solutions:
(a) AgSCN.
0.51Z X2 μ
We must use − log γ X =
1 + 3.3α X μ
For Ag , α Ag+ = 0.25. At μ = 0.065, γ Ag+ = 0.7809; For SCN−, α SCN − = 0.35 and
+
γ SCN = 0.7935 retaining insignificant figures for later calculations.

−
K sp 1.1 × 10 −12
K sp
′ = = = 1.8 × 10−12
γ Ag γ SCN
+ − (0.7809)(0.7935)
(c) La (IO3 )3 .
For La3+, γ La3+ = 0.2158. For IO3−, γ IO − = 0.7935

3
K sp 1.0 × 10 −11
K sp
′ = = = 9.3 × 10 −11
γ La γ IO
3+ − (0.2158)(0.7935)3
3
3
8-13. Use activities to calculate the molar solubility of Zn ( OH)2 in
Solutions:
(a) 0.0150 M KCl.
Zn(OH)2(s)  Zn2+ + 2OH− Ksp = 3.0 × 10−16

μ = ½[0.015 × 12 + 0.015 × 12] = 0.0150
Using Equation 8-5,
γ Zn2+ = 0.6294 γ OH− = 0.8816
2
K sp
′ = aZn2+ aOH− = γ
Zn2+
[Zn2+ ] × γ OH
2 − 2
− [OH ]
3.0 × 10 −16 3.0 × 10 −16

[Zn2 + ][OH− ]2 = = = 6.133 × 10 −16
2
γ Zn γ OH
2+ − (0.6294)(0.8816)2
Solubility = S = [Zn2+] = ½[OH−]

S(2S)2 = 6.133 × 10−16
1/3
 6.133 × 10 −16 
S =  = 5.35 × 10−6 M
 4 
(b) 0.0250 M K 2 SO4 .
μ = ½[2 × 0.0250 × 12 + 0.0250 × 22] = 0.15/2 = 0.075

From Equation 8-5,
γ Zn2+ = 0.434 γ OH− = 0.783
K sp 2
′ = aZn2+ aOH− = γ
Zn2+
[Zn2+ ] × γ OH
2
− [OH ]
− 2
3.0 × 10 −16
[Zn2+ ][OH− ]2 = = 1.127 × 10 −15
(0.434)(0.783)2
Solubility = S = [Zn2+] = ½[OH−]

S(2S)2 = 1.127 × 10−15
1
 1.127 × 10 −15  3
S =  = 6.6 × 10 M
−6
 4 
(c) the solution that results when you mix 40.0 mL of 0.250 M KOH with 60.0 mL of
0.0250 M ZnCl2 .
0.250 mmol
amount of KOH = × 40.0 mL = 10.0 mmol
mL
0.0250 mmol
amount of ZnCl2 = × 60.0 mL = 1.5 mmol
mL
4
10 mmol
[K + ] = = 0.10 M
100.0 mL
[OH− ] =
(10 mmol − (2 × 1.5 mmol) ) = 0.07 M
100.0 mL
2 × 1.5 mmol
[Cl− ] = = 0.03 M
100.0 mL
[Zn2+ ] = 0
μ = ½[0.10 × 12 + 0.07 × 12 + 0.03 × 12] = 0.10
From Table 8-2,
2
γ Zn = 0.40
2+ γ OH = 0.76
−
′ = aZn2+ aOH
K sp − = γ
Zn2+
[Zn2+ ] × γ OH
2 − 2
− [OH ]
3.0 × 10−16 3.0 × 10−16

[Zn2+ ][OH− ]2 = 2
= 2
= 1.298 × 10 −15
γ Zn γ OH
2+ − (0.40)(0.76)
2+
Solubility = S = [Zn ] S (0.07)2 = 1.298 × 10−15
 1.298 × 10−15  −13
S = 2  = 2.6 × 10 M
 (0.07) 
(d) the solution that results when you mix 20.0 mL of 0.100 M KOH with 80.0 mL of
0.0250 M ZnCl2 .
0.100 mmol
amount KOH = × 20.0 mL = 2.0 mmol
mL
0.0250 mmol
amount ZnCl2 = × 80.0 mL = 2.0 mmol
mL
2 mmol
[K + ] = = 0.02 M
100.0 mL
[OH− ] = 0
2 × 2.0 mmol
[Cl− ] = = 0.04 M
100.0 mL
1
2 mmol − (2 mmol)
[Zn2 + ] = 2 = 0.01 M
100.0 mL
1
μ=
2
(
0.02 × 12 + 0.040 × 12 + 0.01× 22 = 0.05 )
From Table 10-2,
γ Zn2+ = 0.48 γ OH− = 0.81
K sp 2
′ = aZn2+ aOH− = γ
Zn2+
[Zn2+ ] × γ OH
2 − 2
− [OH ]
3.0 × 10 −16 3.0 × 10−16

[Zn2+ ][OH− ]2 = = = 9.53 × 10 −16
2
γ Zn γ OH
2+ − (0.48)(0.81)2
5
Solubility = S = [OH− ] / 2
(0.01)[OH− ]2 = 9.53 × 10 −16
1
 9.53 × 10 −16  2
[OH ] = 
−
 = 3.09 × 10 M
−7
 0.01 
( )
S = 3.09 × 10 M /2 = 1.5 × 10 −7 M
−7
8-14. Calculate the solubilities of the following compounds in a 0.0275 M solution of

Mg ( ClO4 )2 using (1) activities and (2) molar concentrations:
Solutions:
(a) AgSCN.
μ = ½[0.0275 × 22 + 2 × 0.0275 × 12] = 0.0825 Cannot use data in Table 8-2. Use
Equation 8-5
AgSCN(s)  Ag+ + SCN−
(1) For Ag+, γ Ag+ = 0.761; for SCN−, γ SCN − = 0.776
K sp = γ Ag+ [Ag + ]γ SCN− [SCN− ] = 1.1× 10 −12

1.1× 10 −12
[Ag + ][SCN− ] = = 1.86 × 10 −12
0.761× 0.776
S = [Ag+] = [SCN−]
S = 1.86 × 10−12 = 1.4 × 10−6 M
(2) S = 1.1× 10−12 = 1.0 × 10−6 M
(b) PbI2 .
PbI2 (s)  Pb2+ + 2I−

(1) γ Pb2+ = 0.388 γ I− = 0.769 K sp
′ = aPb2+ aI2− = γ Pb2+ [Pb2+ ] × (γ I− [I− ])2
7.9 × 10−9 7.9 × 10 −9
[Pb2+ ][I− ]2 = = = 3.44 × 10−8
γ Pb γ I
2+ −
2
(0.388)(0.769)2
1 −
Solubility = S = [Pb2 + ] = [I ]
2
S (2S )2 = 3.44 × 10 −8
1
 3.44 × 10−8  3
S =  = 2.0 × 10 M
−3
 4 
1
 7.9 × 10−9  3
(2) S =  = 1.3 × 10 M
−3
 4 
6
(c) BaSO4 .
BaSO4(s)  Ba2+ + SO42−

γ Ba = 0.40; γ SO
2+ 2− = 0.376
4
1.1× 10 −10 1.1× 10 −10

[Ba2 + ][SO4 2 − ] = = = 7.3 × 10−10
γ Ba γ SO2+ 2− (0.40)(0.376)
4
Solubility = S = [Ba ] = [SO4 2 − ] 2+
S 2 = 7.3 × 10 −10
S = 7.3 × 10 −10 = 2.7 × 10 −5 M
(2) S = 1.1 × 10−10 = 1.0 × 10−5 M
(d) Cd2Fe ( CN)6 .
Cd2Fe(CN)6 (s)  2Cd2+ + Fe(CN)6 4 −

K sp = 3.2 × 10−17
Cd2Fe(CN)6(s)  2Cd2+ + Fe(CN)64−

(1) γ Cd2+ = 0.40 γ Fe(CN) 4− = 0.020
6
3.2 × 10−17 3.2 × 10−17

[Cd ] [Fe(CN)6 ] =
2+ 2 4−
= = 1.00 × 10 −14
2
γ Cd γ Fe(CN)
2+ 4− (0.40) (0.020)
2
6
1
Solubility = S = [Cd2 + ] = [Fe(CN)6 4 − ]
2
(2S )2 S = 1.00 × 10 −14
1
 1.00 × 10 −14  3
S =  = 1.4 × 10 M
−5
 4 
1
 3.2 × 10 −17  3
(2) S =  = 2.0 × 10 M
−6
 4 
8-15. Calculate the solubilities of the following compounds in a 0.0167 M solution of Ba (NO3 )2
using (1) activities and (2) molar concentrations:
Solutions:
(a) AgIO3 .
μ = ½[0.0167 × 22 + 2 × 0.0167 × 12] = 0.050

AgIO3(s)  Ag+ + IO3−
7
(1) γ Ag+ = 0.80 γ IO − = 0.82

3
3.1× 10 −8 3.1× 10 −8
[Ag + ][IO3 − ] = = = 4.7 × 10 −8
γ Ag γ IO
+ − (0.80)(0.82)
3
Solubility = S = [Ag ] = [IO3 − ]

+
S 2 = 4.7 × 10 −8
S = 4.7 × 10−8 = 2.2 × 10 −4 M
(2) S = 3.1× 10−8 = 1.8 × 10 −4 M
(b) Mg ( OH)2 .
Mg(OH)2(s)  Mg2+ + 2OH−

(1) γ Mg = 0.52 γ OH = 0.81
2+ −
7.1× 10 −12 7.1× 10 −12

[Mg2 + ][OH− ]2 = 2
= = 2.081× 10−11
γ Mg γ OH 2+ − (0.52)(0.81)2
1
Solubility = S = [Mg2 + ] = [OH− ]
2
S (2S )2 = 2.081× 10−11
1
 2.081× 10 −11  3 −4
S =  = 1.7 × 10 M
 4 
1
 7.1× 10 −12  3 −4
(2) S =  = 1.2 × 10 M
 4 
(c) BaSO4 .
BaSO4(s)  Ba2+ + SO42−
(1) γ Ba2+ = 0.46 γ SO 2− = 0.44

4
1.1× 10 −10 1.1× 10 −10

2+
[Ba ][SO4 ] = 2−
= = 5.435 × 10 −10
γ Ba γ SO
2+ 2− (0.46)(0.44)
4
Solubility = S = [SO4 ] 2−
(0.0167) × S = 5.435 × 10−10

 5.435 × 10 −10 
S = −8
 = 3.3 × 10 M
 0.0167 
 1.1× 10 −10 
(2) S =  −9
 = 6.6 × 10 M
 0.0167 
8
(d) La (IO3 )3 .
La(IO3)3(s)  La3+ + 3IO3
(1) γ La3+ = 0.24 γ IO = 0.82 K sp = aLa aIO3 = γ La [La3+ ] × (γ IO [IO3 − ])3

− 3+ − 3+ −
3 3 3
1.0 × 10 −11
1.0 × 10−11
[La3+ ][IO3 − ]3 = 3
= = 7.557 × 10 −11
γ La γ IO
3+ − (0.24)(0.82)3
3
1
Solubility = S = [La3 + ] = [IO3 − ]
3
S (3S )3 = 7.557 × 10 −11

1
 7.557 × 10−11  4 −3
S =  = 1.3 × 10 M
 27 
1
 1.0 × 10 −11  4 −4
(2) S =  = 7.8 × 10 M
 27 
8-16. Calculate the % relative error in solubility by using concentrations instead of activities for
the following compounds in 0.0350 M KNO3 using the thermodynamic solubility
products listed in Appendix 2.
Solutions:
(a) CuCl (αCu+ = 0.3 nm)
CuCl(s)  Cu+ + Cl−

Since Cu+ has an effective diameter of 0.3, then
(1) γ Cu+ = 0.83 γ Cl− = 0.83 ′ = a + a − = γ + [Cu+ ] × γ − [Cl− ]
K sp Cu Cl Cu Cl
1.9 × 10 −7 1.9 × 10 −7
[Cu+ ][Cl− ] = = = 2.758 × 10−7
γ Cu γ Cl
+ − (0.83)(0.83)
+
Solubility = S = [Cu ] = [Cl− ]
S 2 = 2.758 × 10−7
S = 2.758 × 10−7 = 5.25 × 10−4 M
(2) S = 1.9 × 10 −7 = 4.4 × 10 −4 M
relative error =
( 4.4 × 10 −4
− 5.25 × 10−4 ) × 100% = −16%
−4
5.25 × 10
9
(c) Fe ( OH)3
Fe(OH)3  Fe3+ + 3OH−
(1) γ Fe3+ = 0.281 γ OH− = 0.835 3

′ = aFe3+ aOH
K sp − = γ
Fe3+
[Fe3+ ] × (γ OH− [OH− ])3
2 × 10 −39 2 × 10−39
[Fe3+ ][OH− ]3 = 3
= = 1.223 × 10 −38 retaining figures until the end
γ Fe γ OH
3+ − (0.281)(0.835)3
1
Solubility = S = [Fe3 + ] = [OH− ]
3
S (3S )3 = 1.223 × 10 −38
1
 1.223 × 10 −38 4
S = −10
 = 1.46 × 10 M
 27
 
1
 2 × 10−39  4
(2) S =   = 9.3 × 10 M
−11
 27 
9.3 × 10−11 − 1.46 × 10−10
relative error = × 100% = −36%
1.46 × 10−10
(e) Ag3 AsO4 (α AsO43− = 0.4 nm)
Ag3(AsO4)(s)  3Ag+ + AsO43−

3
(1) γ Ag+ = 0.827 γ AsO 3− = 0.205 ′ = aAg
K sp + a
AsO 3−
= (γ Ag+ [Ag+ ])3 × γ AsO 3− [AsO4 3 − ]
4 4 4
6 × 10 −23 6 × 10 −23
[Ag + ]3 [AsO4 3 − ] = 3
= = 5.17 × 10 −22
γ Ag γ AsO
+ 3− (0.827)3 (0.205)
4
1
Solubility = S = [AsO3 4 − ] = [Ag + ]
3
(3S )3 S = 5.17 × 10−22
1
 5.17 × 10−22  4
S =  = 2.1× 10 M
−6
 27 
1
 6 × 10 −23  4
(2) S =   = 1.2 × 10 M
−6
 27 
1.2 × 10 −6 − 2.1 × 10 −6
relative error = × 100% = −43%
2.1× 10 −6
10
8-17. Calculate the % relative error in hydronium ion concentration by using concentrations
instead of activities in calculating the pH of the following buffer solutions using the
thermodynamic constants found in Appendix 3.
Solution:
(a) 0.175 M HOAc and 0.275 M NaOAc
In this buffer solution, we assume [HOAc] = cHOAc and [OAC−] = cNaOAc. We also
assume that the ionic strength is contributed solely by NaOAc, neglecting H3O+ and
OH−.
μ = ½[0.275 × 12 + 0.275 × 12] = 0.275
(0.51)(1)2 0.275
− log γ H O+ = = 0.1046 γ H O+ = 0.786
3
1 + (3.3)(0.9) 0.275 3
(0.51)(1)2 0.275
− log γ OAc− = = 0.1541 γ OAc− = 0.701
1 + (3.3)(0.425) 0.275
γ H O+ [H3O+ ]γ OAc− [OAc − ]
Ka = 3
[HOAc]
[H3O+ ][OAc − ] Ka 1.75 × 10 −5
K a′ = = = = 3.176 × 10 −5
[HOAc] γ H O γ OAc
+ − 0.786 × 0.701
3
K a′ [HOAc] 3.176 × 10 −5 × 0.175

[H3O+ ] = = = 2.0 × 10 −5 M
[OAc ] −
0.275
pH = 4.69
With no activity corrections
1.75 × 10 −5 × 0.175
[H3O+ ] = = 1.1× 10 −5 M
0.275
pH = 4.96
1.1× 10 −5 − 2.0 × 10 −5
relative error in [H3O+ ] = × 100% = −45%
2.0 × 10−5
11
© 2022, 978-0-357-45055-0, Chapter 9: Solving Equilibrium Problems for Complex Systems
Chapter 9
9-2. Why are simplifying assumptions in equilibrium problems restricted to relationships that
are sums or differences?
Answer:
To simplify equilibrium calculations, we sometimes assume that the concentrations of
one or more species are negligible and can be approximated as 0.00 M. In a sum or
difference assuming a concentration is 0.00 M leads to an appropriate result. In contrast,
if we were to simplify and equilibrium constant expression by assuming on or more
concentrations are zero, we would be multiplying or dividing by 0.00, which would
render the expression meaningless.
9-4. Why do molar concentrations of some species appear as multiples in charge-balance

equations?
Answer:
A charge-balance equation is derived by relating the concentration of cations and anions
no. mol/L positive charge = no. mol/L negative charge
For a doubly charged ion, such as Ba2+, the concentration of charge for each mole is
twice the molar concentration of the Ba2+. That is,
mol/L positive charge = 2[Ba2+]
Thus, the molar concentration of all multiply charged species is always multiplied by the
charge in a charge-balance equation.
9-5. Write the mass-balance expressions for a solution that is
Solutions:
(a) 0.2 M in HF.
0.20 = [HF] + [F−]
(c) 0.10 M in H3PO4 .
0.10 = [H3PO4] + [H2PO4−] + [HPO42−] + [PO43−]
(e) 0.0500 M in HClO2 and 0.100 M in NaClO2 .
0.0500 + 0.100 = [HClO2] + [ClO2−]

[Na+ ] = cNaClO = 0.100 M
2
1
(g) 0.100 M in NaOH and saturated with Zn(OH)2, which undergoes the reaction
Zn(OH)2 + 2OH−  Zn(OH)42−.

0.100 = [Na+] = [OH−] + 2[Zn(OH)42−]
(i) saturated with PbF2.

[Pb2+] = ½([F−] + [HF])
9-7. Calculate the molar solubility of ZnC2O4 in a solution that has a fixed H3O+
concentration of
Solutions:
(a) 1.0 × 10−6 M.
(c) 1.0 × 10−9 M.
Following the systematic procedure, using part (a)
Step 1 ZnC2O4(s)  Zn2+ + C2O42−
H2C2O4 + H2O  H3O+ + HC2O4−
HC2O4 + H2O  H3O+ + C2O42−
Step 2 S = solubility = [Zn2+] = [C2O42−] + [HC2O4−] + [ H2C2O4]

Step 3 [Zn2+][C2O42−] = Ksp= 8 × 10−9 (1)
[H3O+ ][HC2O4 − ]
= K 1 = 5.6 × 10−2 (2)
[H2C2O4 ]
[H3O+ ][C2 O4 2 − ]
= K 2 = 5.42 × 10 −5 (3)
[HC 2 O4 − ]
Step 4 [Zn+] = [C2O42−] + [HC2O4−] + [ H2C2O4] (4)

[H3O+] = 1.0 × 10−6 M
Step 5 No charge balance because an unknown buffer is maintaining the
pH.
Step 6 Unknowns are [Zn2+], [C2O42−], [HC2O4−], [ H2C2O4]
Step 7 No approximations needed, because we have 4 equations and 4
unkowns.
Step 8 Substituting [H3O+] = 1.0 × 10−6 M into equation (3) and rearranging
gives
1 × 10−6 [C2 O4 2 − ]
[HC2O4 − ] = = 1.845 × 10−2 [C2 O4 2 − ]
5.42 × 10−5
2
Substituting this relationship and [H3O+] = 1.0 × 10−6 M into equation

(2) and rearranging gives
1 × 10 −6 × 1.845 × 10 −2 [C2O4 2 − ]
[H2C2O4 ] = = 3.295 × 10 −7 [C2O4 2 − ]
5.6 × 10 −2
Substituting these last two relationships in to equation (4) gives

[Zn2+] = [C2O42−] + 1.845 × 10−2[C2O42−] + 3.295 × 10−7[C2O42−] =
1.0185[C2O42−]
Substituting this last relationship into equation (1) gives
[Zn2 + ][Zn2+ ]
K sp = = 8 × 10−9
1.0185
[Zn2+] = (8 × 10−9 × 1.0185)1/2 = 9.03 × 10−5
S = [Zn2+] = 9.0× 10−5 M
Substituting other values for [H3O+] gives the following:
[H3O+] S, M
(a) 1.00 × 10 −6
9.0 × 10−5
(c) 1.00 × 10−9 8.9 × 10−5
9-8. Calculate the molar solubility of BaSO4 in a solution in which H3O+  is
Solutions:
(a) 3.5 M.
(c) 0.080 M.
Proceeding as in Problem 9-7, we write
BaSO4  Ba2+ + SO42− Ksp = 1.1 × 10−10
HSO4 + H2O  H3O+ + SO42− K2 = 1.02 × 10−2

S = [Ba2+]
[Ba2+][ SO42−] = 1.1 × 10−10 (1)
[H3O+ ][SO4 2 − ]
= 1.02 × 10 −2 (2)
[HSO4 − ]
Mass balance requires that
[Ba2+] = [SO42−] + [ HSO4−] (3)
The unknowns are [Ba ], [ SO4 ], and [ HSO4 ]
2+ 2− −
We have 3 equations and 3 unknowns so no approximations are needed.

Substituting equation (2) into (3) gives
[H3O+ ][SO4 2 − ]  [H3O+ ] 
[Ba2 + ] = [SO4 2 − ] + = [SO4 2 − ]  1 + 
1.02 × 10 −2  1.02 × 10 −2 

3
Substituting equation (1) to eliminate [SO42−], gives

1.1 × 10 −10  [H3O+ ]  1.1 × 10−10
[Ba2 + ] =
[Ba2 + ]
×  1 +
1.02 × 10
 =
−2 
[Ba2+
]
(
× 1 + 98.0[H3O+ ] )
 
(
S = [Ba2+ ] = 1.1 × 10−10 1 + 98.0[H3O+ ] )= 1.1 × 10−10 + 1.078 × 10−8 [H3O+ ]
Using the different values of [H3O+]
[H3O+] S, M
(a) 3.5 1.9 × 10−4
(c) 0.08 3.1 × 10−5
9-9. Calculate the molar solubility of PbS in a solution in which H3O+  is held constant at (a)
3.0 × 10 −1 M and (b) 3.0 × 10 −4 M.
Solution:
The derivation that follows applies to problems 9-11.
MS(s)  M2+ + S2− Ksp
H2S + H2O  H3O+ + HS− K1 = 9.6 × 10−8
HS + H2O  H3O+ + S2− K2 = 1.3 × 10−14
Overall H2S + 2H2O  2H3O+ + S2− K1K2 = 1.25 × 10−21

S = solubility = [M2+]
[M2+][S2−] = Ksp (1)
[H3O+ ][S2− ]
= K 2 = 1.3 × 10−14 (2)
[HS ]
−
[H3O+ ]2 [S2− ]
= K1K 2 = 1.25 × 10−21 (3)
[H2S]
Mass balance is:
[M2+] = [S2−] + [HS−] + [H2S] (4)
Substituting equation (2) and (3) into (4), gives:
[H3O+ ][S2 − ] [H3O+ ]2 [S2 − ]  [H O+ ] [H3O+ ]2 
[M2 + ] = [S2 − ] + + = [S2 − ]  1+ 3 +  (5)
K2 K 1K 2  K2 K 1K 2 

4
Substituting equation (1) into (5), gives

K sp  [H3O+ ] [H3O+ ]2 
[M2 + ] =  1+ + 
[M2 + ]  K2 K 1K 2 
 [H3O+ ] [H3O+ ]2 
[M2+ ] = K sp  1+ +  (6)
 1.3 × 10−14 1.25 × 10−21 

(a) Substituting Ksp = 3 × 10−28 and [H3O+] = 3.0 × 10−1 into equation (6), gives
 0.30 (0.30)2 
[M2 + ] = solubility = 3 × 10−28  1+ + −21 
= 1.5 × 10−4 M
 1.3 × 10 −14
1.25 × 10 
(b) Using the same Ksp, but [H3O+] = 3.0 × 10−4, gives
[M2+] = solubility = 1.5 × 10−7 M
9-12. Calculate the molar solubility of ZnCO3 in a solution buffered to a pH of 7.00.
Solution:
Proceeding as in Problem 9-9, we find
 [H O+ ] [H3O+ ]2 
[Zn2 + ] = K sp  1+ 3 + 
 K2 K1K 2 

For ZnCO3, Ksp = 1.0 × 10−10. For H2CO3, K1 = 4.45 × 10−7, and K2 = 4.69 × 10−11
 [H3O+ ] [H3O+ ]2 
[Zn2+ ] = 1 × 10−10  1 + + −11 
 4.69 × 10 −11
4.45 × 10 × 4.69 × 10 
−7

For pH = 7.00, [H3O+] = 1.00 × 10−7

[Zn2+] = 5.1 × 10−4 M
9-14. Dilute NaOH is introduced into a solution that is 0.050 M in Cu2+ and 0.040 M in Mn2+ .
Solutions:
[Cu2+][OH−]2 = 4.8 × 10−20 [Mn2+][ OH−]2 = 2 × 10−13
(a) Which hydroxide precipitates first?

Cu(OH)2 precipitates first
5
(b) What OH− concentration is needed to initiate precipitation of the first hydroxide?
Cu2+ begins to precipitate when
4.8 × 10−20
[OH− ] = = 9.8 × 10−10 M
0.05
(c) What is the concentration of the cation forming the less soluble hydroxide when
the more soluble hydroxide begins to form?
Mn2+ begins to precipitate when
2 × 10−13
[OH− ] = = 2.24 × 10−6 M
0.04
[Cu2+] = 4.8 × 10−20/(2.24 × 10−6)2 = 9.6 × 10−9 M
9-16. Silver ion is being considered for separating I− from SCN− in a solution that is 0.040 M in
KI and 0.080 M in NaSCN.
Solutions:
(a) What Ag + concentration is needed to lower the I− concentration to 1.0 × 10 −6 M?
[Ag+] = Ksp/[I−] = 8.3 × 10−17/(1.0 × 10−6) = 8.3 × 10−11 M
(b) What is the Ag + concentration of the solution when AgSCN begins to precipitate?
[Ag+] = Ksp/[SCN−] = 1.1 × 10−12/(0.080) = 1.375 × 10−11 M ≈ 1.4 × 10−11 M
(c) What is the ratio of SCN− to I− when AgSCN begins to precipitate?

[I−] when [Ag+] = 1.375 × 10−11 M
[I−] = 8.3 × 10−17/(1.375 × 10−11) = 6.0 × 10−6 M
[SCN−]/[I−] = 0.080/(6.0 × 10−6) = 1.3 × 104
(d) What is the ratio of SCN− to I− when the Ag + concentration is 1 .0 × 10 −3 M?
[I] = 8.3 × 10−17/(1.0 × 10−3) = 8.3 × 10−14 M

[SCN−] = 1.1 × 10−12/(1.0 × 10−3) = 1.1 × 10−9 M
[SCN−]/[I−] = 1.1 × 10−9/(8.3 × 10−14) = 1.3 × 104
Note that this ratio is independent of [Ag+] as long as some AgSCN(s) is present.
9-18. What mass of AgBr dissolves in 200 mL of 0.200 M NaCN?
Ag+ + 2CN−  Ag(CN)2 − β2 = 1.3 × 1021
Solution:
AgBr  Ag+ + Br− Ksp = 5.0 × 10−13 = [Ag+][Br] (1)
[Ag(CN)2 ] −
Ag+ + 2CN−  Ag(CN)2− β2 = 1.3 × 1021 = (2)
[Ag + ][CN− ]2
6
It is readily shown that CN− + H2O  HCN + OH− can be neglected in this problem so that
only the two equilibria shown above need to be considered.
Solubility = [Br−]
Mass balance requires that
[Br−] = [Ag+] + [Ag(CN)2−] (3)
0.200 = [CN ] + 2[Ag(CN)2 ]
− −
(4)
We now have 4 equations and 4 unknowns.
Because β2 is very large, let us assume that
[CN−] << 2[Ag(CN)2−] and [Ag+] << [Ag(CN)2−]
(4) becomes [Ag(CN)2−] = 0.200/2 = 0.100
and (3) becomes [Br−] = [Ag(CN)2−] = 0.100
To check the assumptions, we calculate [Ag+] by substituting into (1)
[Ag+] = 5.0 × 10−13/0.100 ≅ 5 × 10−12 (5 × 10−12 << 0.100)
To obtain [CN−] we substitute into (2) and rearrange
0.100
[CN] = = 3.9 × 10−6 (3.9 × 10−6 << 0.100)
(5 × 10 )(1.3 × 10 )
−12 21
Thus, the two assumptions are valid and

Solubility = [Br−] = 0.100 M
mmol 0.1877 g
mass AgBr/200 mL = 0.100 × 200 mL ×
mL mmol
= 3.754 g
9-20. In contrast to many salts, calcium sulfate is only partially dissociated in aqueous solution:
CaSO4 (aq)  Ca2+ + SO4 2−

K d = 5.2 × 10 −3
The solubility-product constant for CaSO4 is 2.6 × 10−5. Calculate the solubility of CaSO4
in (a) water and (b) 0.0100 M Na2 SO4 . In addition, calculate the percent of undissociated
CaSO4 in each solution.
Solution:
CaSO4(s)  Ca2+ + SO42− Ksp = [Ca2+][SO42−] = 2.6 × 10−5 (1)
[Ca2 + ][SO4 − ]
CaSO4(aq)  Ca2+ + SO42− Kd = = 5.2 × 10−3 (2)
[CaSO4 ]aq
CaSO4(s)  CaSO4(aq) (3)
7
The mass balance gives

[Ca2+] = [SO42−] (4)
We have 3 equations and 3 unknowns ([Ca2+], [SO42−], and [CaSO4]aq
To solve we divide (1) by (2) to give
[CaSO4]aq = Ksp/Kd = (2.6 × 10−5)/(5.2 × 10−3) = 5.0 × 10−3
Note that this is the equilibrium constant expression for (3) and indicates that the
concentration of un-ionized CaSO4 is always the same in a saturated solution of CaSO4.
Substituting (4) into (1) gives
[Ca2+] = (2.6 × 10−5)1/2 = 5.1 × 10−3 M
and since S = [CaSO4]aq + [Ca2+], we obtain
S = 5.0 × 10−3 + 5.1 × 10−3 = 1.01 × 10−2 M
%CaSO4(aq) = (5.0 × 10−3/1.01 × 10−2) × 100% = 49%
Here [CaSO4]aq is again equal to 5.0 × 10−3 and the mass balance gives
[SO42] = 0.0100 + [Ca2+] (5)
Substituting (1) into (5) and rearranging gives
0 = [SO42−]2 − 0.0100[SO42−] − Ksp
which may be solved using the quadratic equation to give
[SO42−] = 0.0121 and [Ca2+] = 2.14 × 10−3
S = 5.0 × 10 + 2.14 × 10 = 7.14 × 10−3 M
−3 −3
%CaSO4(aq) = (5.0 × 10−3/7.14 × 10−3) × 100% = 70%
8
© 2022, 978-0-357-45055-0, Chapter 10: Gravimetric Methods of Analysis
Chapter 10
10-1. Define
Answers:
(a) digestion.
Digestion is a process in which a precipitate is heated in the presence of the
solution from which it was formed (the mother liquor). Digestion improves the
purity and filterability of the precipitate.
(c) reprecipitation.
In reprecipitation, the filtered solid precipitate is redissolved and reprecipitated.
Because the concentration of the impurity in the new solution is lower, the second
precipitate contains less coprecipitated impurity.
(e) counter-ion layer.

The counter-ion layer describes a layer of solution containing sufficient excess
negative ions that surrounds a charged particle. This counter-ion layer balances the
surface charge on the particle.
(g) supersaturation.
Supersaturation describes an unstable state in which a solution contains higher
solute concentration than a saturated solution. Supersaturation is relieved by
precipitation of excess solute.
10-2. Explain the difference between
Answers:
(a) a colloidal and a crystalline precipitate.
A colloidal precipitate consists of solid particles with dimensions that are less than
10−4 cm. A crystalline precipitate consists of solid particles with dimensions that at
least 10−4 cm or greater. As a result, crystalline precipitates settle rapidly, whereas
colloidal precipitates remain suspended in solution unless caused to agglomerate.
1
(c) precipitation and coprecipitation.

Precipitation is the process by which a solid phase forms and is carried out of
solution when the solubility product of a chemical species is exceeded.
Coprecipitation is a process in which normally soluble compounds are carried out of
solution during precipitate formation.
(e) occlusion and mixed-crystal formation.

Occlusion is a type of coprecipitation in which a compound is trapped within a
pocket formed during rapid crystal formation. Mixed-crystal formation is also a type
of coprecipitation in which a contaminant ion replaces an ion in the crystal lattice.
10-3. Define what constitutes a chelating agent.
Answer:
A chelating agent is an organic compound that contains two or more electron-donor
groups located in such a configuration that five- or six-membered rings are formed when
the donor groups complex a cation.
10-5. An aqueous solution contains NaNO3 and KBr. The bromide ion is precipitated as AgBr
by addition of AgNO3 . After an excess of the precipitating reagent has been added,
Answers:
(a) what is the charge on the surface of the coagulated colloidal particles?
There is positive charge on the surface of the coagulated colloidal particles.
(b) what is the source of the charge?

The positive charge arises from adsorbed Ag+ ions.
(c) what ions make up the counter-ion layer?

NO3– ions make up the counter-ion layer.
10-7. What is peptization, and how is it avoided?
Answer:
In peptization, a coagulated colloid returns to its original dispersed state because of a
decrease in the electrolyte concentration of the solution contacting the precipitate.
Peptization can be avoided by washing the coagulated colloid with an electrolyte solution
instead of pure water.
2
10-9. Write an equation showing how the mass of the substance sought can be converted to
the mass of the weighed substance on the right.
Sought Weighed Sought Weighed
(a) SO2 BaSO4 (e) CuO Cu2 ( SCN)2
(c) In In2O3 (i) Na2B4O7 ⋅10H2O B2O3

Solutions:
MSO
(a) mass SO2 = mass BaSO4 × 2
MBaSO
4
2MIn
(c) mass In = mass In2O3 ×
MIn O
2 3
2MCuO
(e) mass CuO = mass Cu2(SCN)2 ×
MCu
2 (SCN)2
MNa B O
7 •10H2 O
(i) mass Na2B4O7 ⋅ 10H2O = mass B2O3 × 2 4
2MB O
2 3
10-10. Treatment of a 0.3500-g sample of impure potassium chloride with an excess of AgNO3
resulted in the formation of 0.3846 g of AgCl. Calculate the percentage of KCl in the
sample.
Solution:
MAgCl = 143.32 g/mol MKCl = 74.55 g/mol
 1 mol AgCl   1 mol KCl   74.55 g KCl 
0.3846 g AgCl ×  ×  × 
 143.32 g   1 mol AgCl   mol 
× 100% = 57.16%
0.3500 g impure sample
10-12. What mass of Cu (IO3 )2 can be formed from 0.475 g of CuSO4 ⋅ 5H2O?
Solution:
1 mol CuSO4 ⋅ 5H2O 1 mol Cu(IO3 )2
0.475 g CuSO4 ⋅ 5H2 O × ×
249.67 g CuSO4 ⋅ 5H2 O 1 mol CuSO4 ⋅ 5H2O
413.35 g Cu(IO3 )2
× = 0.786 g Cu(IO3 )2
1 mol Cu(IO3 )2
10-14. What mass of AgI can be produced from a 0.512-g sample that assays 20.1% AlI3 ?
Solution:
20.1 g 1 mol AlI3 3 mol AgI 234.77 g AgI
mass AgI = 0.512 g × × × × = 0.178 g
100 g 407.69 g mol AlI3 mol AgI
3
10-18. A 0.2121-g sample of an organic compound was burned in a stream of oxygen, and the
CO2 produced was collected in a solution of barium hydroxide. Calculate the percentage
of carbon in the sample if 0.6006 g of BaCO3 was formed.
Solution:
1 mol BaCO3 1 mol C 12.011 g C
0.6006 g BaCO3 × × ×
197.34 g 1 mol BaCO3 1 mol C
× 100% = 17.23% C
0.2121 g sample
10-20. The mercury in a 1.0451-g sample was precipitated with an excess of paraperiodic acid,
H5IO6 :
5Hg2+ + 2H5IO6 → Hg5 (IO6 )2 + 10H+
The precipitate was filtered, washed free of precipitating agent, dried, and weighed, and
0.5718 g was recovered. Calculate the percentage of Hg2Cl2 in the sample.
Solution:
 1 mol Hg5 (IO6 )2 5 mol Hg2+ 
 0.5718 g Hg 5
(IO )
6 2
× × 
 1448.75 g Hg5 (IO6 )2 1 mol Hg5 (IO6 )2 
 1 mol Hg Cl 472.18 g Hg2Cl2 
×

2 2
× 
 2 mol Hg 2+
1 mol Hg2Cl2  × 100% = 44.58% Hg Cl
2 2
1.0451 g sample
10-22. Ammoniacal nitrogen can be determined by treatment of the sample with chloroplatinic
acid; the product is slightly soluble ammonium chloroplatinate:
H2PtCl6 + 2NH4+ → (NH4 )2 PtCl6 + 2H+
The precipitate decomposes on ignition, yielding metallic platinum and gaseous

products:
(NH )
4 2
PtCl6 → Pt ( s ) + 2Cl2 ( g ) + 2NH3 ( g ) + 2HCl ( g )
Calculate the percentage of ammonia in a sample if 0.1195 g gave rise to 0.2329 g of

platinum.
Solution:
MNH = 17.0306 g/mol MPt = 195.08 g/mol
3
 1 mol Pt   2 mol NH3   17.0306 g NH3 

0.2329 g Pt ×  ×  × 
 195.08 g   1 mol Pt   mol  × 100% = 34.03% NH
3
0.1195 g impure sample
4
10-24. A series of sulfate samples is to be analyzed by precipitation as BaSO4 . If it is known that

the sulfate content in these samples ranges between 20% and 55%, what minimum
sample mass should be taken to ensure that a precipitate mass no smaller than 0.200 g
is produced? What is the maximum precipitate mass to be expected if this quantity of
sample is taken?
Solution:
MBaSO = 233.39 g/mol MSO 2− = 96.064 g/mol
4 4
Let Sw = mass of sample in grams

1 mol BaSO4 1 mol SO4 2−
0.200 g BaSO4 × × = 8.57 × 10−4 mol SO4 2 −
233.39 g 1 mol BaSO4
96.064 g SO4 2−
8.57 × 10 −4 mol SO4 2 − ×
mol × 100% = 20% SO4 2−
Sw g sample
96.064 g SO4 2−
8.57 × 10−4 mol SO4 2 − × × 100%
Sw = mol = 0.412 g sample
20%
The maximum precipitate weight expected given this sample weight is
55 g SO4 2 − 1 mol SO4 2 − 1 mol BaSO4 233.39 g BaSO4
0.412 g sample × × × ×
100 g sample 96.064 g 1 g SO4 2−
1 mol
= 0.550 g BaSO4
10-26. The efficiency of a particular catalyst is highly dependent on its zirconium content. The
starting material for this preparation is received in batches that assay between 68% and
84% ZrCl4 . Routine analysis based on precipitation of AgCl is feasible, it having been
established that there are no sources of chloride ion other than the ZrCl4 in the sample.
Solutions:
Let Sw = mass of sample in grams.
(a) What sample mass should be taken to ensure an AgCl precipitate that weighs at
least 0.350 g?
MAgCl = 143.32 g/mol MZrCl = 233.03 g/mol

4
1 mol AgCl 1 mol ZrCl4 233.03 g ZrCl4

0.350 g AgCl × × ×
143.32 g 4 mol AgCl 1 mol
× 100% = 68% ZrCl4
Sw g sample
1.42 × 10 −1 g ZrCl4 × 100%
Sw = = 0.209 g sample
68%
5
(b) If this sample mass is used, what is the maximum mass of AgCl that can be
expected in this analysis?
84 g ZrCl4 1 mole ZrCl4 4 mole AgCl 143.32 g AgCl

0.209 g sample × × × ×
100 g sample 233.03 g 1 mole ZrCl4 1 mole
= 0.432 g AgCl
(c) To simplify calculations, what sample mass should be taken to have the percentage
of ZrCl4 exceed the mass of AgCl produced by a factor of 100?
1.42 × 10−1 g ZrCl4 × 100%

% ZrCl4 = = 40%
Sw
1.42 × 10−1 g ZrCl4 ×100%
Sw = = 0.355 g sample
40%
10-28. A 0.6407-g sample containing chloride and iodide ions gave a silver halide precipitate
weighing 0.4430 g. This precipitate was then strongly heated in a stream of Cl2 gas to
convert the AgI to AgCl; on completion of this treatment, the precipitate weighed 0.3181 g.
Calculate the percentage of chloride and iodide in the sample.
Solution:
MAgCl = 143.32 g/mol MAgI = 234.77 g/mol
0.4430 g = x g AgCl + y g AgI
 1 mol AgI 1 mol AgCl 143.32 g AgCl 
g AgCl = x g AgCl +  y g AgI × × ×  = 0.3181g
 234.77 g 1 mol AgI 1 mol 
0.3181 = x g AgCl + 0.6104698 y g AgI
Here again, we have 2 equations and 2 unknowns,

x + y = 0.4430
x + 0.6104698y = 0.3181
The spreadsheet is shown on the next page
We would report %Cl = 4.72 and %I = 27.05
6
10-30. What mass in grams of CO2 is evolved in the complete decomposition of a 2.300-g
sample that is 38.0% MgCO3 and 42.0% K 2CO3 by mass?
Solution:
MCO = 44.010 g/mol MMgCO = 84.31 g/mol MK CO = 138.21 g/mol
2 3 2 3
mol CO2 = mol MgCO3 + mol K 2CO3

 38 g MgCO3 1 mol MgCO3 
=  2.300 g sample × × +
 100 g sample 84.31g 
 42 g K 2CO3 1 mol K 2CO3 
 2.300 g sample × × 
 100 g sample 138.21g 
amount CO2 = 0.0104 + 6.989 × 10−3 = 0.01736 mol
44.010 g CO2
mass CO2 = 0.01736 mole × = 0.764 g
1mole
7
10-32. A 50.0-mL portion of a solution containing 0.200 g of BaCl2 ⋅ 2H2O is mixed with 50.0 mL
of a solution containing 0.300 g of NaIO3 . Assume that the solubility of Ba (IO3 )2 in water
is negligibly small and calculate
MBaCl = 244.26 g/mol MNaIO = 197.89 g/mol MBa(IO = 487.13 g/mol

2 ⋅ 2H2 O 3 3 )2
1mol BaCl2 ⋅ 2H2O 1mol Ba 2+

0.200 g BaCl2 ⋅ 2H2O × ×
244.26 g 1mol BaCl2 ⋅ 2H2O
= 8.188 × 10−4 mol Ba2+
1mol NaIO3 1mol IO3 −
0.300 g NaIO3 × × = 1.516 × 10−3 mol IO3 −
197.89 g 1mol NaIO3
Solutions:
Because IO3− is the limiting reagent,
(a) the mass of the precipitated Ba (IO3 )2 .
1.516 × 10−3 mol

amount Ba(IO3 )2 = = 7.580 × 10−4 mol
2
487.13 g Ba(IO3 )2
mass Ba(IO3 )2 = 7.580 × 10−4 mol × = 0.369 g Ba(IO3 )2
1mol
(b) the mass of the unreacted compound that remains in solution.
( )
amount BaCl2 ⋅ 2H2O remaining = (8.188 × 10−4 ) − (7.580 × 10−4 ) mol = 6.080×10−5 mol
244.26 g BaCl2 ⋅ 2H2O
mass BaCl2 ⋅ 2H2O = 6.08 × 10−5 mol BaCl2 ⋅ 2H2O ×
1mol
= 0.0149 g
8
© 2022, 978-0-357-45055-0, Chapter 11: Titrations in Analytical Chemistry
Chapter 11
11-1. Define
Answers:
(a) millimole.
The millimole is the amount of an elementary species, such as an atom, an ion, a
molecule, or an electron. A millimole contains
particles mol particles

6.02 ×1023 × = 6.02 × 1020
mol 1000 mmol mmol
(c) stoichiometric ratio.

The stoichiometric ratio is the molar ratio of two chemical species that appear in a
balanced chemical equation.
Answer:
(a) the equivalence point and the end point of a titration.
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.
11-5. Calculations of volumetric analysis ordinarily consist of transforming the quantity of

titrant used (in chemical units) to a chemically equivalent quantity of analyte (also in
chemical units) through use of a stoichiometric factor. Use chemical formulas (NO
CALCULATIONS REQUIRED) to express this ratio for calculation of the percentage of
Solutions:
(a) hydrazine in rocket fuel by titration with standard iodine. Reaction:
H2NNH2 + 2I2 → N2 ( g ) + 4I− + 4H+
1 mol H2NNH2
2 mol I2
1
(c) boron in a sample of borax, Na2B4O7 ⋅10H2O, by titration with standard acid.
Reaction:
B4 O72− + 2H+ + 5H2 O → 4H3BO3
1 mole Na2B4 O7 ⋅10H2O

2 moles H+
11-7. How many millimoles of solute are contained in
Solutions:
(a) 2.95 mL of 0.0789 MKH2PO4 ?
0.0789 mmol
2.95 mL × = 0.233 mmol
mL
(b) 0.2011 L of 0.0564 MHgCl2 ?
0.0564 mol 1000 mmol

0.2011 L × × = 11.34 mmol
L mol
(c) 2.56 L of a 47.5 ppm solution of Mg (NO3 )2 ?
47.5 g Mg(NO3 )2 1000 g soln 1 mol 1000 mmol

6
× × × 2.56 L ×
10 g soln L 148.31 g Mg(NO3 )2 mol
= 0.820 mmol
(d) 79.8 mL of 0.1379 MNH4 VO3 (116.98 g/mol) ?
0.1379 mmol
79.8 mL × = 11.00 mmol
mL
11-9. What mass of solute in grams is contained in
Solutions:
(a) 450.0 mL of 0.0986 MH2O2 ?
0.0986 mol H2O2 34.02 g 1L

450.0 mL × × × = 1.51 g
L mol H2O2 1000 mL
(b) 26.4 mL of 9 .3 6 × 10 −4 M benzoic acid (122.1 g/mol)?
9.36 × 10−4 mol 122.1 g 1L

26.4 mL × × × = 3.02 × 10−3 g
L mol 1000 mL
2
(c) 2.50 L of a solution that contains 23.4 ppm SnCl2 ?
23.4 mg 1g
2.50 L × × = 0.0585 g (1 ppm = 1 mg/L)
L 1000 mg
(d) 21.7 mL of 0.0214 MKBrO3 ?
0.0214 mol 167.0 g 1 L

21.7 mL × × × = 0.0776 g
L mol 1000 mL
11-11. Calculate the molar concentration of a 20.0% solution (w/w) of KCl that has a specific
gravity of 1.13.
Solution:
20.0 g KCl 1.13 g soln 1 mmol KCl mmol KCl
× × = 3.03 = 3.03 M
100 g soln mL 0.07455 g KCl mL
Solutions:
(a) 1.00 L of 0.150MKMnO4 from the solid reagent.
0.150 mol 158.03 g

1.00 L × × = 23.70 g
L mol
Dissolve 23.70 g KMnO4 in water and dilute to 1.00 L total volume.
(b) 2.50 L of 0.500MHClO4 , starting with a 9.00 M solution of the reagent.
0.500 mol
2.50 L of 0.500 M HClO4 contains 2.50 L × = 1.25 mol
L
1.25 mol
Need to take a volume of = 0.139 L
9.00 mol /L
Take 139 mL of concentrated (9.00 M) reagent and dilute to 2.50 L.
(c) 400 mL of a solution that is 0.0500 M in I− , starting with MgI2 .
0.0500 mol I− 1L 1 mol MgI2 278.11 g

400 mL × × × × = 2.78 g
L 1000 mL 2 mol I −
mol MgI2
Dissolve 2.78 g MgI2 in water and bring to 400 mL total volume.
3
(d) 200 mL of 1.00% (w/v) aqueous CuSO4 from a 0.218MCuSO4 solution.
1.00 g CuSO4 1 mol 1L 1000 mL

200 mL × × × × = 57.5 mL
100 mL 159.61 g CuSO4 0.218 mol 1L
Take 57.5 mL of the 0.218 M solution and dilute to a volume of 200 mL.
(e) 1.50 L of 0.215 M NaOH from the concentrated commercial reagent

[50% NaOH (w/w), specific gravity = 1.525].
In 1.50 L of 0.215 M NaOH, there are
0.215 mole NaOH
× 1.50 L = 0.3225 mole NaOH
L
The commercial reagent is
1.525 × 103 g 50 g NaOH mole
× × = 19.06 M
L 100 g 40.00 g NaOH
L
Thus, volume = 0.3225 mole NaOH × = 0.0169 L
19.06 mole NaOH
Take 16.9 mL of the concentrated reagent and dilute to 1.50 L.
(f) 1.50 L of a solution that is 12.0 ppm in K + , starting with solid K 4F e ( CN )6 .
12 mg K +
12 ppmK + = × 1.50 L = 18 mg K +
L
1 g mole K + mole K 4Fe(CN)6 368.3 g

18 mg × × × ×
1000 mg 39.10 g 4 mole K +
mole K 4Fe(CN)6
= 0.0424 g K 4Fe(CN)6
Dissolve 42.4 mg K4Fe(CN)6 in water and dilute to 1.50 L.
11-15. A 0.4723-g sample of primary-standard-grade Na2CO3 required 34.78 mL of an H2SO4

solution to reach the end point in the reaction
CO 3 2 − + 2H+ → H2 O + CO 2 ( g )
What is the molar concentration of the H2 SO4 ?
Solution:
g
MNa CO = 105.99
2 3
mole
CO2−
3
+ 2H+  H2O + CO2 (g)
4
1 mole Na2CO3 2 mole H+ 1 mole H2SO4 1000 mmol

0.4723 g Na2CO3 × × × ×
105.99 g Na2CO3 mole Na2CO3 2 mole H +
mole H2SO4
34.78 mL
= 0.1281 M
11-17. A 0.4126-g sample of primary-standard Na2CO3 was treated with 40.00 mL of dilute
perchloric acid. The solution was boiled to remove CO2 , following which the excess
HClO4 was back-titrated with 9.20 mL of dilute NaOH. In a separate experiment, it was
established that 26.93 mL of the HClO4 neutralized the NaOH in a 25.00-mL portion.
Calculate the molarities of the HClO4 and NaOH.
Solution:
VHClO 26.93 mL HClO4 mL HClO4
4
= = 1.0772
VNaOH 25.00 mL NaOH mL NaOH
The volume of HClO4 needed to titrate 0.4126 g of Na2CO3 is

1.0772 mL HClO4
40.00 mL HClO4 – 9.20 mL NaOH × = 30.09 mL
mL NaOH
0.4126 g Na2CO3 1 mmol Na2CO3 2 mmol HClO4
Thus, × × = 0.2587 M HClO4
30.09 mL HClO4 0.10599 g Na2CO3 mmol Na2CO3
VHClO
and cNaOH = cHClO4 × 4
VNaOH
0.2587 mmol HClO4 1.0772 mL HClO4 1 mmol NaOH

= × × = 0.2787 M
mL HClO4 mL NaOH mmol HClO4
11-19. Titration of the I2 produced from 0.1142 g of primary-standard KIO3 required 27.95 mL
of sodium thiosulfate.
IO3 − + 5I− + 6H+ → 3I2 + 3H2O

I2 + 2S2O32 − → 2I− + S4 O62 −
Calculate the concentration of the Na2S2O3 .
Solution:
Each mole of KIO3 consumes 6 moles of S2O2−
3
1 mol KIO3 1000 mmol Na2 SO3 6 mol Na2 SO3

0.1142 g KIO3 × × ×
214.001 g KIO3 mol Na2 SO3 mol KIO3
27.95 mL Na2 SO3
= 0.1146 M Na2 SO3
5
11-21. A 100.0-mL sample of spring water was treated to convert any iron present to Fe 2+ .
Addition of 25.00 mL of 0.002517 MK 2Cr2O7 resulted in the reaction
6Fe2 + + Cr2O7 2 − + 14H+ → 6Fe3+ + 2Cr 3+ + 7H2O
The excess K 2Cr2O7 was back-titrated with 8.53 mL of 0.00949 M Fe2+ solution. Calculate
the concentration of iron in the sample in parts per million.
Solution:
0.002517 mmol Cr2O27 − 6 mmol Fe2+
No. mmol Fe2+ = 25.00 mL × × = 0.37755
mL mmol Cr2O2−
7
= no. mmol analyte Fe2+ + no. mmol Fe2+ back titrated

No. mmol analyte Fe2+ = 0.37755 – 8.53 × 0.00949 M = 0.2966
0.2966 mmol Fe 0.055845 g 1 mL
× × × 106 ppm = 165.6 ppm Fe
100 mL mmol Fe g
11-23. The thiourea in a 1.455-g sample of organic material was extracted into a dilute H2SO4
solution and titrated with 37.31 mL of 0.009372MHg2+ via the reaction
4 (NH2 )2 CS + Hg 2 + → (NH2 )2 CS  Hg2 +

4
Find the percentage of (NH2 )2 CS ( 76.12 g/mol) in the sample.
Solution:
0.009372 mmol Hg2+ 4 mmol 0.07612 g
37.31 mL Hg2+ × × ×
mL Hg2+ mmol Hg2+ mmol
× 100%
1.455 g
= 7.317% (NH2)2CS
11-25. The ethyl acetate concentration in an alcoholic solution was determined by diluting a
10.00-mL sample to 100.00 mL. A 20.00-mL portion of the diluted solution was refluxed
with 40.00 mL of 0.04672 M KOH:
CH3COOC2H5 + OH− → CH3COO− + C2H5OH
After cooling, the excess OH− was back-titrated with 3.41 mL of 0.05042MH2SO4 .
Calculate the amount of ethyl acetate (88.11 g/mol) in the original sample in grams.
Solution:
Total amount KOH = 40.00 mL × 0.04672 mmol/mL = 1.8688 mmol
KOH reacting with H2SO4
0.05042 mmol H2SO4 2 mmol KOH
= 3.41 mL H2SO4 × × = 0.34386 mmol
mL H2SO4 mmol H2SO4
6
1 mmol EtOAc 0.08811 g

mass EtOAc = (1.8688 − 0.34386) mmol KOH × ×
mmol KOH mmol EtOAc
= 0.13436 g in the 20.00-mL portion. In the entire 100.00-mL there are
5 × 0.13326 g or 0.6718 g.
11-27. (a) A 0.3147-g sample of primary-standard-grade Na2C2O4 was dissolved in H2SO4 and
titrated with 31.67 mL of dilute KMnO4 :
2MnO4 − + 5C2O4 2 − + 16H+ → 2Mn2 + + 10CO2 ( g ) + 8H2O
Calculate the molar concentration of the KMnO4 solution.
Solution:
0.3147 g Na2C2O4 2 mmol KMnO4
× = 0.9394 mmol KMnO4
0.1340 g Na2C2O4 / mmol Na2C2O 5 mmol Na2C2O4
4
0.9394 mmol KMnO4

= 0.02966 M KMnO4
31.67 mL
(b) The iron in a 0.6656-g ore sample was reduced quantitatively to the +2 state and
then titrated with 26.75 mL of the KMnO4 solution from part (a). Calculate the
percent Fe2O3 in the sample.
Solution:
MnO4− + 5Fe2+ + 8H+  Mn2+ + 5Fe3+ + 4H2O
26.75 mL KMnO4 × 0.02966 M = 0.7934 mmol KMnO4. Each mmol KMnO4 consumes
5 mmol Fe2+. So
mmol Fe2+ = 5 × 0.7934 = 3.967
1 mmol Fe2O3 0.15969 g Fe2O3
3.967 mmol Fe2+ × ×
2 mmol Fe 2+
mmol Fe2O3
× 100% = 47.59%
0.6656 g
11-29. A solution was prepared by dissolving 7.48 g of KCl ⋅ MgCl2 ⋅ 6H2O ( 277.85 g/mol) in
sufficient water to give 2.000 L. Calculate
Solutions:
(a) the molar analytical concentration of KCl⋅MgCl2 in this solution.
1 mol
7.48 g ×
277.85 g
c= = 1.35 × 10 −2 M
2.000 L
7
(b) the molar concentration of Mg2 + .
[Mg2+] = 1.35 × 10–2 M
(c) the molar concentration of Cl− .

There are 3 moles of Cl– for each mole of KCl ⋅ MgCl2 ⋅ 6H2O. Hence,
[Cl–] = 3 × 1.346 × 10–2 = 4.038 × 10–2 M
(d) the weight/volume percentage of KCl ⋅ MgCl2 ⋅ 6H2O.

7.48 g 1L
× × 100% = 0.374% (w/v)
2.00 L 1000 mL
(e) the number of millimoles of Cl− in 25.0 mL of this solution.
1.346 × 10−2 mmol KCl·MgCl 2 3 mmol Cl−

× × 25.00 mL = 1.0095 mmol Cl−
mL mmol KCl·MgCl2
(f) the concentration of K + in ppm.
1.346 × 10 −2 mmol KCl·MgCl2 1 mmol K + 39.10 mg 1000 mL 526 mg K +

× × × =
mL mmol KCl·MgCl2 mmol K + L L
= 526 ppm K +
8
© 2022, 978-0-357-45055-0, Chapter 12: Principles of Neutralization Titrations
Chapter 12
12-1. Why does the typical acid-base indicator exhibit its color change over a range of about
2 pH units?
Answer:
The eye has limited sensitivity. To see the color change requires a roughly tenfold excess
of one or the other form of the indicator. This change corresponds to a pH range of the
indicator pKa ± 1 pH unit, a total range of 2 pH units.
12-3. Consider curves for the titration of 0.10 M NaOH and 0.010 M NH3 with 0.10 M HCl.
Answers:
(a) Briefly account for the differences between curves for the two titrations.
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) In what respect will the two curves be indistinguishable?

Beyond the equivalence point, the pH is determined by the excess titrant. Thus, the
curves become identical in this region.
12-5. What variables can cause the pH range of an indicator to shift?
Answer:
The variables are temperature, ionic strength, and the presence of organic solvents and
colloidal particles.
12-6. Which solute would provide the sharper end point in a titration with 0.10 M HCl:
Solutions:
The sharper end point will be observed with the solute having the larger Kb.
(a) 0.10 M NaOCl or 0.10 M hydroxylamine?
1.00 × 10 −14
For NaOCl, Kb = = 3.3 × 10 −7
3.0 × 10 −8
1.00 × 10 −14
For hydroxylamine Kb = = 9.1 × 10 −9 Thus, NaOCl
1.1 × 10 −6
(c) 0.10 M methylamine or 0.10 M hydroxylamine?

For hydroxylamine, Kb = 9.1 × 10−9 (part a)
−14
1.00 × 10
For methylamine, Kb = = 4.3 × 10 −4 Thus, methylamine
2.3 × 10 −11
12-7. Which solute would provide the sharper end point in a titration with 0.10 M NaOH:
Solutions:
The sharper end point will be observed with the solute having the larger Ka.
(a) 0.10 M nitrous acid or 0.10 M iodic acid?

For nitrous acid Ka = 7.1 × 10−4
For iodic acid Ka = 1.7 × 10−1 Thus, iodic acid
(c) 0.10 M hypochlorous acid or 0.10 M pyruvic acid?

For hypochlorous acid Ka = 3.0 × 10−8
For pyruvic acid Ka = 3.2 × 10−3 Thus, pyruvic acid
12-9. The procedure described in Problem 12-8 was used to determine pH with methyl orange
as the indicator. The concentration ratio of the acid to base form of the indicator was
1.84. Calculate the pH of the solution.
Solution:
[H3O+ ][In]
InH+ + H2O  In + H3O+ = Ka
[InH+ ]
For methyl orange, pKa = 3.46 (Table 12-1)

Ka = antilog(−3.46) = 3.47 × 10 −4
[InH+]/[In] = 1.84
Substituting these values into the equilibrium expression and rearranging gives
[H3O+] = 3.47 × 10−4 × 1.84 = 6.385 × 10−4
pH = −log(6.385 × 10−4) = 3.19
2
12-11. Using the data in Problem 12-10, calculate pK w at
Solution:
(b) 50°C.
At 50oC, pKw = −log(5.47 × 10−14) = 13.26
12-12. Using the data in Problem 12-10, calculate the pH of a 1.50 × 1022 MNaOH solution at
Solution:
(b) 50°C.
pH = 13.26 − 1.82 = 11.44
12-13. What is the pH of an aqueous solution that is 3.00% HCl by mass and has a density of
1.015 g/mL?
Solution:
3.00 g HCl 1.015 g 1 mmol HCl
× × = 0.835 M
100 g mL 0.03646 g HCl
[H3O+] = 0.835 M; pH = −log 0.835 = 0.078
12-15. What is the pH of a solution that is 2.00 × 10 −8 M in NaOH? (Hint: In such a dilute solution,
you must take into account the contribution of H2O to the hydroxide ion concentration.)
Solution:
The solution is so dilute that we must take into account the contribution of water to
[OH−] which is equal to [H3O+]. Thus,
1.00 × 10−14
[OH−] = 2.00 × 10−8 + [H3O+] = 2.00 × 10−8 +
[OH− ]
[OH−]2 − 2.00 × 10−8[OH−] − 1.00 × 10−14 = 0
Solving the quadratic equation yields, [OH−] = 1.105 × 10−7 M
pOH = −log 1.105 × 10−7 = 6.957; pH = 14.00 − 6.957 = 7.04
12-17. What is the pH of the solution that results when 0.093 g of Mg ( OH)2 is mixed with
Solutions:
(a) 75.0 mL of 0.0500 M HCl?
0.093 g Mg(OH)2
amount of Mg(OH)2 taken = = 1.595 mmol
0.05832 g Mg(OH)2 / mmol
cHCl = (75.0 × 0.0500 − 1.595 × 2)/75.0 = 7.467 × 10−3 M

[H3O+] = 7.467 × 10−3; pH = −log(7.467 × 10−3) = 2.13
3
(b) 100.0 mL of 0.0500 M HCl?

cHCl = 100.0 × 0.0500 − 1.595 × 2)/100.0 = 0.0181 M
pH = −log(0.0181) = 1.74
(c) 15.0 mL of 0.0500 M HCl?

15.0 × 0.050 = 0.750 mmol HCl added. Solid Mg(OH)2 remains and
1 mmol Mg2+ 1
[Mg2+] = 0.750 mmol HCl × × = 0.0250 M
2 mmol HCl 15.0 mL
Ksp = 7.1 × 10−12 = [Mg2+][OH−]2
7.1 × 10−12
[OH−] = = 1.68 × 10−5 M
0.0250
pH = 14.00 − (−log(1.68 × 10−5)) = 9.22
(d) 30.0 mL of 0.0500 MMgCl2 ?
Since Mg(OH)2 is fairly insoluble, the Mg2+ essentially all comes from the added
MgCl2, and [Mg2+] = 0.0500 M
7.1 × 10−12
[OH−] = = 1.19 × 10−5 M
0.0500
pH = 14.00 − (−log(1.19 × 10−5)) = 9.08
12-19. Calculate the hydronium ion concentration and pH of a solution that is 0.0500 M in HCl
Solutions:
(a) neglecting activities.
[H3O+] = 0.0500 M; pH = −log(0.0500) = 1.30
(b) using activities (see Chapter 8).

μ = ½ {(0.0500)(+1)2 + (0.0500)(−1)2} = 0.0500
γ H O = 0.85 (Table 8-2)
+
3
aH O+ = 0.85 × 0.0500 = 0.0425

3
pH = −log(0.0425) = 1.37
12-21. Calculate the pH of an aqueous solution that is
Solutions:
(a) 1.00 × 10 −1 M HOCl.
[H3O+ ][OCl− ]
HOCl + H2O  H3O+ + OCl− Ka = = 3.0 × 10−8
[HOCl]
4
(b) 1.00 × 10−2 MHOCl.

[H3O+] = [OCl−] and [HOCl] = cHOCl − [H3O+]
(c) 1.00 × 10−4 MHOCl.

[H3O+]2/(cHOCl − [H3O+]) = 3.0 × 10−8
rearranging gives: [H3O+]2 + 3 × 10−8[H3O+] − cHOCl × 3.0 × 10−8 = 0
cHOCl [H3O+] pH
(a) 0.100 5.476 × 10−5 4.26
(b) 0.0100 1.731 × 10 −5
4.76
(c) 1.00 × 10 −4
1.717 × 10 −6
5.76
12-23. Calculate the pH of an ammonia solution that is
Solutions:
(a) 1 .0 0 × 10 −1 M NH3 .
1.00 × 10 −14
NH3 + H2O  NH4+ + OH− Kb = = 1.75 × 10 −5
5.7 × 10 −10
(b) 1 .0 0 × 10 −2 M NH3 .
[NH4+] = [OH−] and [NH3] = cNH3 − [OH−]
(c) 1 .0 0 × 10 −4 M NH3 .
[OH−]2/( cNH3 − [OH−]) = 1.75 × 10−5
rearranging gives: [OH−]2 + 1.75 × 10−5[OH−] − cNH3 × 1.75 × 10−5 = 0
cNH [OH−] pOH pH

3
(a) 0.150 1.314 × 10−3 2.88 11.12

(b) 0.0150 4.097 × 10 −4
3.39 10.62
(c) 1.50 × 10 −4
3.399 × 10 −5
4.47 9.53
12-25. Calculate the pH of a solution in which the concentration of piperidine is
Solutions:
(a) 1.00 × 10−1 M.
1.00 × 10 −14
C5H11N + H2O  C5H11NH+ + OH− Kb = = 1.333 × 10 −3
7.5 × 10 −12
5
(b) 1.00 × 10 −2 M.
[C5H11NH+] = [OH−] and [C5H11N] = cC5H11N − [OH−]
(c) 1.00 × 10 −4 M.
[OH−]2/( cC5H11N − [OH−]) = 1.333 × 10−3
rearranging gives: [OH−]2 + 1.333 × 10−3[OH−] − cC5H11N × 1.333 × 10−3 = 0
cC H [OH−] pOH pH
5 11N
(a) 0.100 1.090 × 10−2 1.96 12.04

(b) 0.0100 3.045 × 10 −3
2.52 11.48
(c) 1.00 × 10 −4
9.345 × 10 −5
4.03 9.97
12-27. Calculate the pH of a solution prepared by
Solutions:
(a) dissolving 36.5 g of lactic acid in water and diluting to 500 mL.
1 mmol HA 1
cHA = 36.5 g HA × × = 0.8104 M HA
0.090079 g HA 500 mL soln
HL + H2O  H3O+ + L− Ka = 1.38 × 10−4

[H3O+] = [L−] and [HL] = 0.8104 − [H3O+]
[H3O+]2/(0.8104 − [H3O+]) = 1.38 × 10−4
rearranging and solving the quadratic gives: [H3O+] = 0.0105 and pH = 1.98
(b) diluting 25.0 mL of the solution in (a) to 250 mL.

cHA = 0.8104 × 25.0/250.0 = 0.08104 M HL
Proceeding as in part (a) we obtain: [H3O+] = 3.28 × 10−3 and pH = 2.48
(c) diluting 10.0 mL of the solution in (b) to 1.00 L.

cHA = 0.08104 × 10.0/1000.0 = 8.104 × 10−4 M HL
Proceeding as in part (a) we obtain: [H3O+] = 2.72 × 10−4 and pH = 3.56
12-29. Calculate the pH of the solution that results when 20.0 mL of 0.1750 M formic acid is
Solutions:
(a) diluted to 45.0 mL with distilled water.
0.1750 mmol
amount HFm taken = 20.00 mL × = 3.50 mmol
mL
HFm + H2O  H3O+ + Fm− Ka = 1.80 × 10−4
cHFm = 3.50/45.0 = 7.78 × 10−2 M
6
[H3O+] = [Fm−] and [HFm] = 0.0778 − [H3O+]

[H3O+]2/(0.0778 − [H3O+]) = 1.80 × 10−4
rearranging and solving the quadratic gives: [H3O+] = 3.65 × 10−3 and pH = 2.44
(b) mixed with 25.0 mL of 0.140 M NaOH solution.

amount NaOH added = 25.0 × 0.140 = 3.50 mmol
Since all the formic acid has been neutralized, we are left with a solution of NaFm.
Fm− + H2O  OH− + HFm Kb = 1.00 × 10−14/(1.80 × 10−4) = 5.56 × 10−11
cFm − = 3.00/45.0 = 7.78 × 10−2 M
[OH−] = [HFm] and [Fm−] 0.0778 − [OH−]

[OH−]2/(0.0778 − [OH−]) = 5.56 × 10−11
rearranging and solving the quadratic gives: [OH−] = 2.08 × 10−6 and pH = 8.32
(c) mixed with 25.0 mL of 0.200 M NaOH solution.

amount NaOH added = 25.0 × 0.200 = 5.00 mmol
therefore, we have an excess of NaOH; the pH is determined by the excess [OH−].
[OH−] = (5.00 − 3.50)/45.0 = 3.333 × 10−2 M
pH = 14 − pOH = 12.52
(d) mixed with 25.0 mL of 0.200 sodium formate solution.

amount NaFm added = 25.0 × 0.200 = 5.00 mmol
[HFm] = 3.50/45.0 = 0.0778
[Fm−] = 5.00/45.00 = 0.1111
[H3O+ ] × 0.1111/0.0778 = 1.80 × 10−4
[H3O+] = 1.260 × 10−4 and pH = 3.90
12-31. A solution is 0.0500 M in NH4Cl and 0.0300 M in NH3 . Calculate its OH− concentration
and its pH
Solutions:
(a) neglecting activities.
[H3O+ ][NH3 ]
NH4+ + H2O  H3O+ + NH3 Ka = 5.70 × 10− =
[NH4+ ]
[NH3] = 0.0300 M and [NH4+] = 0.0500 M
[H3O+] = 5.70 × 10−10 × 0.0500/0.0300 = 9.50 × 10−10 M
[OH−] = 1.00 × 10−14/9.50 × 10−10 = 1.05 × 10−5 M
pH = −log(9.50 × 10−10) = 9.02
7
(b) taking activities into account.

μ = ½ {(0.0500)(+1)2 + (0.0500)(−1)2} = 0.0500
From Table 8-2 γ NH = 0.80
+ and γ NH = 1.0
3
4
K aγ NH+ [NH4+ ] 5.70 × 10−10 × 0.80 × 0.0500

aH O+ = 4
= = 7.60 × 10−10
3 γ NH [NH3 ]
3
1.00 × 0.0300
pH = −log(7.60 × 10−10) = 9.12
12-33. What is the pH of a solution that is
Solutions:
In each of the parts of this problem, we are dealing with a weak base B and its conjugate
acid BHCl or (BH)2SO4. The pH determining equilibrium can then be written as
BH+ + H2O  H3O+ + B
The equilibrium concentration of BH+ and B are given by

[BH+] = cBHCl + [OH−] − [H3O+] (1)
[B] = cB − [OH ] + [H3O ]
− +
(2)
In many cases [OH−] and [H3O+] will be much smaller than cB and cBHCl and [BH+] ≈ cBHCl
and [B] ≈ cB so that
cBHCl
[H3O+] = K a × (3)
cB
(a) prepared by dissolving 3.30 g of (NH4 )2 SO4 in water, adding 125.0 mL of 0.1011 M
NaOH, and diluting to 500.0 mL?
1 mmol (NH4 )2 SO4 2 mmol NH+4
Amount NH4+ = 3.30 g (NH4 )2 SO4 × ×
0.13214 g (NH4 )2 SO4 mmol (NH4 )2 SO4
= 49.95 mmol
Amount NaOH = 125.0 mL × 0.1011 mmol/mL = 12.64 mmol
1 mmol NH3 1
cNH = 12.64 mmol NaOH × × = 2.528 × 10−2 M
3
mmol NaOH 500.0 mL
1
cNH+ = (49.95 − 12.64) mmol NH4+ × = 7.462 × 10−2 M
4 500.0 mL
Substituting these relationships in equation (3) gives
cBHCl
[H3O+] = K a × = 5.70 × 10−10 × 7.462 × 10−2 /(2.528 × 10−2) = 1.682 × 10−9 M
cB
[OH−] = 1.00 × 10−14/1.682 × 10−9 = 5.95 × 10−6 M
8
Note, [H3O+] and [OH−] are small compared to cNH3 and cNH+ so our assumption is
4
valid.
pH = −log(1.682 × 10−9) = 8.77
(b) 0.120 M in piperidine and 0.010 M in its chloride salt?

Substituting into equation (3) gives
[H3O+] = 7.5 × 10−12 × 0.010/0.120 = 6.25 × 10−13 M
[OH−] = 1.00 × 10−14/6.25 × 10−13 = 1.60 × 10−2 M
Again our assumption is valid and
pH = −log(6.25 × 10−13) = 12.20
(c) 0.050 M in ethylamine and 0.167 M in its chloride salt?

cB = 0.050 M and cBHCl = 0.167 M
[H3O+] = 2.31 × 10−11 × 0.167/0.050 = 7.715 × 10−11 M
[OH−] = 1.00 × 10−14/7.715 × 10−11 = 1.30 × 10−4 M
The assumption is valid and
pH = −log(7.715 × 10−11) = 10.11
(d) prepared by dissolving 2.32 g of aniline (93.13 g/mol) in 100 mL of 0.0200 M HCl
and diluting to 250.0 mL?
1 mmol
Original amount B = 2.32 g B × = 24.91 mmol
0.09313 g B
Amount HCl = 100 mL × 0.0200 mmol/mL = 2.00 mmol

cB = (24.91 − 2.00)/250.0 = 9.164 × 10−2 M
cBH + = 2.00/250.0 = 8.00 × 10−3 M
[H3O+] = 2.51 × 10−5 × 8.00 × 10−3/(9.164 × 10−2) = 2.191 × 10−6 M

[OH−] = 1.00 × 10−14/2.191 × 10−6 = 4.56 × 10−9 M
Our assumptions are valid, so
pH = −log(2.191 × 10−6) = 5.66
12-34. Calculate the change in pH that occurs in each of the following solutions as a result of a
tenfold dilution with water. Round calculated values for pH to three figures to the right
of the decimal point.
Solutions:
(a) H2O
0.00
9
(c) 0.0500 MNaOH

pH diluted solution = 14.000 − [−log(0.00500)] = 11.699
pH undiluted solution = 14.000 − [−log(0.0500)] = 12.699
ΔpH = 11.699 − 12.699 = −1.000
(e) 0.0500 M CH3COONa
OAc− + H2O  HOAc + OH

[HOAc][OH- ] 1.00 × 10−14
Kb = = = 5.71 × 10−10
[OAc- ] 1.75 × 10−5
Here we can use an approximation because Kb is very small. For the undiluted
sample:
[OH− ]2
= 5.71 × 10 −10
0.0500
[OH−] = (5.71 × 10−10 × 0.0500)1/2 = 5.343 × 10−6 M
pH = 14.00 − [−log(5.343 × 10−6)] = 8.728
For the diluted sample
[OH−] = (5.71 × 10−10 × 0.00500)1/2 = 1.690 × 10−6 M
pH = 14.00 − [−log(1.690 × 10−6)] = 8.228
ΔpH = 8.228 − 8.728 = −0.500
(g) 0.500 M CH3COOH + 0.500 M CH3COONa

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,
ΔpH = 0.000
Note a more concentrated buffer compared to part (f) gives an even smaller pH change.
12-35. Calculate the change in pH that occurs when 1.00 mmol of a strong acid is added to 100
mL of the solutions listed in Problem 12-34.
Solutions:
(a) After addition of acid, [H3O+] = 1 mmol/100 mL = 0.0100 M and pH = 2.00
Since original pH = 7.00
ΔpH = 2.00 − 7.00 = −5.00
(b) After addition of acid

cHCl = (100 × 0.0500 + 1.00)/100 = 0.0600 M
ΔpH = −log(0.0600) − [−log(0.0500)] = 1.222 − 1.301 = −0.079
10
(c) After addition of acid,

cNaOH = (100 × 0.0500 − 1.00)/100 = 0.0400 M
[OH−] = 0.0400 M and pH = 14.00 − [−log(0.0400)] = 12.602
From Problem 12-34 (c), original pH = 12.699
ΔpH = −0.097
(d) From Solution 12-34 (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
ΔpH = 2.000 − 3.033 = −1.033
(If the contribution of the dissociation of HOAc to the pH is taken into account, a pH
of 1.996 is obtained and ΔpH = −1.037 is obtained.)
(e) From Solution 12-34 (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
[H3O+] = 1.75 × 10−5 × 0.0100/0.0400 = 4.375 × 10−6 M
pH = −log(4.375 × 10−6) = 5.359
ΔpH = 5.359 − 8.728 = −3.369
(f) From Solution 12-34 (f), original pH = 4.757

With the addition of 1.00 mmol of HCl we have a buffer whose concentrations are
cHOAc = 0.0500 + 1.00/100 = 0.0600 M
cNaOAc = 0.0500 − 1.00/100 = 0.0400 M
Proceeding as in part (e), we obtain
[H3O+] = 2.625 × 10−5 M and pH = 4.581
ΔpH = 4.581 − 4.757 = −0.176
Note again the very small pH change as compared to unbuffered solutions.
(g) For the original solution

[H3O+] = 1.75 × 10−5 × 0.500/0.500 = 1.75 × 10−5 M
pH = −log(1.75 × 10−5) = 4.757
After addition of 1.00 mmol HCl
cHOAc = 0.500 + 1.00/100 = 0.510 M
cNaOAc = 0.500 − 1.00/100 = 0.490 M
Proceeding as in part (e), we obtain
11
[H3O+] = 1.75 × 10−5 × 0.510/0.490 = 1.821 × 10−5 M

pH = −log(1.821 × 10−5) = 4.740
ΔpH = 4.740 − 4.757 = −0.017
Note that the more concentrated buffer is even more effective in resisting pH
changes.
12-37. Calculate the change in pH to three decimal places that occurs when 0.50 mmol of a
strong acid is added to 100 mL of
Solution:
For lactic acid, Ka = 1.38 × 10−4 = [H3O+][L−]/[HL]
Throughout this problem we will base calculations on Equations 7-25 and 7-26
[L−] = cNaL + [H3O+] − [OH−] ≈ cNaL + [H3O+]
[HL] = cHL − [H3O+] − [OH−] ≈ cHL − [H3O+]
(
[H3O+ ] cNaL + [H3O+ ] ) = 1.38 × 10 −4
cHL − [H3O ]
+
This equation rearranges to

[H3O+]2 + (1.38 × 10−4 + cNaL)[H3O+] − 1.38 × 10−4 × cHL = 0
(b) 0.0800Mlactic acid + 0.0200 Msodium lactate.

Before addition of acid
[H3O+]2 + (1.38 × 10−4 + 0.0200)[H3O+] − 1.38 × 10−4 × 0.0800 = 0
[H3O+] = 5.341 × 10−4 and pH = 3.272
After adding acid
cHL = (100 × 0.0800 + 0.500)/100 = 0.0850 M
cNaL = (100 × 0.0200 − 0.500)/100 = 0.0150 M
[H3O+]2 + (1.38 × 10−4 + 0.0150)[H3O+] − 1.38 × 10−4 × 0.0850 = 0
[H3O+] = 7.388 × 10−4 and pH = 3.131
ΔpH = 3.131 − 3.272 = −0.141
12-39. In a titration of 50.00 mL of 0.05000 M formic acid with 0.1000 M KOH, the titration error
must be smaller than 0.05 mL. What indicator can be chosen to realize this goal?
Solution:
The end point will occur when 25.00 mL of titrant have been added. Let us calculate pH
when 24.95 and 25.05 mL of reagent have been added.
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
12
(50.00 × 0.0500 − 24.95 × 0.1000) mmol HA

=
74.95 mL soln
2.500 − 2.495 0.005
= = = 6.67 × 10−5 M
74.95 74.95
Substituting into Equation 9-????
cHA 1.80 × 10−4 × 6.67 × 10−5
[H3O+ ] = K a = = 3.607 × 10−7 M
cA − 0.03329
pH = −log(3.607 × 10−7) = 6.44

At 25.05 mL KOH
amount KOH added − initial amount HA
cKOH = [OH−] =
total volume soln
25.05 × 0.1000 − 50.00 × 0.05000
= = 6.66 × 10−5 M
75.05 mL soln
pH = 14.00 − [−log(6.66 × 10−5)] = 9.82
Thus, the indicator should change color in the range of pH 6.5 to 9.8. Cresol purple
(range 7.6 to 9.2, Table 12-1) would be quite suitable.
12-41. Calculate the pH after addition of 0.00, 5.00, 15.00, 25.00, 40.00, 45.00, 49.00, 50.00,
51.00, 55.00, and 60.00 mL of 0.1000 M NaOH in the titration of 50.00 mL of
(a) 0.1000 MHNO2 .
13
(c) 0.1000 M lactic acid.
12-43. Calculate the pH after addition of 0.00, 5.00, 15.00, 25.00, 40.00, 49.00, 50.00, 51.00,
55.00, and 60.00 mL of reagent in the titration of 50.0 mL of
Solutions:
(a) 0.01000 M chloroacetic acid with 0.01000 M NaOH.
This titration of a weak acid with strong base follows the same basic spreadsheet as
Pb 12-41 with the concentrations changed. A Scatter plot of pH vs. volume of NaOH
is produced from the data.
14
15
(c) 0.1000 M hypochlorous acid with 0.1000 M NaOH.
12-44. Calculate α0 and α1 for
(a) acetic acid in a solution with a pH of 5.320.

(c) hypochlorous acid in a solution with a pH of 7.00.
(e) piperidine in a solution with a pH of 10.08.
16
Solution:
Here, we make use of Equations 7-36 And 7-37
[H3O+ ] Ka
α0 = +
α1 =
[H3O ] + K a [H3O+ ] + K a
12-45. Calculate the equilibrium concentration of methyl ammonia in a solution that has a
molar analytical CH3NH2 concentration of 0.120 and a pH of 11.471.
Solution:
[H3O+] = 3.38 × 10−12 M. For CH3NH3+, Equation 7-37 takes the form,
[CH3NH2 ] Ka 2.3 × 10 −11
α1 = = = = 0.872
cT [H3O+ ] + K a 3.38 × 10 −12 + 2.3 × 10 −11
[CH3NH2] = 0.872 × 0.120 = 0.105 M
12-47. Supply the missing data in the following table.
Molar Analytical
Concentration, cT
Acid (cT = cHA + cA−) pH [HA] [A−] α0 α1
Lactic 0.120 ___ ____ ____ 0.640 ____
Butanoic ____ 5.00 0.644 ____ ____ ____
Sulfamic 0.250 1.20 ____ ____ ____ ____
Solution:
For lactic acid, Ka = 1.38 × 10−4
[H3O+ ] [H3O+ ]
α0 = =
K a + [H3O+ ] 1.38 × 10−4 + [H3O+ ]
[HA] [HA]
α0 = 0.640 = =
cT 0.120
17
[HA] = 0.640 × 0.120 = 0.0768 M

α1 = 1.000 − 0.640 = 0.360
[A−] = α1 × 0.120 = (1.000 − 0.640) × 0.120 = 0.0432 M
[H3O+] = Ka × cHA/cA- = 1.38 × 10−4 × 0.640/(1 − 0.640) = 2.453 × 10−4 M
pH = −log(2.453 × 10−4) = 3.61
The remaining entries in the table are obtained in a similar manner. Bolded entries are
the missing data points.
Acid cT pH [HA] [A−] α0 α1

Lactic 0.120 3.61 0.0768 0.0432 0.640 0.360
Butanoic 0.162 5.00 0.644 0.0979 0.397 0.604
Sulfamic 0.250 1.20 0.095 0.155 0.380 0.620
18
© 2022, 978-0-357-45055-0, Chapter 13: Complex Acid-Base Systems
Chapter 13
13-1. As its name implies, NaHA is an “acid salt” because it has a proton available to donate to
a base. Briefly explain why a pH calculation for a solution of NaHA differs from that for a
weak acid of the type HA.
Solution:
Not only is NaHA a proton donor, it is also the conjugate base of the parent acid H2A.
HA−+ H2O  H3O+ + A2−
HA− + H2O  H2A + OH−

Solutions of acid salts can be acidic or alkaline, depending on which of the above
equilibria predominates. In order to calculate the pH of solutions of this type, it is
necessary to take both equilibria into account.
13-4. Why is it impossible to titrate all three protons of phosphoric acid in aqueous solution?
Answer:
The species HPO42− is such a weak acid (Ka3 = 4.5 × 10−13) that the change in pH in the
vicinity of the third equivalence point is too small to be observable.
13-5. Indicate whether an aqueous solution of the following compounds is acidic, neutral, or
basic. Explain your answer.
Solutions:
(a) NaH2PO4
H2PO4− + H2O  HPO42− + H3O+ Ka2 = 6.32 × 10−8
1.00 × 10−14
H2PO4− + H2O  H3PO4 + OH− Kb3 = = 1.4 × 10−12
7.11 × 10−3
Solution will be acidic
(c) NaNO3
Neither Na+ nor NO3 − reacts with H2O. Solution will be neutral
1
(e) Na2C 2O 4
1.00 × 10 −14
C2O42− + H2O  HC2O4− + OH− Kb = = 1.84 × 10 −10
5.42 × 10 −5
Solution will be basic
(g) NH4 OAc
NH4+ + H2O  NH3 + H3O+ Ka = 5.70 × 10−10

K w 1.00 × 10 −14
OAc− + H2O  HOAc + OH− Kb = = = 5.71 × 10 −10
K a 1.75 × 10 −5
Since the K’s are essentially identical, the solution should be approximately neutral
13-6. Suggest an indicator that could be used to provide an end point for the titration of the
first proton in H3 AsO4 .
Solution:
We can approximate the [H3O+] at the first equivalence point by Equation 13-16. Thus,
[H3O+ ] = 5.8 × 10−3 × 1.1 × 10−7 = 2.53 × 10−5

pH = –log(2.53 × 10−5) = 4.60
Bromocresol green would be a satisfactory indicator.
13-8. Suggest a method for determining the amounts of H3PO 4 and NaH2PO 4 in an aqueous
solution.
Solution:
Curve A in figure 13-4 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 millimoles 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.
13-9. Suggest a suitable indicator for a titration based on each of the following reactions. Use
0.05 M if an equivalence point concentration is needed.
Solutions:
(a) H2CO3 + NaOH → NaHCO3 + H2O
To obtain the approximate equivalence point pH, we employ Equation 13-16

[H3O+ ] = K a1K a2 = 4.2 × 10−7 × 4.69 × 10−11 = 4.4 × 10−9
pH = 8.4
Cresol purple (7.6 to 9.2) would be suitable.
2
(c) H2 T + 2NaOH → Na2 T + 2H2O(H2 T = tartaric acid)
As in part (b)
[OH−] = (0.05 × 1.00 × 10−14/4.31 × 10−5)1/2 = 3.41 × 10−6 M
pH = 14.00 − [−log(3.41 × 10−6)] = 8.53
Cresol purple (7.6 to 9.2)
(e) NH2C 2H4NH2 + 2HCl → ClNH3C 2H4NH3Cl
NH3C2H4NH32+ + H2O  NH3C2H4NH2+ + H3O+ Ka1 = 1.42 × 10−7

[H3O+] = (0.05 × 1.42 × 10−7)1/2 = 8.43 × 10−5 M
pH = −log(8.43 × 10−5) = 4.07
Bromocresol green (3.8 to 5.4)
(g) H2 SO3 + 2NaOH → Na2 SO3 + 2H2O
Proceeding as in part (b) we obtain pH = 9.94

Phenolphthalein (8.5 to 10.0)
13-10. Calculate the pH of a solution that is 0.0400 M in
Solutions:
(a) H3P O 4 .
H3PO4 + H2O  H3O+ + H2PO4− Ka1 = 7.11 × 10−3
[H3O+ ][H2PO4− ] [H3O+ ]2

= = 7.11 × 10−3
[H3PO4 ] 0.040 − [H3O+ ]
[H3O+]2 + 7.11 × 10−3[H3O+] − 0.040 × 7.11 × 10−3 = 0
Solving by the quadratic formula or by successive approximations, gives
[H3O+] = 1.37 × 10−2 M pH = −log(1.37 × 10−2) = 1.86
(c) H3P O 3 .
pH = 1.64
(e) H2 S.
pH = 4.21
Solutions:
Throughout this problem, we will use Equation 13-15 or one of its simplifications.
3
(a) NaH2PO4 .
0.0400 × 6.32 × 10−8

[H3O+ ] = = 1.95 × 10−5
1 + 0.0400/(7.11 × 10−3 )
pH = −log(1.95 × 10−5) = 4.71
(c) NaH2PO3 .
pH = 4.28
(e) NaHS.
pH = 9.80
Solutions:
(a) Na3PO4 .
Kw 1.00 × 10 −14
PO34− + H2O  HPO24− + OH− Kb = = = 2.2. × 10 −2
K a3 4.5 × 10 −13
[OH− ]2
= 2.22 × 10−2
0.040 − [OH− ]
[OH−]2 + 2.22 × 10−2[OH−] − 8.88 × 10−4 = 0
Solving gives [OH−] = 2.07 × 10−2 M
pH = 14.00 − [−log(2.07 × 10−2)] = 12.32
(c) Na2HPO3 .
Proceeding as in part (b), we obtain pH = 9.70.
(e) Na2 S.
Proceeding as in part (a), gives pH = 12.58
13-14. Calculate the pH of a solution that contains the following analytical concentrations:
Solutions:
(a) 0.225 M in H3PO 4 and 0.414 M in NaH2PO4 .
Proceeding as in Problem 13-13(a), [H3O+] = 3.77 × 10−3 M and pH = 2.42
(b) 0.0670 M in Na2 SO3 and 0.0315 M in NaHSO3 .
Proceeding as in 13-13(b), [H3O+] = 3.10 × 10−8 M and pH = 7.51
4
(c) 0.640 M in HOC 2H4NH2 and 0.750 M in HOC 2H4NH3Cl.
HOC2H4NH3+ + H2O  HOC2H4NH2 + H3O+ Ka = 3.18 × 10−10

Proceeding as in 13-13(b) we obtain [H3O+] = 3.73 × 10−10 M and pH = 9.43
(d) 0.0240 in H2C 2O4 (oxalic acid) and 0.0360 M in Na2C 2O 4 .
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 13-13(a), we obtain [H3O+] = 2.17 × 10−4 M and pH = 3.66
(e) 0.0100 M in Na2C 2O 4 and 0.0400 M in NaHC 2O 4 .
Proceeding as in 13-13(b), we obtain [H3O+] = 2.17 × 10−4 and pH = 3.66
13-16. Calculate the pH of a solution that is
Solutions:
(a) 0.0100 M in HClO4 and 0.0300 M in monochloroacetic acid.
Proceeding as in 13-15(a), we obtain [H3O+] = 1.287 × 10−2 M and pH = 1.89
(b) 0.0100 M in HCl and 0.0150 M in H2 S O 4 .
Recognizing that the first proton of H2SO4 completely dissociates we obtain

HSO4− + H2O  SO42− + H3O+ Ka2 = 1.02 × 10−2
[H3O+ ][SO24− ] (0.0100 + 0.0150 + x ) x

1.02 × 10−2 = =
[HSO ]−
4
0.0150 − x
Rearranging gives x2 + (0.0250 + 1.02 × 10−2)x − (1.02 × 10−2)(0.0150) = 0
Solving the quadratic, gives x = 3.91 × 10−3
The total [H3O+] = 0.0250 + x = 0.0289 M and pH = 1.54
(c) 0.0100 M in NaOH and 0.0300 M in Na2 S.
Proceeding as in 13-15(c) we obtain [OH−] = 0.0382 M and pH = 12.58
(d) 0.0100 M in NaOH and 0.0300 M in sodium acetate.
1.00 × 10 −14
CH3COO− + H2O  CH3COOH + OH− Kb1 = = 5.7 × 10−10
1.75 × 10 −5
CH3COO− is such a weak base that it makes no significant contribution to [OH−]
Therefore, [OH−] = 0.010 M and pH = 12.00
5
13-18. Identify the principal conjugate acid-base pair and calculate the ratio between them in a
solution that is buffered to pH 9.00 and contains
Solutions:
(a) H2 S.
Proceeding as in Problem 13-17(a) with [H3O+] = 1.00 × 10−9 we obtain

[H2S]/[HS−] = 0.010
(b) ethylenediamine dihydrochloride.

Formulating the three species as BH22+, BH+ and B, where B is the symbol for
NH2C2H5NH2.
[H3O+ ][BH+ ] [H3O+ ][B]
= Ka1 = 1.42 × 10−7 and = Ka2 = 1.18 × 10−10
[BH22+ ] [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 < [B] and [BH+]/[B] = 1.00/0.118 = 8.5
(c) H3 AsO4 .
Proceeding as in Problem 13-17(b) we find

[H2AsO4−]/[HAsO42−] = 9.1 × 10−3
(d) H2C O 3 .
Proceeding as in Problem 13-17(a) we find

[HCO3−]/[CO32−] = 21
13-20. What mass (g) of dipotassium phthalate must be added to 750 mL of 0.0500 M phthalic
acid to give a buffer of pH 5.75?
Solution:
pH = 5.75; [H3O+] = antilog (−5.75) = 1.778 × 10−6
Ka2 = [H3O+][P2−]/[HP−] = 3.91 × 10−6
[P2−]/[HP−] = 3.91 × 10−6/(1.778 × 10−6) = 2.199
P2− + H2P → 2HP−
amount H2P present = 750 mL × 0.0500 M = 37.5 mmol
amount HP− in the buffer = 2 × 37.5 mmol = 75.0 mmol
amount P2− needed in the buffer = 2.199 × 75.0 mmol = 164.9 mmol
Thus, we need 37.5 + 164.9 = 202.4 mmol of K2P.
mass K2P = 202.4 mmol × 0.24232 g/mmol = 49.0 g
6
13-22. What is the pH of the buffer formed by adding 100 mL of 0.150 M potassium hydrogen
phthalate to
Solutions:
(a) 100.0 mL of 0.0800 M NaOH?
amount KHP = 100 mL × 0.150 M = 15.0 mmol
amount P− = 100 mL × 0.0800 M = 8.00 mmol
amount KHP = 15.0 − 8.00 = 7.00 mmol
cHP- = 7.00/200 = 0.0350 M; cP2- = 8.00/200 = 0.0400 M
Proceeding as in Problem 13-13(b), we obtain pH = 5.47
(b) 100.0 mL of 0.0800 M HCl?

cH P = 8.00/200 = 0.0400 M; cHP- = (15.00 − 8.00)/200 = 0.0350 M
2
Proceeding as in Problem 13-13(a), we obtain pH = 2.92
13-24. How would you prepare 1.00 L of a buffer with a pH of 7.00 from 0.200 M H3PO 4 and
0.160 M NaOH?
Solution:
[H3O+][HPO42−]/[H2PO4−] = 6.32 × 10−8
[HPO2− ] 6.32 × 10−8
4
= = 0.632 (1)
[H2PO ]
−
4
1.00 × 10−7
Let VH3PO4 and VNaOH be the volume in milliliters of the two reagents. Then
VH PO + VNaOH = 1000 mL (2)

3 4
From mass-balance considerations we may write that in the 1000 mL

amount NaH2PO4 + amount Na2HPO4 = 0.200 × VH3PO4 mmol (3)
amount NaH2PO4 + 2 × amount Na2HPO4 = 0.160 × VNaOH mmol (4)

Equation (1) can be rewritten
no. mmol Na2HPO4 /1000 no. mmol Na2HPO4
= = 0.632 (5)
no. mmol NaH2PO4 /1000 no. mmol NaH2PO4
Thus, we have four equations, (2), (3), (4) and (5), and four unknowns: VH3PO4 , VNaOH, no.
mmol NaH2PO4 and no. mmol Na2HPO4. Subtracting Equation (3) from (4) yields
no. mmol Na2HPO4 = 0.160 VNaOH − 0.200 VH3PO4 (6)
Substituting Equation (6) into (3) gives

no. mmo NaH2PO4 + 0.160 VNaOH − 0.200 VH3PO4 = 0.200 VH3PO4
no. mmo NaH2PO4 = −0.160 VNaOH + 0.400 VH3PO4 (7)
7
Substituting Equations (6) and (7) into (5) gives

0.160VNaOH − 0.200VH PO
3 4
= 0.632
0.400VH PO − 0.160VNaOH
3 4
This equation rearranges to

0.2611 VNaOH = 0.4528 VH3PO4
Substituting Equation (2) gives

0.2611 (1000 − VH3PO4 ) = 0.4528 VH3PO4
VH PO = 261.1/0.7139 = 366 mL and VNaOH = 1000 − 366 = 634 mL

3 4
Thus, mix 366 mL H3PO4 with 634 mL NaOH
13-28. Briefly explain why curve B cannot describe the titration of a mixture consisting of H3PO4
and NaH2PO4 .
Solution:
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 end 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.
13-32. Formulate equilibrium constants for the following equilibria, and determine numerical
values for the constants:
Solutions:
(a) 2H2 AsO−4  H3 AsO4 + HAsO4

 2−
2H2 AsO4−  H3 AsO4 + HAsO24−
[H3O+ ][H2 AsO4− ]

Ka1 = = 5.8 × 10−3 (1)
[H3 AsO4 ]
[H3O+ ][HAsO24− ]
Ka2 = = 1.1 × 10−7 (2)
[H2 AsO4− ]
[H3O+ ][AsO34− ]
Ka3 = = 3.2 × 10−12 (3)
[HAsO24− ]
Dividing Equation (2) by Equation (1) leads to
K a2 [H3 AsO4 ][HAsO24− ]
= = 1.9 × 10−5
K a1 [H2 AsO4− ]2
which is the desired equilibrium constant expression.
8
(b) 2HAsO24−  AsO4 + H2 AsO4


 3− −
2HAsO24−  AsO34− + H2 AsO4−
Here we divide Equation (3) by Equation (2)

K a3 [AsO3− ][H2 AsO4− ]
= 4
= 2.9 × 10−5
K a2 [HAsO24− ]2
13-34. For pH values of 2.00, 6.00, and 10.00, calculate the alpha values for each species in an
aqueous solution of
(a) phthalic acid.

(c) citric acid.
(e) phosphorous acid.
Solutions:
9
© 2022, 978-0-357-45055-0, Chapter 14: Applications of Neutralization Titrations
Chapter 14
14-1. Why is nitric acid seldom used to prepare standard acid solutions?
Solution:
Nitric acid is seldom used as a standard because it is an oxidizing agent and thus will
react with reducible species in titration mixtures.
14-3. The boiling points of HCl and CO2 are nearly the same ( −85°C and −78°C ). Explain why
CO2 can be removed from an aqueous solution by boiling briefly while essentially no HCl
is lost even after boiling for 1 hour or more.
Solution:
Carbon dioxide is not strongly bonded by water molecules, and thus is readily volatilized
from aqueous solution by briefly boiling. On the other hand, HCl molecules are fully
dissociated into H3O+ and Cl− when dissolved in water. Neither the H3O+ nor the Cl−
species is volatile.
14-5. Give two reasons why KH (IO3 )2 is preferred over benzoic acid as a primary standard for
a 0.010 M NaOH solution.
Solution:
Let us consider the standardization of 40 mL of 0.010 M NaOH using KH(IO3)2,
0.010 mmol NaOH 1mmol KH(IO3 )2 390 g KH(IO3 )2
× 40 mL NaOH × × = 0.16 g KH(IO3 )2
mL 1mmol NaOH 1000 mmol
Now using benzoic acid,

0.010 mmol NaOH 1mmol C6H5COOH
× 40 mL NaOH × ×
mL 1mmol NaOH
122 g C6H5COOH
= 0.049 g C6H5COOH
1000 mmol
The primary standard KH(IO3)2 is preferable because the relative mass measurement
error would be less with a 0.16 g sample of KH(IO3)2 as opposed to 0.049 g sample of
benzoic acid. A second reason for preferring KH(IO3)2 is because it is a strong acid and
benzoic acid is not. A smaller titration error occurs when using a strong acid as a primary
standard and the choice of indicator is not critical.
1
14-7. Briefly describe the circumstance where the concentration of a sodium hydroxide
solution will apparently be unaffected by the absorption of carbon dioxide.
Solution:
If the sodium hydroxide solution is to be used for titrations with an acid-range indicator,
the carbonate in the base solution will consume two analyte hydronium ions just as
would the two hydroxides lost in the formation of Na2CO3.
14-9. How would you prepare 2.00 L of
Solutions:
(a) 0.10 M KOH from the solid?
0.10 mole KOH 56.106 g KOH

× 2.00 L × = 11 g KOH
L mole
Dissolve 11 g KOH in water and dilute to 2.00 L total volume.
(b) 0.010 MBa ( OH)2 ⋅ 8H2O from the solid?
0.010 mole Ba(OH)2 ⋅ 8H2O 315.46 g Ba(OH)2 ⋅ 8H2O

× 2.00 L × = 6.3 g Ba(OH)2 ⋅ 8H2O
L mole
Dissolve 6.3 g Ba(OH)2·8H2O in water and dilute to 2.00 L total volume.
(c) 0.150 M HCl from a reagent that has a density of 1.0579 g/mL and is 11.50% HCl
(w/w)?
0.150 mole HCl 36.461g HCl mL reagent 100 g reagent

× 2.00 L × × ×
L mole 1.0579 g reagent 11.50 g HCl
= 90 mL reagent
Dilute 90 mL reagent to 2.00 L total volume.
14-11. The concentration of a perchloric acid solution was established by titration against
primary-standard sodium carbonate (product: CO 2 ); the following data were obtained.
Mass Na2CO3 , g 0.2068 0.1997 0.2245 0.2137
Volume HClO4 , mL 36.31 35.11 39.00 37.54
Solutions:
For the first data set,
1000 mmolNa2CO3 2 mmolHClO4
0.2068 g Na2CO3 × ×
105.99 g 1mmolNa2CO3
csample 1 = = 0.10747 MHClO4
36.31mL HClO4
The results in the accompanying table were calculated in the same way.
2
Sample csample i, M csample i2

1 0.10747 1.15499×10−2
2 0.10733 1.15196×10−2
3 0.10862 1.17987×10−2
4 0.10742 1.15385×10−2
c sample i
= 0.43084 c sample i
2
= 4.64069 × 10 −2
(a) Calculate the average molar concentration of the acid.

0.43084
csample i = = 0.1077 M HClO4
4
(b) Calculate the standard deviation for the data and the coefficient of variation for the
data.
(4.64069 × 10 −2 ) − (0.43084)2 / 4 1.11420 × 10 −6

s = = = 6.1 × 10 −4
3 3
6.1 × 10 −4
CV = × 100% = 0.57%
0.1077
(c) Use statistics to decide whether the outlier should be retained or rejected.
0.10862 − 0.10747
Q= = 0.89
0.10862 − 0.10733
Qcrit = 0.829 at the 95% confidence level
Qcrit = 0.926 at the 99% confidence level
Thus, 0.10862 could be rejected at 95% level but must be retained at 99% level.
14-13. A NaOH solution was 0.1019 M immediately after standardization. Exactly 500.0 mL of
the reagent was left exposed to air for several days and absorbed 0.652 g of CO2 .
Calculate the relative carbonate error in the determination of acetic acid with this
solution if the titrations were performed with phenolphthalein.
Solution:
As in part (a) of problem 14-12,
 0.1019 mmolNaOH   1000 mmol CO2 1mmolNaOH 
 × 500 mL  −  0.652 g CO2 × × 
 mL   44.01g 1mmol CO2 
cbase =
500 mL
= 0.07227 M NaOH
0.07227 − 0.1019
relative carbonate error = × 100% = − 29%
0.1019
3
14-15. Calculate the molar concentration of a dilute Ba ( OH)2 solution if
Solutions:
(a) 50.00 mL yielded 0.1791 g of BaSO 4 .
1000 mmolBaSO4 1mmolBa(OH)2

0.1791g BaSO4 × ×
233.39 g 1mmolBaSO4
= 0.01535 M Ba(OH)2
50.00 mL Ba(OH)2
(b) titration of 0.4512 g of primary-standard potassium hydrogen phthalate (KHP)

required 26.46 mL of the base.
1000 mmol KHP 1mmol Ba(OH)2

0.4512 g KHP × ×
204.224 g 2 mmol KHP
= 0.04175 M Ba(OH)2
26.46 mL Ba(OH)2
(c) addition of 50.00 mL of the base to 0.3912 g of benzoic acid required a 4.67-mL
back-titration with 0.05317 M HCl.
1000 mmol C6H5COOH
amnt C6H5COOH = 0.3912 g C6H5COOH × = 3.2033 mmol
122.123 g
0.05317 mmol HCl
amnt HCl = × 4.67 mL HCl = 0.2483 mmol
mL
total amnt acid = 3.2034 + 0.2483 = 3.4516 mmol
1mmolBa(OH)2
3.4516 mmol acid ×
2 mmol acid
= 0.03452 M Ba(OH)2
50.00 mL Ba(OH)2
14-17. Calculate the relative standard deviation in the computed molar concentration of 0.0200
M HCl if this acid was standardized against the masses found in Example 14-1 for (a)
TRIS, (b) Na2CO3 , and (c) Na2B 4O7 ⋅ 10H2O. Assume that the absolute standard deviation
in the mass measurement is 0.0001 g and that this measurement limits the precision of
the computed concentration.
Solutions:
In Example 14-1, we found that 20.00 mL of 0.0200 M HCl requires 0.048 g TRIS, 0.021 g
Na2CO3 and 0.08 g Na2B4O7·10H2O. In each case, the absolute standard deviation in
computed molarity of 0.0200 M HCl is
0.0001
TRIS: sc = × 0.0200 M = 4 × 10−5 M
0.048
0.0001
Na2CO3: sc = × 0.0200 M = 1 × 10−4 M
0.021
0.0001
Na2B4O7·10H2O: sc = × 0.0200 M = 2.5 × 10−5 M ≈ 3.0 × 10−5 M
0.076
4
Proceeding as above, we calculate the relative standard deviation in the computed molar
concentrations of 30.00 mL, 40.00 mL and 50.00 mL of 0.0200 M HCl and the results are
shown in the table that follows.
V0.0200 M HCl (mL) Calculated masses (g) sc (0.0200 M HCl)

30.00
TRIS 0.073 3 × 10−5
Na2CO3 0.032 6 × 10−5
Na2B4O7·10H2O 0.11 2 × 10−5
40.00
TRIS 0.097 2 × 10−5
Na2CO3 0.042 5 × 10−5
Na2B4O7·10H2O 0.15 1 × 10−5
50.00
TRIS 0.12 2 ×1 0−5
Na2CO3 0.053 4 × 10−5
Na2B4O7·10H2O 0.19 1 × 10−5
14-19. A 50.00-mL sample of a white dinner wine required 24.57 mL of 0.03291 M NaOH to
achieve a phenolphthalein end point. Express the acidity of the wine in grams of tartaric
acid (H2C 4H4O6 ; 150.09 g/mol) per 100 mL. (Assume that two hydrogens of the acid are
titrated.) Tartaric acid is not found in many fruits or plants, but it is the primary acid in
wine grapes.
Solution:
0.03291mmolNaOH
amnt NaOH = × 24.57 mL NaOH = 0.80860 molNaOH
mL
 1mmolH2C 4H4O6 150.09 g H2C 4H4O6 
 0.80860 molNaOH × × 
 2 mmolNaOH 1000 mmol  × 100 mL
50.00 mL
= 0.1214 g H2C 4H4O6 per 100 mL
14-21. Titration of a 0.7513-g sample of impure Na2B 4O7 required 30.79 mL of 0.1129 M HCl
(see Problem 14-16f for reaction). Express the results of this analysis in terms of percent
Solutions:
For each part, we can write
0.1129 mmolHCl
× 30.79 mL HCl mmolHCl
mL = 4.6269
0.7513 g sample g sample
5
(a) Na2B 4O7 .
mmolHCl 1mmolNa2B4O7 201.222 g Na2B4O7

4.6269 × × × 100% = 46.55% Na2B4O7
g sample 2 mmolHCl 1000 mmol
Proceeding in the same way
(b) Na2B 4O7 ⋅ 10H2O.
mmolHCl 1mmolNa2B4O7 ⋅ 10H2O 381.372 g Na2B4O7 ⋅ 10H2O

4.6269 × × × 100%
g sample 2 mmolHCl 1000 mmol
= 88.23% Na2B4O7 ⋅ 10H2O
(c) B 2 O3 .
mmolHCl 1mmolB2O3 69.620 g B2O3

4.6269 × × × 100% = 32.21% B2O3
g sample 1mmolHCl 1000 mmol
(d) B.
mmolHCl 2 mmolB 10.811g B

4.6269 × × × 100% = 10.00% B
g sample 1mmolHCl 1000 mmol
14-23. The formaldehyde (HCHO) content of a pesticide preparation was determined by

weighing 0.2985 g of the liquid sample into a flask containing 50.0 mL of 0.0959 M NaOH
and 50 mL of 3% H2O2 . Upon heating, the following reaction took place:
OH− + HCHO + H2 O2 → HCOO− + 2H2O
After cooling, the excess base was titrated with 22.71 mL of 0.053700 MH2SO4 . Calculate
the percentage of HCHO (30.026 g/mol) in the sample.
Solution:
 0.0959 mmolNaOH 
amnt NaOH consumed =  × 50.0 mL NaOH  −
 mL 
 0.05370 mmolH2SO4 2 mmolNaOH 
 × 22.71mL H2SO4 ×  = 2.356 mmol
 mL 1mmolH2SO4 
1mmolHCHO 30.026 g HCHO
2.356 mmolNaOH × ×
1mmolNaOH 1000 mmol
× 100% = 23.7% HCHO
0.2985 g sample
14-25. The active ingredient in Antabuse, a drug used for the treatment of chronic alcoholism, is
tetraethylthiuram disulfide,
S S
 
(C2H5 )2 NCSSCN(C2H5 )2
6
(296.54 g/mol). The sulfur in a 0.4169-g sample of an Antabuse preparation was oxidized
to SO2 , which was absorbed in H2O2 to give H2SO4 . The acid was titrated with 19.25 mL
of 0.04216 M base. Calculate the percentage of active ingredient in the preparation.
Solution:
Tetraethylthiuram disulfide, TS4
1 mmol TS4 ≡ 4 mmol SO2 ≡ 4 mmol H2SO4 ≡ 8 mmol NaOH
 0.04216 mmolNaOH 1mmol TS4 296.54 g TS4 
 × 19.25 mL NaOH × × 
 mL 8 mmolNaOH 1000 mmol 
× 100%
0.4169 g sample
= 7.216% TS4
14-27. A 0.1401-g sample of a purified carbonate was dissolved in 50.00 mL of 0.1140 M HCl
and boiled to eliminate CO2 . Back-titration of the excess HCl required 24.21 mL of
0.09802 M NaOH. Identify the carbonate.
Solution:
amnt HCl = mmolNaOH − 2 × mmol CO32−
 0.1140 mmolHCl   0.09802 mmolNaOH 
 × 50.00 mL HCl  −  × 24.21mL NaOH 
mL mL
amnt CO32 − =    
2
=1.6635 mmol CO32 −
0.1401g salt 1000 mmol g salt
molar mass carbonate salt = × = 84.22
1.6635 mmol CO32− mole mole CO32−
 g salt 1mole CO32−  g CO32−

molar mass of carbonate salt cation =  84.22 ×  − 60.01
 mole CO32− 1mole salt  mole

g cation
= 24.21
mole
MgCO3 with a molar mass of 84.31g/mole appears to be a likely candidate
14-29. A 3.00-L sample of urban air was bubbled through a solution containing 50.0 mL of
0.0116 MBa ( OH)2 , which caused the CO2 in the sample to precipitate as BaCO3 . The
excess base was back-titrated to a phenolphthalein end point with 23.6 mL of 0.0108 M
HCl. Calculate concentration of CO2 in the air in parts per million (that is,
mL CO2 /106 mL air); use 1.98 g/L for the density of CO2 .
7
Solution:
mmol HCl
amnt Ba(OH)2 = mmol CO2 +
2
 0.0108 mmol HCl 
 0.0116 mmol Ba(OH)2   ×23.6 mL HCl 
amnt CO2 =  × 50.0 mL Ba(OH)2  −  mL 
 mL   2 
 
 
= 4.526 × 10 mmol
−1
44.01g CO2
0.4526 mmol CO2 ×
1000 mmol 1L CO2
× × 106 ppm = 3.35 × 103 ppm CO2
3.00 L 1.98 g CO2
14-31. The digestion of a 0.1417-g sample of a phosphorus-containing compound in a mixture

of HNO3 and H2SO4 resulted in the formation of CO2 , H2O , and H3PO4 . Addition of
ammonium molybdate yielded a solid having the composition
(NH4 )3 PO4 ⋅ 12MoO3 (1876.3 g/mol) . This precipitate was filtered, washed, and dissolved
in 50.00 mL of 0.2000 M NaOH:
(NH )4 3
PO 4 ⋅ 12MoO3 ( s ) + 26OH− → HPO4 2 −
+12MoO4 2 − + 14H2 O + 3NH3 ( g )
After the solution was boiled to remove the NH3 , the excess NaOH was titrated with
14.17 mL of 0.1741 M HCl to a phenolphthalein end point. Calculate the percentage of
phosphorus in the sample.
Solution:
(NH4 )3PO4 ⋅ 12MoO3 (s) + 26OH− → HPO42− + 12MoO4 2− + 14H2O + 3NH3 (g )
amnt NaOH consumed =  × 50.00 mL NaOH  −
 mL 
 0.1741mmolHCl 
 × 14.17 mL HCl  = 7.533 mmol
 mL 
1mmol (NH4 )3PO4 ⋅ 12MoO3
amnt P = 7.533 mmolNaOH × ×
26 mmolNaOH
1mmolP
= 2.897×10−1 mmol
1mmol (NH4 )3PO4 ⋅ 12MoO3
30.974 g P
2.897 × 10−1 mmolP ×
1000 mmol
× 100% = 6.333% P
0.1417 g sample
14-33. Neohetramine, C16H22 ON4 ( 286.37 g/mol) , is a common antihistamine. A 0.1247-g

sample containing this compound was analyzed by the Kjeldahl method. The ammonia
produced was collected in H3BO3 ; the resulting H2BO3−2 was titrated with 26.13 mL of
0.01477 M HCl. Calculate the percentage of neohetramine in the sample.
8
Solution:
Neohetramine, C16H22ON4 = RN4
1mmol RN4 ≡ 4 mmol NH3 ≡ 4 mmol HCl
0.01477 mmol HCl 1mmol RN4 286.37 g RN4
× 26.13 mL HCl × ×
mL 4 mmol HCl 1000 mmol
× 100% = 22.16% RN4
0.1247 g sample
14-35. A 0.917-g sample of canned tuna was analyzed by the Kjeldahl method. A volume of
20.59 mL of 0.1249 M HCl was required to titrate the liberated ammonia. Calculate the
percentage of nitrogen in the sample.
Solution:
 0.1249 mmolHCl  1mmolN 14.007 g N
 × 20.59 mL HCl  × ×
mL mmolHCl 1000 mmol
%N =   × 100% = 3.93% N
0.917 g sample
14-37. A 0.5843-g sample of a plant food preparation was analyzed for its N content by the
Kjeldahl method, the liberated NH3 being collected in 50.00 mL of 0.1062 M HCl. The
excess acid required an 11.89 mL back-titration with 0.0925 M NaOH. Express the results
of this analysis in terms of
(a) %N. (c) % (NH4 )2 SO4 .
(b) %urea, H2NCONH2 . (d) % (NH4 )3 PO4 .
Solutions:
9
14-39. A 1.219-g sample containing (NH4)2SO4, NH4NO3, and nonreactive substances was
diluted to 200 mL in a volumetric flask. A 50.00-mL aliquot was made basic with strong
alkali, and the liberated NH3 was distilled into 30.00 mL of 0.08421 M HCl. The excess
HCl required 10.17 mL of 0.08802 M NaOH for neutralization. A 25.00-mL aliquot of the
sample was made alkaline after the addition of Devarda’s alloy, and the NO3− was
reduced to NH3 . The NH3 from both NH4 + and NO3− was then distilled into 30.00 mL of
the standard acid and back-titrated with 14.16 mL of the base. Calculate the percentage
of (NH4 )2 SO4 and NH4NO3 in the sample.
Solution:
In the first titration,
 0.08421mmolHCl 
amnt HCl consumed =  × 30.00 mL  −
 mL 
 × 10.17 mL  = 1.63114 mmol
 mL 
and
1.63114 mmolHCl = mmolNH4NO3 + ( 2 × mmol (NH4 )2SO4 )
The amounts of the two species in the original sample are

200 mL
mmolNH4NO3 + ( 2 × mmol (NH4 )2SO4 ) = 1.63114 mmol × = 6.5246 mmol (1)
50 mL
In the second titration,
 0.08421mmolHCl 
amnt HCl consumed =  × 30.00 mL  −
 mL 
 × 14.16 mL  = 1.27994 mmolHCl
 mL 
and
1.27994 mmol HCl = (2 × mmol NH4NO3 ) + ( 2 × mmol (NH4 )2 SO4 )
The amounts of the two species in the original sample are

(2 × mmolNH4NO3 ) + ( 2×mmol (NH4 )2SO4 ) = 1.27994 mmol ×
200 mL (2)
= 10.2395 mmol
25 mL
Subtracting equation (1) from equation (2) gives
10
amnt NH4NO3 = 10.2395 mmol − 6.52455 mmol = 3.7149 mmol

10.2395 mmol − (2 × 3.7149 mmol)
amnt (NH4 )2 SO4 = = 1.4048 mmol
2
80.04 g NH4NO3
3.7149 mmol NH4NO3 ×
1000 mmol
percentage NH4NO3 = × 100% = 24.39%
1.219 g sample
132.14 g (NH4 )2 SO4
1.4048 mmol (NH4 )2 SO4 ×
1000 mmol
percentage (NH4 )2 SO4 = × 100%
1.219 g sample
= 15.23%
14-41. A 0.5000-g sample containing NaHCO3 , Na2 CO3 , and H2O was dissolved and diluted to
250.0 mL. A 25.00-mL aliquot was then boiled with 50.00 mL of 0.01255 M HCl. After
cooling, the excess acid in the solution required 2.34 mL of 0.01063 M NaOH when
titrated to a phenolphthalein end point. A second 25.00-mL aliquot was then treated
with an excess of BaCl2 and 25.00 mL of the base. All the carbonate precipitated, and
7.63 mL of the HCl was required to titrate the excess base. Determine the composition of
the mixture.
Solution:
For the first aliquot,
amnt HCl = mmolNaOH + mmolNaHCO3 + (2 × mmolNa2CO3 )
 0.01255 mmolHCl 
mmolNaHCO3 + (2 × mmolNa2CO3 ) =  × 50.00 mL HCl  −
 mL 
 × 2.34 mL NaOH  = 0.6026 mmol
 mL 
For the second aliquot,
amnt NaHCO3 = mmol NaOH − mmol HCl
 0.01063 mmol NaOH   0.01255 mmol HCl 
= × 25.00 mL NaOH  −  × 7.63 mL HCl 
 mL   mL 
= 0.1700 mmol
84.01g NaHCO3
0.1700 mmolNaHCO3 ×
1000 mmol
percentage NaHCO3 = × 100% = 28.56%
 25.00 g 
 0.5000 g × 
 250.0 g 
105.99 g Na2CO3
0.2163 mmolNa2CO3 ×
1000 mmol
percentage Na2CO3 = × 100% = 45.85%
 25.00 mL 
 0.5000 g × 
 250.0 mL 
100% − (28.56% + 45.85%) = 25.59% H2O
11
14-43. Calculate the volume of 0.07731 M NaOH needed to titrate
(a) 25.00 mL of a solution that is 0.03000 M in HCl and 0.01000 M in H3PO4 to a

bromocresol green end point.
(b) the solution in (a) to a thymolphthalein end point.
(c) 30.00 mL of 0.06407 MNaH2PO4 to a thymolphthalein end point.
(d) 25.00 mL of a solution that is 0.02000 M in H3PO4 and 0.03000 M in NaH2PO 4 to a

thymolphthalein end point.
Solutions:
12
14-45. A series of solutions containing NaOH , Na2CO3 , and NaHCO3 , alone or in compatible
combination, was titrated with 0.1202 M HCl. In the following table are the volumes of
acid needed to titrate 25.00-mL portions of each solution to (1) a phenolphthalein and (2)
a bromocresol green end point. Use this information to deduce the composition of the
solutions. In addition, calculate the mass in milligrams of each solute per milliliter of solution.
(1) (2)
(a) 22.42 22.44

(b) 15.67 42.13
(c) 29.64 36.42
(d) 16.12 32.23
(e) 0.00 33.333
Solutions:
14-47. Calculate the equivalent mass of oxalic acid dehydrate (H2C2O4 ⋅ 2H2O , 126.066 g/mol)
when it is titrated to (a) a bromocresol green end point and (b) a phenolphthalein end
point.
Solutions:
(a) With bromocresol green, only one of the two protons in the oxalic acid will react.
Therefore, the equivalent mass is the molar mass, or 126.066 g.
(b) When phenolphthalein is the indicator, two of the protons are consumed.
Therefore, the equivalent mass of oxalic acid is one-half the molar mass, or 63.03 g.
13
© 2022, 978-0-357-45055-0, Chapter 15: Complexation and Precipitation Reactions and Titrations
Chapter 15
15-1. Define
Solutions:
(a) ligand.
A ligand is a species that contains one or more electron pair donor groups that
tend to form bonds with metal ions.
(c) tetradentate chelating agent.

A tetradentate chelating agent is a molecule that contains four pairs of donor
electron located in such positions that they all can bond to a metal ion, thus
forming two rings.
(e) argentometric titration.

Argentometric titrations are titrations based on the formation of precipitates with
standard solutions of silver nitrate. An example is the titration of a halide ion with
silver nitrate to form the isoluble silver halide.
(g) EDTA displacement titration.

In an EDTA displacement titration, an unmeasured excess of a solution containing
the magnesium or zinc complex of EDTA is introduced into the solution of an
analyte that forms a more stable complex than that of magnesium or zinc. The
liberated magnesium or zinc ions are then titrated with a standard solution of
EDTA. Displacement titrations are used for the determination of cations for which
no good indicator exists.
15-3. Describe three general methods for performing EDTA titrations. What are the
advantages of each?
Solution:
Three general methods for performing EDTA titrations are (1) direct titration, (2) back
titration, and (3) displacement titration. Method (1) is simple, rapid, but requires one
standard reagent. Method (2) is advantageous for those metals that react so slowly with
EDTA as to make direct titration inconvenient. In addition, this procedure is useful for
cations for which satisfactory indicators are not available. Finally, it is useful for analyzing
samples that contain anions that form sparingly soluble precipitates with the analyte
1
under analytical conditions. Method (3) is particularly useful in situations where no

satisfactory indicators are available for direct titration.
15-4. Write chemical equations and equilibrium-constant expressions for the stepwise
formation of
Solution:
(a) Ag(S2O3)23−.
[Ag(S2O3 ) − ]
Ag+ + S2O32−  Ag(S2O3)− K1 =
[Ag + ][S2O32− ]
[Ag(S2O3 )23− ]
Ag(S2O3)− + S2O32−  Ag(S2O3)23− K2 =
[Ag(S2O3 ) − ][S2O32− ]
15-5. Explain how stepwise and overall formation constants are related.
Solution:
The overall formation constant βn is equal to the product of the individual stepwise
constants. Thus, the overall constant for formation of Ag(S2O3)23−− in Problem 15.4 (a) is
[Ag(S2O3 )23−
β 2 = K1K2 =
[Ag + ][S2O32− ]2
15-7. In what respect is the Fajans method superior to the Volhard method for the titration of
chloride ion?
Solution:
The Fajans determination of chloride involves a direct titration, while a Volhard titration
requires two standard solutions and a filtration step to remove AgCl before back titration
of the excess SCN−.
15-9. Why does the charge on the surface of precipitate particles change sign at the
equivalence point of a titration?
Solution:
The ions that are preferentially absorbed on the surface of an ionic solid are generally
lattice ions. Thus, in the beginning stages of a precipitation 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.
2
15-11. Write equations in terms of the acid dissociation constants and [H+] for the highest alpha
value for each of the following weak acid ligands:
Solutions:
(a) acetate (α1).
Acetate (OAc−)
[OAc − ][H+ ]
HOAc  OAc− + H+ Ka =
[HOAc]
cT = [HOAc] + [OAc−]
[OAc − ][H+ ]  [H+ ]   [H+ ] + K a 
= + [OAc− ] = [OAc− ]  + 1 = [OAc− ]  
Ka  K a   Ka 
[OAc − ] K
α1 = = + a
cT [H ] + K a
(b) tartrate (α2).

Tartrate (T2−)
[HT − ][H+ ]
H2T  HT− + H+ K a1 =
[H2 T]
[T 2− ][H+ ]
HT−  T2− + H+ K a2 =
[HT − ]
cT = [H2T] + [HT−] + [T2−]
[HT − ][H+ ] [T 2− ][H+ ] [T 2− ][H+ ]2 [T2− ][H+ ]
= + + [T2− ] = + + [T2− ]
K a1 K a2 K a1K a2 K a2
 [H ] + K a1[H ] + K a1K a2 
+ 2
 [H+ ]2 [H+ ]  +
= [T2− ]  + + 1 = [T2− ]  
 K a1K a2 K a2   K a1K a2 
[T 2− ] K a1K a2
α2 = = + 2
cT [H ] + K a1[H+ ] + K a1K a2
(c) phosphate (α3).

Phosphate
[H2PO4 − ][H+ ]
H3PO4  H2PO4− + H+ K a1 =
[H3PO4 ]
[HPO4 2 − ][H+ ]
H2PO4−  HPO42− + H+ K a2 =
[H2PO4 − ]
[PO4 3− ][H+ ]
HPO42−  PO43− + H+ K a3 =
[HPO4 2− ]
cT = [H3PO4] + [H2PO4−] + [HPO42−] + [PO43−]
3
Proceeding as in the preceeding problem, we obtain

 [H+ ]3 + K a1[H+ ]2 + K a1K a2 [H+ ] + K a1K a2K a3 
cT = [PO4 3− ]  
 K a1K a2K a3 
[PO4 3− ] K a1K a2K a3

α3 = = + 3
cT + 2
[H ] + K a1[H ] + K a1K a2 [H+ ] + K a1K a2K a3
15-13. Write a conditional overall formation constant for [Fe(Ox)3]3− in terms of α2 for oxalic acid
and the β value for the complex. Also express the conditional constant in terms of
concentrations as in Equation 15-20.
Solution:
[Fe(Ox)33 − ]
Fe3+ + 3Ox2−  Fe(Ox)33− β3 =
[Fe3 + ][Ox2 − ]3
[Ox2− ]
α2 = so [Ox2−] = α 2 cT
cT
[Fe(Ox)33 − ] [Fe(Ox)33 − ]
β3 = =
[Fe3 + ][Ox 2 − ]3 [Fe3+ ](α 2 cT )3
[Fe(Ox)33− ]
β 3′ = (α 2 )3 β 3 =
[Fe3 + ](cT )3
15-15. Given an overall complex formation reaction of M + nL  ML n , with an overall formation

constant of βn, show that the following relationship holds:
log βn = pM + npL − pMLn

Solution:
[ML n ]
βn =
[M][L]n
Taking the logarithm of both sides of the above equation yields

log βn = log[MLn] − log[M] − nlog[L]
Now write the right hand side of the equation as a p function (i.e., pM = −log[M]).
log βn = pM +npL − pMLn
15-17. An EDTA solution was prepared by dissolving 3.426 g of purified and dried Na2H2Y · 2H2O
in sufficient water to give 1.000 L. Calculate the molar concentration, given that the
solute contained 0.3% excess moisture (see Section 15D-1).
Solution:
99.7 g Na2H2 Y ⋅ 2H2O 1 mole EDTA
3.426 g reagent × ×
100 g reagent 372.24 g Na2H2 Y ⋅ 2H2O
= 0.00918 M EDTA
1.000 L
4
15-19. A solution contains 1.569 mg of CoSO4 (155.0 g/mol) per milliliter. Calculate
Solutions:
First calculate the CoSO4 concentration
1.569 mg 1 mmol CoSO4
× = 0.010123 M
mL 155.0 mg
In each part 25.00 mL of this solution is taken, so

0.010123 mmol
amount CoSO4 = 25.00 mL × = 0.25306 mmol
mL
(a) the volume of 0.007840 M EDTA needed to titrate a 25.00-mL aliquot of this
solution.
1 mmol EDTA 1 mL
Vol. EDTA = 0.25306 mmol CoSO4 × × = 32.28 mL
mmol CoSO4 0.007840 mmol EDTA
(b) the volume of 0.009275M Zn2+ needed to titrate the excess reagent after addition
of 50.00 mL of 0.007840 M EDTA to a 25.00-mL aliquot of this solution.
 0.007840 mmol 
amnt excess EDTA =  × 50.00 mL 
 mL 
 1 mmol 
−  0.25306 mmol CoSO4 ×  = 0.1389 mmol
 mmol CoSO4 
1 mmol Zn2 + 1 mL
Vol. Zn2+ = 0.1389 mmol EDTA × × = 14.98 mL
mmol EDTA 0.009275 mmol Zn2+
(c) the volume of 0.007840 M EDTA needed to titrate the Zn2+ displaced by Co2+
following addition of an unmeasured excess of ZnY2− to a 25.00-mL aliquot of the
CoSO4 solution. The reaction is
Co2+ + ZnY 2− → CoY 2− + Zn2+

1 mmol Zn2+ 1 mmol EDTA 1 mL
Vol. EDTA = 0.25306 mmol CoSO4 × × ×
mmol CoSO4 mmol Zn 2+
0.007840 mmol EDTA
= 32.28 mL
15-20. Calculate the volume of 0.0500 M EDTA needed to titrate
Solution:
(a) 29.13 mL of 0.0598 MMg (NO3 )2 .
0.0598 mmol Mg(NO3 )2 1 mmol EDTA mL

Vol. EDTA = × 29.13 mL × ×
mL mmol Mg(NO3 ) 0.0500 mmol EDTA
2
= 34.84 mL
5
(c) the Ca in a 0.4861-g mineral specimen that is 81.4% brushite, CaHPO4·2H2O (172.09
g/mol).
81.4 g CaHPO4 ⋅ 2H2O 1000 mmol

Amnt. CaHPO4 ⋅ 2H2O = 0.4861 g × ×
100 g 172.09 g CaHPO4 ⋅ 2H2O
= 2.2993 mmol
1 mmol EDTA 1 mL
Vol. EDTA = 2.2993 mmol CaHPO4 ⋅ 2H2O × ×
mmol CaHPO4 ⋅ 2H2O 0.0500 mmol EDTA
= 45.99 mL
(e) the Ca and Mg in a 0.1612-g sample that is 92.5% dolomite, CaCO3·MgCO3 (184.4
g/mol).
92.5 g 1000 mmol dolo 2 mmol EDTA 1 mL

Vol. EDTA = 0.1612 g × × × ×
100 g 184.4 g mmol dolo 0.0500 mmol EDTA
= 32.34 mL
15-21. The Zn in a 0.7457-g sample of foot powder was titrated with 22.57 mL of 0.01639 M
EDTA. Calculate the percent Zn in this sample.
Solution:
0.01639 mmol EDTA 1 mmol Zn2+ 65.39 g
Wt. Zn = × 22.57 mL × × = 0.024189 g
mL mmol EDT A 1000 mmol Zn2+
0.024189 g Zn
Percentage Zn = × 100% = 3.244%
0.7457 g sample
15-23. A silver nitrate solution contains 14.77 g of primary-standard AgNO3 in 1.00 L. What
volume of this solution will be needed to react with
Solutions:
14.77 g 1 mol AgNO3
Conc. AgNO3 = × = 0.08695 M
L 169.873 g
(a) 0.2631 g of NaCl?
mmol NaCl 1 mmol AgNO3 1 mL AgNO3

Vol. AgNO3 = 0.2631 g × × × = 51.78 mL
0.05844 g mmol NaCl 0.08695 mmol AgNO3
(c) 64.13 mg of Na3 AsO4 ?
mmol Na3 AsO4 3 mmol AgNO3 1 mL

VAgNO = 64.13 mg × × × = 10.64 mL
3
207.89 mg mmol Na3 AsO4 0.08695 mmol AgNO3
6
(e) 25.00 mL of 0.05361MNa3PO4 ?
0.05361 mmol Na3PO4 3 mmol AgNO3 1 mL

VAgNO3 = 25.00 mL × × ×
mL mmol Na3PO4 0.08695 mmol AgNO3
= 46.24 mL
15-25. What minimum volume of 0.09621M AgNO3 will be needed to assure an excess of silver
ion in the titration of
Solutions:
(a) an impure NaCl sample that weighs 0.2513 g?
An excess is assured if the calculation is based on a pure sample.
1 mmol NaCl 1 mmol AgNO3 1 mL

Vol. AgNO3 = 0.2513 g × × ×
0.05844 g mmol NaCl 0.09621 mmol AgNO3
= 44.70 mL
(c) 25.00 mL of 0.01907 M AlCl3 ?
0.01907 mmolAlCl3 3 mmol AgNO3 1 mL

Vol. AgNO3 = 25.00 mL × × × = 14.87 mL
mL mmolAlCl3 0.09621 mmol AgNO3
15-27. The Tl in a 9.57-g sample of rodenticide was oxidized to the trivalent state and treated
with an unmeasured excess of Mg/EDTA solution. The reaction is
Tl3 + + MgY 2 − → TlY − + Mg2 +
Titration of the liberated Mg2+ required 12.77 mL of 0.03610 M EDTA. Calculate the
percent Tl2SO4 (504.8 g/mol) in the sample.
Solution:
 0.03610 mmol EDTA 1 mmol Tl2SO4 0.5048 g 
 × 12.77 mL × × 
 mL 2 mmol EDTA mmol Tl2SO4 
Percent Tl2SO4 =   × 100%
9.57 g sample
= 1.216%
15-29. A 50.00-mL aliquot of a solution containing iron(II) and iron(III) required 10.98 mL of
0.01500 M EDTA when titrated at pH 2.0 and 23.70 mL when titrated at pH 6.0. Express
the concentration of each solute in parts per million.
7
Solution:
0.01500 mmol EDTA 1mmol Fe3 +
Amnt Fe3 + = × 10.98 mL × = 0.1647 mmol
mL mmol EDTA
0.01500 mmol EDTA 1mmol Fe2+
Amnt Fe2+ = × ( 23.70 − 10.98 ) mL × = 0.1908 mmol
mL mmol EDTA
 3+ 55.847 mg 
 0.1647 mmol Fe × 
mmol Fe3+
Conc. Fe3+ =   = 183.96 ppm ≈ 184.0 ppm
L
50.00 mL ×
1000 mL
 2+ 55.847 mg 
 0.1908 mmol Fe × 
mmol Fe2+
Conc. Fe2+ =   = 213.1 ppm
L
50.00 mL ×
1000 mL
15-31. A 1.509-g sample of a Pb/Cd alloy was dissolved in acid and diluted to exactly 250.0 mL in
a volumetric flask. A 50.00-mL aliquot of the diluted solution was brought to a pH of 10.0
with a NH4 + / NH3 buffer; the subsequent titration involved both cations and required
28.89 mL of 0.06950 M EDTA. A second 50.00-mL aliquot was brought to a pH of 10.0
with an HCN/NaCN buffer, which also served to mask the Cd2+ ; 11.56 mL of the EDTA
solution were needed to titrate the Pb2+. Calculate the percent Pb and Cd in the sample.
Solution:
Amount Cd2+ + Pb2+ =
0.06950 mmolEDTA 1 mmol (Cd2+ + Pb2+ )
×28.89 mL EDTA× =2.00786 mmol
mL mmolEDTA
0.06950 mmolEDTA 1mmolPb2+
Amnt Pb2+ = ×11.56 mL EDTA× =0.80342 mmol
mL mmolEDTA
Amnt Cd2+ =2.00786 mmol − 0.80342 mmol = 1.20444 mmol
 2+ 207.2 g Pb
2+

 0.80342 mmolPb × 
 1000 mmol 
×100% = 55.16% Pb2+
50.00 mL
1.509 g sample×
250.0 mL
 2+ 112.41g Cd
2+

 1.204 mmol Cd × 
 1000 mmol 
×100% = 44.86% Cd2+
50.00 mL
1.509 g sample×
250.0 mL
8
15-33. Calamine, which is used for relief of skin irritations, is a mixture of zinc and iron oxides. A
1.056-g sample of dried calamine was dissolved in acid and diluted to 250.0 mL.
Potassium fluoride was added to a 10.00-mL aliquot of the diluted solution to mask the
iron; after suitable adjustment of the pH, Zn2+ consumed 38.37 mL of 0.01133 M EDTA. A
second 50.00-mL aliquot was suitably buffered and titrated with 2.30 mL of
0.002647 M ZnY 2− solution:
Fe3 + + ZnY 2 − → FeY − + Zn2 +
Calculate the percentages of ZnO and Fe2O3 in the sample.
Solution:
 0.01133 mmol EDTA 1mmol ZnO 81.379 g ZnO 
 ×38.37 mL EDTA× × 
 mL mmol EDTA 1000 mmol 
×100%
10.00 mL
1.056 g sample×
250.0 mL
= 83.75% ZnO
 0.002647 mmol ZnY 2− 1mmol Fe2O3 159.69 g Fe2O3 

 ×2.30 mL ZnY 2 − × × 
 mL 2 mmol ZnY 2− 1000 mmol  ×100%
50.00 mL
1.056 g sample×
250.0 mL
= 0.230% Fe2O3
15-34. A 3.650-g sample containing bromate and bromide was dissolved in sufficient water to
give 250.0 mL. After acidification, silver nitrate was introduced to a 25.00-mL aliquot to
precipitate AgBr, which was filtered, washed, and then redissolved in an ammoniacal
solution of potassium tetracyanonickelate(II):
Ni(CN)42− + 2AgBr(s) → 2Ag(CN)2− + Ni2+ + 2Br−
The liberated nickel ion required 26.73 mL of 0.02089 M EDTA. The bromate in a 10.00-
mL aliquot was reduced to bromide with arsenic(III) prior to the addition of silver nitrate.
The same procedure was followed, and the released nickel ion was titrated with 21.94
mL of the EDTA solution. Calculate the percentages of NaBr and NaBrO3 in the sample.
Solution:
1 mmol EDTA ≡ 1 mmol Ni2+ ≡ 2 mmol NaBr ≡ 2 mmol NaBrO3
For the 10.00 mL aliquot,
Amnt NaBr + amnt NaBrO3
=
mL sample solution
 0.02089 mmolEDTA 2 (mmolNaBr+mmolNaBrO3 ) 
 × 21.94 mL EDTA × 
 mL mmolEDTA 
  = 0.09166 M
10.00 mL
9
For the 25.00 mL aliquot,

Amnt NaBr
=
mL sample solution
 0.02089 mmolEDTA 2 mmolNaBr 
 × 26.73 mL EDTA× 
 mL mmolEDTA 
= 0.04467 MNaBr
25.00 mL
Amnt NaBrO3
= 0.09166 − 0.04467 = 0.04699 MNaBrO3
mL sample solution
 0.04467 mmolNaBr 102.9 g NaBr 

 × 250.0 mL × 
 mL 1000 mmol 
× 100% = 31.48% NaBr
3.650 g sample
 0.04699 mmolNaBrO3 150.9 g NaBrO3 
 × 250.0 mL × 
 mL 1000 mmol 
× 100% = 48.57% NaBrO3
3.650 g sample
15-36. Chromel is an alloy composed of nickel, iron, and chromium. A 0.6553-g sample was
dissolved and diluted to 250.0 mL. When a 50.00-mL aliquot of 0.05173 M EDTA was
mixed with an equal volume of the diluted sample, all three ions were chelated, and a
5.34-mL back-titration with 0.06139 M copper(II) was required. The chromium in a
second 50.0-mL aliquot was masked through the addition of hexamethylenetetramine;
titration of the Fe and Ni required 36.98 mL of 0.05173 M EDTA. Iron and chromium were
masked with pyrophosphate in a third 50.0-mL aliquot, and the nickel was titrated with
24.53 mL of the EDTA solution. Calculate the percentages of nickel, chromium, and iron
in the alloy.
Solution:
 0.05173 mmolEDTA 
Amnt EDTA reacted in 50.00 mL =  × 50.00 mL EDTA  −
 mL 
 0.06139 mmol Cu2+
1mmolEDTA 
 × 5.34 mL Cu2+ ×  = 2.2587 mmol
 mL mmol Cu2+ 
2.2587 mmol
Amnt EDTA reacted in 250.0 mL = Amnt (Ni+ Fe+ Cr) = = 11.2934 mmol
 50.00 mL 
 
 250.0 mL 
10
 × 36.98 mL EDTA 
mL
Amnt (Ni + Fe) =   = 9.5649 mmol
50.00 mL
250.0 mL
Amnt Cr = 11.2934 mmol − 9.5649 mmol = 1.7285 mmol
 0.05173 mmolEDTA 1mmolNi 
 × 24.53 mL EDTA × 
 mL mmolEDTA 
Amnt Ni = = 6.3447 mmol
50.00 mL
250.0 mL
Amnt Fe =9.5649 mmol − 6.3447 mmol = 3.2202 mmol
51.996 g Cr
1.7285 mmol Cr ×
1000 mmol
%Cr = ×100% = 13.72%
0.6553 g
58.69 g Ni
6.3447 mmolNi ×
1000 mmol
%Ni = × 100% = 56.82%
0.6553 g
55.847 g Fe
3.2202 mmolFe ×
1000 mmol
%Fe = × 100% = 27.44%
0.6553 g
15-38. Calculate conditional constants for the formation of the EDTA complex of Fe2+ at a pH of
(a) 6.0, (b) 8.0, and (c) 10.0.
Solutions:
15-42. Titration of Ca2+ and Mg2+ in a 50.00-mL sample of hard water required 23.65 mL of
0.01205 M EDTA. A second 50.00-mL aliquot was made strongly basic with NaOH to
precipitate Mg2+ as Mg ( OH)2 ( s ) . The supernatant liquid was titrated with 14.53 mL of
the EDTA solution. Calculate
11
Solutions:
Amnt Ca2+ + Amnt Mg 2+ =  × 23.65 mL EDTA  = 0.2850 mmol
 mL 
 0.01205 mmolEDTA 1mmol Ca 2+

Amnt Ca2+ =  × 14.53 mL EDTA ×  = 0.1751mmol
 mL mmolEDTA 
Amnt Mg2+ = 0.2850 − 0.1751 = 0.1099 mmol
(a) the total hardness of the water sample, expressed as ppm CaCO3 .
See discussion of water hardness in 15D-9.

Water hardness ≅ Conc. CaCO3 in ppm ≈ conc. Ca2+ + Mg2+ in ppm
100.087 mg CaCO3
0.2850 mmol ×
= mmol = 570.5 ppm CaCO3
L
50.00 mL ×
1000 mL
(b) the concentration of CaCO3 in the sample in ppm.
 1mmol CaCO3 100.08 mg CaCO3 

 0.1751 mmol Ca × ×
2+

 mmol Ca 2+
mmol  = 350.5 ppm CaCO
L 3
50.00 mL ×
1000 mL
(c) the concentration of MgCO3 in the sample in ppm.
 1mmolMgCO3 84.30 mg MgCO3 

 0.1099 mmol Mg × ×
2+

 mmolMg 2+
mmol  = 185.3 ppm MgCO
L 3
50.00 mL ×
1000 mL
12
© 2022, 978-0-357-45055-0, Chapter 16: Introduction to Electrochemistry
Chapter 16
16-1. Briefly describe or define
Answers:
(a) oxidation.
Oxidation is a process in which a species loses one or more electrons.
(c) salt bridge.

A salt bridge provides electrical contact but prevents mixing of dissimilar solutions
in an electrochemical cell.
(e) Nernst equation.

The Nernst equation relates the potential to the concentrations (strictly, activities) of
the participants in an electrochemical reaction.
Answers:
(a) electrode potential.
The electrode potential is the potential of an electrochemical cell in which a standard
hydrogen electrode acts as the reference electrode on the left and the half-cell of
interest is on the right.
(c) standard electrode potential.

The standard electrode potential is the potential of a cell consisting of the half-
reaction of interest on the right and a standard hydrogen electrode on the left. The
activities of all the participants in the half-reaction are specified as having a value of
unity. The standard electrode potential is always a reduction potential.
16-3. Make a clear distinction between
Answers:
(a) oxidation and oxidizing agent.
Oxidation is the process whereby a substance loses electrons; an oxidizing agent
causes the loss of electrons.
1
(c) the cathode of an electrochemical cell and the right-hand electrode.

The cathode of a cell is the electrode at which reduction occurs. The right-hand
electrode is the electrode on the right in the cell diagram.
(e) the standard electrode potential and formal potential.

The standard electrode potential is the potential of a cell in which the standard
hydrogen electrode acts as the reference electrode on the left and all participants
in the right-hand electrode process have unit activity. The formal potential differs in
that the molar concentrations of all the reactants and products are unity and the
concentration of other species in the solution are carefully specified.
16-4. The following entries are found in a table of standard electrode potentials:
I2 ( s) + 2e−  2l− E 0 = 0.5355 V

I2 (aq) + 2e−  2l− E 0 = 0.615 V
What is the significance of the difference between these two standard potentials?
Answer:
The first standard potential is for a solution saturated with I2, which has an I2(aq) activity
significantly less than one. The second potential is for a hypothetical half-cell in which the
I2(aq) activity is unity.
16-5. Why is it necessary to bubble hydrogen through the electrolyte in a hydrogen electrode?
Answer:
To keep the solution saturated with H2(g). Only then is the hydrogen activity constant
and the electrode potential constant and reproducible.
16-7. Write balanced net ionic equations for the following reactions. Supply H+ and/or H2O as
needed to obtain balance.
Solutions:
(a) Fe3+ + Sn2+ → Fe2+ + Sn4+
2Fe3+ + Sn2+ → 2Fe2+ + Sn4+
(c) NO3− + Cu ( s ) → NO2 ( g ) + Cu2 +
2NO3− + Cu(s) +4 H+ → 2 NO2(g) + 2H2O + Cu2+
Ti3 + + Fe ( CN)6 → TiO2 + + Fe ( CN)6

3− 4−
(e)
Ti3+ + Fe(CN)63− + H2O → TiO2+ + Fe(CN)64− + 2H+
2
(g) Ag ( s ) + I− + Sn4 + → AgI ( s ) + Sn2 +
2Ag(s) + 2I− + Sn4+ → 2AgI(s) + Sn2
(i) HNO2 + MnO4− → NO3− + Mn2 +
5HNO2 + 2MnO4 − + H+ → 5NO3− + 2Mn2+ + 3H2O
16-8. Identify the oxidizing agent and the reducing agent on the left side of each equation in
Problem 16-7; write a balanced equation for each half-reaction.
Solutions:
(a) Oxidizing agent Fe3+; Fe3+ + e−  Fe2+
Reducing agent Sn2+; Sn2+  Sn4+ + 2e−
(c) Oxidizing agent NO3−, NO3− + 2H+ + e−  NO2(g) + H2O
Reducing agent Cu; Cu(s)  Cu2+ + 2e−
(e) Oxidizing agent Fe(CN)63− ; Fe(CN)63− + e−  Fe(CN)6 4 −
Reducing agent Ti3+; Ti3+ + H2O  TiO2+ +2H+ + e−
(g) Oxidizing agent Sn4+; Sn4+ + 2e−  Sn2+
Reducing agent Ag; Ag(s) + I−  AgI(s) + e−
(i) Oxidizing agent MnO4− ; MnO4− + 8H− + 5e−  Mn2+ + 4H2O
Reducing agent HNO2; HNO2 + H2O  NO3 − + 3H+ + 2e−
16-9. Write balanced net ionic equations for the following reactions. Supply H+ and/or H2O as
needed to obtain balance.
Solutions:
MnO4− + VO2 + → Mn2 + + V ( OH)4
+
(a)
MnO4 − + 5VO2+ + 11H2O → Mn2+ + 5V(OH) 4 + + 2H+
3
(c) Cr2O27− + U4 + → Cr 3+ + UO22+
Cr2O72− + 3U4+ + 2H+ → 2Cr 3+ + 3UO22+ + H2O
(e) IO3− + I− → I2 ( aq )
IO3−+ 5I− + 6H+ → 3I2 + 3H2O
(g) HPO23− + MnO4− + OH− → PO34− + MnO24−
HPO32 − + 2MnO4 − + 3OH− → PO43− + 2MnO4 2− + 2H2O
V 2+ + V ( OH)4 → VO2+
+
(i)
V2+ + 2V(OH)4+ + 2H+ → 3VO2+ + 5H2O
16-11. Consider the following oxidation/reduction reactions:
AgBr ( s ) + V 2 + → Ag ( s ) + V 3+ + Br −
Tl3+ + 2Fe ( CN)6 → Tl+ + 2Fe ( CN)6

4+ 3−
2V 3+ + Zn ( s ) → 2V 2 + + Zn2 +
Fe (CN)6 + Ag ( s ) + Br − → Fe ( CN)6 + AgBr ( s )

3− 4−
S2O82− + Tl− → 2SO24− + Tl3+
(a) Write each net process in terms of two balanced half-reactions.

(b) Express each half-reaction as a reduction.
(c) Arrange the half-reactions in (b) in order of decreasing effectiveness as electron
acceptors.
Solutions:
AgBr(s) + e−  Ag(s) + Br− V2+  V3+ + e−
Tl3+ + 2e−  Tl+ Fe(CN)6 4 −  Fe(CN)63 − + e−
V3+ + e−  V2+ Zn  Zn2+ + 2e−
Fe(CN)6 3 − + e−  Fe(CN)6 4 − Ag(s) + Br−  AgBr(s) + e−
S2O82 − + 2e−  2SO4 2 − Tl+  Tl3+ + 2e−
4
(b), (c) E0
S2O82 − + 2e−  2SO4 2 − 2.01
Tl3+ + 2e−  Tl+ 1.25
Fe(CN)6 3 − + e−  Fe(CN)6 4 − 0.36
AgBr(s) + e−  Ag(s) + Br− 0.073
V3+ + e−  V2+ − 0.256
Zn2+ + 2e−  Zn(s) − 0.763
16-13. Calculate the potential of a copper electrode immersed in
Solutions:
(a) 0.0380 MCu (NO3 )2 .
0.0592  1 
ECu = 0.337 − log   = 0.295 V
2  0.0380 
(b) 0.0650 M in NaCl and saturated with CuCl.
K CuCl = 1.9 × 10 −7 = [Cu+ ][Cl− ]

0.0592  1  0.0592  [Cl− ] 
ECu = 0.521 − log  + 
= 0.521 − log  
1  [Cu ]  1  K CuCl 
0.0592  0.0650  0.0592
= 0.521 − log  −7 
= 0.521 − log(3.42 × 105 )
1  1.9 × 10  1
= 0.521 − 0.328 = 0.193 V
(c) 0.0350 M in NaOH and saturated with Cu ( OH)2 .
KCu(OH) = 4.8 × 10−20 = [Cu2+ ][OH− ]2

2
0.0592  1  0.0592  [OH− ]2 

ECu = 0.337 − log  2+ 
= 0.337 − log  
2  [Cu ]  2  K Cu(OH) 
 2 
 ( 0.0350 )2 
0.0592  = 0.337 − 0.0592 log(2.55 × 1016 )
= 0.337 − log 
2  4.8 × 10 −20
2
 
= 0.337 − 0.486 = − 0.149 V
5
0.0375 M in Cu (NH3 )4 and 0.108 M in NH3 ( β 4 for Cu (NH3 )4

2+ 2+
(d) is 5.62 × 1011 ).
[Cu(NH3 )42+ ]
β 4 = 5.62 × 1011 =
[Cu2+ ][NH3 ]4
0.0592  1  0.0592  β 4 [NH3 ]4 

ECu = 0.337 − log  2+ 
= 0.337 − log  
2+ 
2  [Cu ]  2  [Cu(NH3 )4 ] 
 5.62 × 1011 ( 0.108 )4 
0.0592  =0.337 − 0.0592 log(2.04 × 109 )
= 0.337 − log 
2  0.0375  2
 
= 0.337 − 0.276 = 0.061 V
(e) a solution in which the molar analytical concentration of Cu (NO3 )2 is 3.90 × 10−3 M,
that for H2 Y 2− is 3.90 × 10 −2 M ( Y = EDTA ) , and the pH is fixed at 4.00.
[CuY 2 − ]
[Cu2+ ]cT
( ) ( )
= α 4 K CuY = 3.6 × 10 −9 × 6.3 × 1018 = 2.3 × 1010
[CuY 2 − ] ≈ 3.90 × 10 −3
( ) ( )
cT = 3.90 × 10 −2 − 3.90 × 10 −3 = 0.0351
0.0592  1  0.0592  α 4 K CuY2- cT 

ECu = 0.337 − log   = 0.337 − log  
2  [Cu ] 
2+
2  [CuY 2 − ] 
 
0.0592  2.3 × 1010 ( 0.0351)  0.0592
= 0.337 − log   = 0.337 − log(2.07 × 1011 )
2  3.90 × 10 −3  2
 
= 0.337 − 0.335 = 0.002 V
16-16. Calculate the potential of a platinum electrode immersed in a solution that is
Solutions:
(a) 0.0160 M in K 2PtCl4 and 0.2450 M in KCl.
PtCl42− + 2e−  Pt(s) + 4 Cl− E0 = 0.755 V
 ( 0.2450 )4 
0.0592
EPt = 0.755 − log   = 0.755 − (−0.019) = 0.75 V
2  0.0160 
 
(b) 0.0650 M in Sn ( SO4 )2 and 3.5 × 10−3 M in SnSO4 .
E0 = 0.154
0.0592  3.50 × 10−3 
EPt = 0.154 − log  −2 
= 0.154 − ( −0.038) = 0.192 V
2  6.50 × 10 
6
(c) buffered to a pH of 6.50 and saturated with H2 ( g ) at 1.00 atm.
pH = 6.50, [H+] = 3.16 × 10−7

 
0.0592 1.00
EPt = 0.000 − log   = −0.385 V

2
( )
2
 3.16 × 10 −7 
 
(d) 0.0255 M in VOSO4 , 0.0686M in V2 ( SO4 )3 , and 0.100 M in HClO4 .
E0 = 0.337 V
 ( 0.0686 ) × 2 
0.0592
EPt = 0.337 − log   = 0.337 − 0.162 = 0.175 V
1  
 ( 0.0255 ) × ( 0.100 )
2

(e) prepared by mixing 25.00 mL of 0.0918MSnCl2 with an equal volume of

0.1568MFeCl3 .
2Fe3+ + Sn2+  2Fe2+ + Sn4+

0.0918 mmol SnCl2 1mmol Sn2+
amount Sn2+ consumed = × × 25.00 mL = 2.295 mmol
mL mmol SnCl2
0.1568 mmol FeCl3 1mmol Fe3+

amount Fe3+ consumed = × × 25.00 mL = 3.920 mmol
mL mmol FeCl3
1mmol Sn4+
amount Sn4+ formed = 3.920 mmol Fe3+ × = 1.960 mmol
2 mmol Fe3+
amount Sn2+ remaining = 2.295 − 1.960 = 0.335 mmol
0.0592  ( 0.335 ) / 50.0 

EPt = 0.154 − log   = 0.154 − ( −0.023) = 0.177 V
2  (1.960 ) / 50.0 
 
(f) prepared by mixing 25.00 mL of 0.0832 M V(OH)4+ with 50.00 mL of 0.01087 M

V2(SO4)3 and has a pH of 1.00.
V(OH) 4 + + V 3+ +  2VO2+ + 2H2O
V(OH)4+ + 2H+ + 2e−  VO2+ + 3H2O E0 = 1.00 V
0.0832 mmol V(OH) 4 +

amountV(OH) 4 +consumed = × 25.00 mL = 2.08 mmol
mL
0.01087 mmol V2 (SO4 )3 2 mmol V 3+
amount V 3+consumed = × × 50.00 mL = 1.087 mmol
mL mmol V2 (SO4 )3
2 mmol VO2+
amount VO2+ formed = 1.087 mmol V 3+ × = 2.174 mmol
mmol V 3+
amount V(OH)4 +remaining = 2.08 − 1.087 = 0.993 mmol
7
 ( 2.174 ) / 75.00 
EPt = 1.00 − 0.0592log   = 1.00 − 0.139 = 0.86 V
 0.993 / 75.00 0.1000 2 
( )( ) 
16-18. If the following half-cells are the right-hand electrode in a galvanic cell with a standard
hydrogen electrode on the left, calculate the cell potential. If the cell were shorted,
indicate whether the electrodes shown would act as an anode or a cathode.
Solutions:
(a) Ni|Ni2 + ( 0.0883 M)
0.0592  1.00 
ENi = −0.250 − log   = −0.250 − 0.031 = −0.281V anode
2  0.0883 
(b) Ag|AgI ( sat 'd) , KI(0.0898 M)
E Ag = −0.151 − 0.0592log ( 0.0898 ) = −0.151 − ( −0.062) = −0.089 V anode
(c) (
Pt|O2 ( 780 torr ) , HCl 2.50 × 10−4 M )
 
0.0592 1.00
EO = 1.229 − log   = 1.229 − 0.213 = 1.016 V cathode

4
( )
4
 ( 780 / 760 ) 2.50 × 10 −4
2

 
(d) Pt|Sn2 + ( 0.0893 M) , Sn4 + ( 0.215 M)
0.0592  0.0893 
EPt = 0.154 − log   = 0.154 − (−0.011) = 0.165 V cathode
2  0.215 
Ag|Ag ( S2O3 )2 ( 0.00891 M) , Na S O ( 0.1035 M)

3−
(e) 2 2 3
 ( 0.1035 )2 
E Ag = 0.017 − 0.0592log   = 0.017 − 0.005 = 0.012 V cathode
 0.00891 
 
16-20. The solubility-product constant for Ag2SO3 is 1.5 × 10−14. Calculate E 0 for the process
Ag2 SO3 ( s) + 2e−  2Ag + SO32 −
Solution:
2 Ag+ + 2e−  2Ag( s) E o = 0.779
[Ag+ ]2 [SO32− ] = 1.5 × 10−14 = Ksp
0.0592  1  0.0592  [SO32− ] 
E = 0.799 − log  + 2 
= 0.799 − log  
2  [Ag ]  2  Ksp 
 
8
When [SO32−] =1.00, E = Eo for Ag2SO3 (s) + 2e−  2Ag( s) + SO32− .Thus,
0.0592  1.00  0.0592  1.00 

E = 0.799 − log   = 0.799 − log  −14 
= 0.799 − 0.409 = 0.390 V
2  
 K sp  2  1.5 × 10 
16-22. The solubility-product constant for Tl2S is 6 × 10−22. Calculate E 0 for the reaction
Tl2S(s) + 2e − 
 2Tl(s) + S

 2−
Solution:
2Tl+ + 2e−  2Tl(s) E o = −0.336
[Tl+ ]2 [S2 − ] = 6 × 10 −22 = K sp
0.0592  1  0.0592  [S2 − ] 
E = −0.336 − log  + 2  = −0.336 − log  
2  [Tl ]  2  K sp 
 
When [S2−] =1.00, E = Eo for Tl2S(s) + 2e−  2Tl(s ) + S2− .
Thus,
0.0592  1.00  0.0592  1.00 

E = −0.336 − log   = −0.336 − log  −22 
2  K sp  2  6 × 10 
 
= −0.336 − 0.628 = −0.96 V
16-24. Compute E 0 for the process
ZnY 2 − + 2e − 
 Zn(s ) + Y

 4−
where Y 4 − is the completely deprotonated anion of EDTA. The formation constant for
16
ZnY 2 − is 3.2 × 10 .
Solution:
0.0592  1 
E = −0.763 − log  2+ 
2  [Zn ] 
[ZnY 2− ]
= 3.2 × 1016
[Zn2+ ][Y 4 − ]
E = −0.763 −
0.0592
log 
(
 [Y 4 − ] 3.2 × 1016 ) 
2  [ZnY 2 − ] 
 
When [Y4−] = [ZnY2−] = 1.00, E = EZnY
o
2−
E = −0.763 −
0.0592
log 
(
 1.00 3.2 × 1016 )  = −0.763 − 0.489 = −1.25 V
2  1.00 
 
9
16-25. Given the formation constants
Fe3+ + Y 4 − 
 FeY

 −
K 1 = 1.3 × 1025
Fe2 + + Y 4 − 
 FeY

 2−
K 1 = 2.1× 1014
calculate E 0 for the process

FeY − + e−  FeY 2 −
Solution:
[FeY − ] [FeY 2− ]
[Fe3+ ] = and [Fe2+ ] =
(
[Y 4 − ] 1.3 × 1025 ) (
[Y 4 − ] 2.1× 1014 )
 [Fe2+ ] 
E = 0.771 − 0.0592log  3+ 
 [Fe ] 
 [FeY 2 − ] 1.3 × 1025
= 0.771 − 0.0592log 
( ) 
 [FeY − ] 2.1× 1014
 ( ) 
o
When [FeY2−] = [FeY−] = 1.00, E = EFeY −
 1.00 1.3 × 1025

E = 0.771 − 0.0592log 
( )  = 0.771− 0.64 = 0.13 V
 1.00 2.1× 1014
 ( ) 
10
© 2022, 978-0-357-45055-0, Chapter 17: Applications of Standard Electrode Potentials
Chapter 17
17-1. Briefly define the electrode potential of a system that contains two or more redox
couples.
Answer:
The electrode potential of a system that contains two or more redox couples is the
electrode potential of all half-cell processes at equilibrium in the system.
17-2. For an oxidation/reduction titration, briefly distinguish between
Answer:
(a) equilibrium and equivalence.
Equilibrium is the state that a system assumes after each addition of reagent.
Equivalence refers to a particular equilibrium state when a stoichiometric amount of
titrant has been added.
17-4. How is an oxidation/reduction titration curve generated through the use of standard
electrode potentials for the analyte species and the volumetric titrant?
Answer:
For points before the equivalence point, potential data are computed from the analyte
standard potential and the analytical concentrations of the analyte and its reaction product.
Post-equivalence point data are based upon the standard potential for the titrant and its
analytical concentrations. The equivalence point potential is computed from the two standard
potentials and the stoichiometric relation between the analyte and titrant.
17-6. Under what circumstance is the curve for an oxidation/reduction titration asymmetric
about the equivalence point?
Answer:
An asymmetric titration curve will be encountered whenever the titrant and the analyte
react in a ratio that is not 1:1.
1
17-8. Calculate the theoretical cell potential of the following cells. If the cell is short-circuited,
indicate the direction of the spontaneous cell reaction.
Solutions:
(a) Zn | Zn2+ (0.1000 M) || Co2+ (5.87 × 10−4 M) | Co
0.0592  1 
Eright = −0.277 − log  −4 
= −0.373 V
2  5.87 × 10 
0.0592  1 
Eleft = −0.763 − log   = −0.793 V
2  0.100 
Ecell = Eright − Eleft = −0.373 − (−0.793) = 0.420 V
Because Ecell is positive, the reaction would proceed spontaneously in the direction
considered (oxidation on the left, reduction on the right).
(b) Pt | Fe3+ (0.1600 M), Fe2+ (0.0700 M) || Hg2+ (0.0350 M) | Hg
0.0592  1 
Eright = 0.854 − log   = 0.811V
2  0.0350 
0.0592  0.0700 
Eleft = 0.771 − log   = 0.782 V
2  0.1600 
Ecell = Eright − Eleft = 0.811 − 0.782 = 0.029 V
Because Ecell is positive, the spontaneous reaction would be oxidation on the left
and reduction on the right.
(c) Ag | Ag+ (0.0575 M) | H+ (0.0333 M) | O2 (1.12 atm), Pt
 
0.0592 1
Eright = 1.229 − log   = 1.142 V
4  1.12 0.0333 4 
 ( ) 
 1 
Eleft = 0.799 − 0.0592log   = 0.726 V
 0.0575 
Ecell = Eright − Eleft = 1.142 − 0.726 = 0.416 V
The spontaneous reaction would be oxidation on the left, reduction on the right.
(d) Cu | Cu2+ (0.0420 M) || I−(0.1220 M), AgI(sat’d) | Ag
Eright = −0.151 − 0.0592log ( 0.1220 ) = −0.097 V

0.0592  1 
Eleft = 0.337 − log   = 0.296 V
2  0.0420 
Ecell = Eright − Eleft = −0.097 − 0.296 = −0.393 V
The spontaneous reaction would be reduction on the left, oxidation on the right,
not the reaction in the direction considered.
(e) SHE || HCOOH(0.1400 M), HCOO−(0.0700 M) | H2 (1.00 atm), Pt
[H3O+ ][HCOO− ] [H O+ ]0.0700

= 1.80 × 10−4 = 3
[HCOOH] 0.1400
+
[H O ] =
(1.80 × 10 ) (0.1400 ) = 3.60 × 10
−4
−4
3
0.0700
 
0.0592 1.00
Eright = 0.000 − log  
 = −0.204 V
2
( )
2
 3.60 × 10−4 
 
Eleft = 0.000 V
Ecell = −0.204 − 0.000 = −0.204 V
Because Ecell is negative, the reaction woulds not proceed spontaneously in the
direction considered (reduction on the left, oxidation on the right).
(f) Pt | UO22+ (8.00 × 10−3 M), U4+ (4.00 × 10−2 M), H+ (1.00 × 10−3 M) || Fe3+ (0.003876 M), Fe2+
(0.1134 M) | Pt
 0.1134 
Eright = 0.771 − 0.0592log   = 0.684 V
 0.003876 
 
0.0592 4.00 × 10−2
Eleft = 0.334 − log   = −0.042 V

2
( )( )
4
 8.00 × 10−3 1.00 × 10−3 
 
Ecell = Eright − Eleft = 0.684 − (−0.042) = 0.726 V
The direction considered (oxidation on the left, reduction on the right) is the
spontaneous direction.
17-9. Calculate the potential of the following two half-cells that are connected by a salt bridge:
Solutions:
(a) a galvanic cell consisting of a lead electrode (right electrode) immersed in 0.0250 M
Pb2+ and a zinc electrode in contact with 0.1000 M Zn2+.
0.0592  1 
EPb2+ = −0.126 − log   = −0.173 V
2  0.0250 
0.0592  1 
EZn2+ = −0.763 − log   = −0.793 V
2  0.1000 
Ecell = Eright − Eleft = −0.173 − (−0.793) = 0.620 V
(c) a galvanic cell consisting of a standard hydrogen electrode on the left and a
platinum electrode immersed in a solution that is 4.50 × 10−3 M in TiO2+, 0.09000 M
in Ti3+, and buffered to a pH of 3.00.
ESHE = 0.000 V
 
0.09000
E TiO2+ = 0.099 − 0.0592log   = −0.333 V

( )( )
2
 4.50 × 10 −3 10 −3 
 
Ecell = Eright − Eleft = −0.333 − 0.000 = –0.333 V
17-11. Generate equilibrium-constant expressions for the following reactions. Calculate

numerical values for Keq.
Solutions:
Note that in these calculations, it is necessary to round the answers to either one or two
significant figures because the final step involves taking the antilogarithm of a large
number.
(a) Fe3+ + V 2+  Fe2+ + V 3+
Fe3+ + V2 +  Fe2+ + V 3+ EFe

o
3+ = 0.771 EVo3+ = −0.255
 [Fe2+ ]   [V 2+ ] 
0.771− 0.0592log  3+ 
= −0.255 − 0.0592log  3+ 
 [Fe ]   [V ] 
0.771− ( −0.255 )  [Fe2+ ][V 3+ ] 
= log  2+ 
= log K eq = 17.348
0.0592  [Fe ][V ] 
3+
K eq = 2.23 × 1017 (2.2 × 1017)
(c) 2V(OH)4+ + U4+  2VO2+ + UO22+ + 4H2O
2V(OH)4 + + U4+  2VO2+ + UO22+ + 4H2O E V(OH)

o
+ = 1.00 EUoO 2+ = 0.334
4 2
0.0592  [VO2+ ]2  0.0592  [U4+ ] 

1.00 − log   = 0.334 − log  
2  + 2 + 4
2  2+ + 4
 [V(OH)4 ] [H ]   [UO2 ][H ] 
(1.00 − 0.334 ) 2 = log  [VO2+ ]2 [UO22+ ]  = log K = 22.50
0.0592  [V(OH) + ]2 [U4+ ]  eq
 4 
K eq = 3.2 × 1022 (3 × 1022)
(e) 2Ce4+ + H3 AsO3 + H2O  2Ce3+ + H3 AsO4 + 2H+ (1MHClO4 )
2Ce4+ + H3 AsO3 + H2O  2Ce3+ + H3 AsO4 + 2H+

o
ECe 4+ (in 1M HClO4 ) = 1.70 EHo AsO = 0.577
3 4
0.0592  [Ce3+ ]2
 0.0592  [H3 AsO4 ] 
1.70 − log   = 0.577 − log  
2 4+ 2
2  [H AsO ][H+ ]2
 [Ce ]
  3 3 
( 1.70 − 0.577 ) = log [Ce ] [H3 AsO3 ][H ] = log K = 37.94
2  3+ 2 + 2

  eq
0.0592 4+ 2
 [Ce ] [H3 AsO4 ] 
K eq = 8.9 × 1037 (9 × 1037 )
(g) VO2+ + V 2+ + 2H+  2V 3+ + H2O
VO2+ + V 2+ + 2H+  2V 3+ + H2O EVO

o
2+ = 0.337 EVo3+ = −0.255
 [V 3+ ]   [V 2+ ] 
0.359 − 0.0592log  + 2 
= −0.256 − 0.0592log  3+ 
 [VO ][H ]   [V ] 
2+
0.359 − ( −0.256 )  [V ]
3+ 2

= log  2+ 
= log K eq = 10.389
0.0592  [VO ][H ] [V ] 
2+ + 2
Keq = 2.4 × 1010
17-14. Select an indicator from Table 17-3 that might be suitable for each of the titrations in
Problem 17-11. Write NONE if no indicator listed in Table 17-3 is suitable.
Solutions:
Eeq, V Indicator
(a) 0.258 Phenosafranine
(c) 0.444 Indigo tetrasulfonate or Methylene blue
(e) 0.951 Erioglaucin A
(g) −0.008 None
© 2022, 978-0-357-45055-0, Chapter 18: Applications of Oxidation/Reduction Titrations
Chapter 18
18-1. Write balanced net ionic equations to describe
Solutions:
(a) the oxidation of Mn2+ to MnO4− by ammonium peroxydisulfate.
2Mn2+ + 5S2O8 2 − + 8H2 O → 10SO4 2 − + 2MnO4 − + 16H+
(c) the oxidation of U4+ to UO22+ by H2O2.

H2 O2 + U4 + → UO22 + + 2H+
(e) the titration of H2O2 with KMnO4.
2MnO4 − + 5H2O2 + 6H+ → 5O2 + 2Mn2 + + 8H2 O
18-2. Why is a Walden reductor always used with solutions that contain appreciable
concentrations of HCl?
Solution:
Only in the presence of Cl− ion is Ag a sufficiently good reducing agent to be very useful
for prereductions. In the presence of Cl−, the half-reaction occurring in the Walden
reductor is
Ag(s) + Cl− → AgCl(s) + e −
The excess HCl increases the tendency of this reaction to occur by the common ion
effect.
18-4. Why are standard solutions of reductants less often used for titrations than standard
solutions of oxidants?
Answer:
Standard solutions of reductants find somewhat limited use because of their
susceptibility to air oxidation.
1
18-6. Why are KMnO4 solutions filtered before they are standardized?
Answer:
Freshly prepared solutions of permanganate are inevitably contaminated with small
amounts of solid manganese dioxide, which catalyzes the further decompositions of
permanganate ion. By removing the dioxide at the outset, a much more stable standard
reagent is produced.
18-8. What is the primary use of standard K2Cr2O7 solutions?
Answer:
Solutions of K2Cr2O7 are used extensively for back-titrating solutions of Fe2+ when the
latter is being used as a standard reductant for the determination of oxidizing agents.
18-10. Suggest a way in which a solution of KIO3 could be used as a source of known quantities
of I2 .
Solution:
When a measured volume of a standard solution of KIO3 is introduced into an acidic
solution containing an excess of iodide ion, a known amount of iodine is produced as a
result of:
IO3 − + 5I− + 6H+ → 3I2 + 3H2O
18-12. In the titration of I2 solutions with Na2S2O3 , the starch indicator is never added until just
before chemical equivalence. Why?
Answer:
Starch decomposes in the presence of high concentrations of iodine to give products
that do not behave satisfactorily as indicators. This reaction is prevented by delaying the
addition of the starch until the iodine concentration is very small.
18-13. A solution prepared by dissolving a 0.2541-g sample of electrolytic iron wire in acid was
passed through a Jones reductor. The iron(II) in the resulting solution required a 36.76-
mL titration. Calculate the molar oxidant concentration if the titrant used was
Solutions:
1000 mmol Fe2 +
0.2541 g sample × = 4.5499 mmol Fe2 +
55.847 g
(a) Ce4 + (product: Ce3+ ).
4.5499 mmol Fe2 + 1mmol Ce4 +

× = 0.1238 M Ce4 +
36.76 mL mmol Fe 2+
2
(c) MnO4− (product: Mn2+).
4.5499 mmol Fe2 + 1mmol MnO4 −

× = 0.02475 M MnO4 −
36.76 mL 5 mmol Fe2 +
(e) IO3− (product: ICl2−).
4.5499 mmol Fe2 + 1mmol IO3 −

× = 0.03094 M IO3 −
36.76 mL 4 mmol Fe2 +
18-14. How would you prepare 1.000 L of 0.05000 M KBrO3?
Solution:
0.05000 mol KBrO3 167.001g KBrO3
× 1.000 L × = 8.350 g KBrO3
L mol
Dissolve 8.350 g KBrO3 in water and dilute to 1.000 L.
18-16. A 0.2219-g sample of pure iron wire was dissolved in acid, reduced to the +2 state, and
titrated with 34.65 mL of cerium(IV). Calculate the molar concentration of the Ce4 +
solution.
Solution:
Ce 4 + + Fe 2 + → Ce3 + + Fe3 +
0.2219 g 1000 mL 1 mol Fe 1mol Fe2 + 1mol Ce 4 +

× × × × = 0.1147 M Ce4 +
34.65 mL Ce 4+
L 55.847 g mol Fe mol Fe 2+
18-18. Calculate the percentage of MnO2 in a mineral specimen if the I2 liberated by a 0.1267-g
sample in the net reaction
MnO2(s) + 4H+ + 2I− → Mn2+ + I2 + 2H2O

required 29.62 mL of 0.08041M Na2S2O3 .
Solution:
MnO2 + 2I− + 4H+ → Mn2 + + I2 + 2H2 O
I2 + 2S2 O32 − → 2I− + S4 O62 −
1 mmol MnO2 = 1 mmol I2 = 2 mmol S2O32−
 0.08041mmol 1mmol MnO2 86.937 g MnO2 
 × 29.62 mL Na2 S2O3 × × 
 mL 2 mmol Na2 S2O3 1000 mmol  × 100%
0.1267 g sample
= 81.71% MnO2
3
18-20. Treatment of hydroxylamine (H2NOH) with an excess of Fe(III) results in the formation of
N2O and an equivalent amount of Fe(II):
2H2NOH + 4Fe3+ → N2O(g) + 4Fe2+ + 4H+ + H2O

Calculate the molar concentration of an H2NOH solution if the Fe(II) produced by
treatment of a 25.00-mL aliquot required 14.48 mL of 0.01528 M K2Cr2O7.
Solution:
2H2NOH + 4Fe3 +  N2O(g ) + 4Fe2 + + 4H+ + H2 O
Cr2O72 − + 6Fe2 + + 14H+  2Cr 3 + + 6Fe3+ + 7H2O
1 mmol Cr2O72−= 6 mmol Fe3+ = 3 mmol H2NOH
 0.01528 mmol K 2Cr2O7 3 mmol H2NOH 
 × 14.48 mL K 2Cr2O7 × 
 mL mmol K 2Cr2O7 
25.00 mL sample
= 0.0266 M H2NOH
18-22. An 8.13-g sample of an ant-control preparation was decomposed by wet ashing with
H2SO4 and HNO3. The As in the residue was reduced to the trivalent state with hydrazine.
After removal of the excess reducing agent, the As(III) required a 31.46-mL titration with
0.03142 MI2 in a faintly alkaline medium. Express the results of this analysis in terms of
percentage of As2O3 in the original sample.
Solution:
H3 AsO3 + I2 + H2O → H3 AsO4 + 2I− + 2H+
1 mmol I2 = 1 mmol H3AsO3 = ½ mmol As2O3
 0.03142 mmol I2 1mmol As2O3 197.841g As2O3 
 × 31.46 mL I2 × × 
 mL 2 mmol I2 1000 mmol 
× 100%
8.13 g sample
= 1.202% As2O3
18-24. A sensitive method for I− in the presence of CI− and Br − entails oxidation of the I− to
IO3− with Br2. The excess Br2 is then removed by boiling or by reduction with formate ion.
The IO3− produced is determined by addition of excess I− and titration of the resulting I2 A
1.307-g sample of mixed halides was dissolved and analyzed by the foregoing procedure.
A volume of 19.72 mL of 0.04926 M thiosulfate was required for the titration. Calculate
the percentage of KI in the sample.
Solution:
2I− + Br2 → I2 + 2Br −
IO3 − + 5I− + 6H+ → 3I2 + 3H2 O
I2 + 2S2O32 − → 2I− + S4 O62 −
4
1 mmol KI = 1 mmol IO3− = 3 mmol I2 = 6 mmol S2O32−

 0.04926 mmol Na2 S2 O3 1mmol KI 166.00 g KI 
 × 19.72 mL Na2 S2 O3 × × 
 mL 6 mmol Na2 S2 O3 1000 mmol 
× 100%
1.307 g sample
= 2.056% KI
18-26. A gas mixture was passed at the rate of 2.50 L/min through a solution of sodium
hydroxide for a total of 59.00 min. The SO2 in the mixture was retained as sulfite ion:
SO2( g) + 2OH− → SO32− + H2O

After acidification with HCl, the sulfite was titrated with 5.15 mL of 0.002997 M KIO3 :
IO3− + 2H2SO3 + 2Cl− → ICl2− + 2SO42− + 2H+ + H2O

Use 1.20 g/L for the density of the mixture and calculate the concentration of SO2 in
ppm.
Solution:
SO2 (g ) + 2OH− → SO32 − + H2O
IO3 − + 2H2 SO3 + 2Cl− → ICl2 − + SO4 2 − + 2H+
1 mmol IO3− = 2 mmol H2SO3 = 2 mmol SO2
2.50 L
In × 59.00 min = 147.5 L of sample, there are
min
0.002997 mmol KIO3 2 mmol SO2 64.065 g SO2
× 5.15 mL KIO3 × × = 1.9776 × 10−3 g SO2
mL mmol KIO3 1000 mmol
 
 1.9776 × 10 −3 g SO 
 2
 × 106 ppm
 147.5 L × 1.20 g 
 
 L 
= 11.2 ppm SO2
18-28. The Winkler method for dissolved oxygen in water is based on the rapid oxidation of
solid Mn(OH)2 to Mn(OH)3 in alkaline medium. When acidified, the Mn(III) readily
releases iodine from iodide. A 250-mL water sample, in a stoppered vessel, was treated
with 1.00 mL of a concentrated solution of NaI and NaOH and 1.00 mL of a
manganese(II) solution. Oxidation of the Mn(OH)2 was complete in about 1 minute. The
precipitates were then dissolved by addition of 2.00 mL of concentrated H2SO4 ,
whereupon an amount of iodine equivalent to the Mn(OH)3 (and hence to the dissolved
O2) was liberated. A 25.0-mL aliquot (of the 254 mL) was titrated with 14.6 mL of 0.00897
M thiosulfate. Calculate the mass in milligrams of O2 per milliliter sample. Assume that
the concentrated reagents are O2 free and take their dilutions of the sample into
account.
5
Solution:
O2 + 4Mn(OH)2 (s) + 2H2O  4Mn(OH)3 (s)
4Mn(OH)3 (s) + 12H+ + 4I−  4Mn2 + + 2I2 + 12H2O
0.00897 mmol S2O32− 1mmol O2 32.0 mg O2

× 14.60 mL S2O32− × × = 1.0477 mg O2
mL 4 mmol S2O32− mmol
1.0477 mg O2
 250 mL 
 25 mL sample × 
 254 mL 
= 0.0426 mg O2/mL sample
6
© 2022, 978-0-357-45055-0, Chapter 19: Potentiometry
Chapter 19
Answers:
(a) indicator electrode.
An indicator electrode is an electrode used in potentiometry that responds to
variations in the activity of an analyte ion or molecule.
(c) electrode of the first kind.

An electrode of the first kind is a metal electrode that responds to the activity of its
cation in solution.
Answers:
(a) liquid junction potential.
A liquid junction potential is the potential that develops across the interface
between two solutions having different electrolyte compositions.
(c) asymmetry potential.

The asymmetry potential is a potential that develops across an ion-sensitive
membrane when the concentrations of the ion are the same on either side of the
membrane. This potential arises from dissimilarities between the inner and outer
surface of the membrane.
19-3. You need to choose between determining an analyte by measuring an electrode

potential or by performing a titration. Explain which you would choose if you needed to
know
Answer:
(a) the absolute amount of the analyte to a few parts per thousand.
A titration is generally more accurate than measurements of electrode potential.
Therefore, if ppt accuracy is needed, a titration should be picked.
1
(b) the activity of the analyte.

Electrode potentials are related to the activity of the analyte. Thus, pick potential
measurements if activity is the desired quantity.
19-5. Describe the source of pH dependence in a glass-membrane electrode.
Solution:
The potential arises from the difference in positions of dissociation equilibria on each of
the two surfaces. These equilibria are described by
H+ Gl−  H+ + Gl−
membrane solution membrane
The surface exposed to the solution having the higher H+ concentration becomes
positive with respect to the other surface. This charge difference, or potential, serves as
the analytical parameter when the pH of the solution on one side of the membrane is
held constant.
19-7. List several sources of uncertainty in pH measurements with a glass/calomel electrode

system.
Answer:
Uncertainties include (1) the acid error in highly acidic solutions, (2) the alkaline error in
strongly basic solutions, (3) the error that arises when the ionic strength of the
calibration standards differs from that of the analyte solution, (4) uncertainties in the pH
of the standard buffers, (5) nonreproducible junction potentials with solutions of low
ionic strength and (6) dehydration of the working surface.
19-9. Describe the alkaline error in the measurement of pH. Under what circumstances is this
error appreciable? How are pH data affected by alkaline error?
Answer:
The alkaline error arises when a glass electrode is employed to measure the pH of
solutions having pH values in the 10 to 12 range or greater. In the presence of alkali ions,
the glass surface becomes responsive to not only hydrogen ions but also alkali metal
ions. Measured pH values are low as a result.
19-11. What is the source of
Solutions:
(b) the boundary potential in a membrane electrode?
The boundary potential for a membrane electrode is a potential that develops when
the membrane separates two solutions that have different concentrations of a
cation or an anion that the membrane binds selectively. For an aqueous solution,
the following equilibria develop when the membrane is positioned between two
solutions of A+:
2
A +M− →
A+ + M−
membrane1 ← solution1 membrane1
A +M− →
A+ + M−
membrane2 ← solution2 membrane2
where the subscripts refer to the two sides of the membrane. A potential develops
across this membrane if one of these equilibria proceeds further to the right than
the other, and this potential is the boundary potential. For example, if the
concentration of A+ is greater in solution 1 than in solution 2, the negative charge
on side 1 of the membrane will be less than that of side 2 because the equilibrium
on side 1 will lie further to the left. Thus, a greater fraction of the negative charge
on side 1 will be neutralized by A+.
(d) the potential of a crystalline-membrane electrode used to determine the

concentration of F − ?
The membrane in a solid-state electrode for F− is crystalline LaF3, which when
immersed in aqueous solution, dissociates according to the equation
LaF3 (s)  La3 + + 3F −
Thus, the boundary potential develops across this membrane when it separates
two solutions of F− ion concentration. The source of this potential is the same as
described in part (b).
19-12. How does information supplied by a direct potentiometric measurements of pH differ

from that obtained from a potentiometric acid-base titration?
Answer:
The direct potentiometric measurement of pH provides a measure of the equilibrium
activity of hydronium ions in the sample. A potentiometric titration provides information
on the amount of reactive protons, both ionized and nonionized, in the sample.
19-15. (a) Calculate E 0 for the process
AgIO3 (s) + e−  Ag(s) + IO3 −
Solutions:
AgIO3 (s) + e−  Ag(s) + IO3 −
 1 
E Ag = 0.799 − 0.0592log  + 
K sp = [Ag + ][IO3 − ] = 3.1 × 10−8
 [Ag ] 
 [IO3 − ] 
E Ag = 0.799 − 0.0592log  
 K sp 
 
When [IO3−] = 1.00, EAg is equal to E AgIO

o
3
for the reduction of AgIO3, that is,
 1.00 
E AgIO
o
= 0.799 − 0.0592log   = 0.354 V
3
 3.1 × 10 −8 
3
(b) Use the shorthand notation to describe a cell consisting of a saturated calomel
reference electrode and a silver indicator electrode that could be used to measure
pIO 3 .
SCE  IO3− (x M), AgIO3(sat’d)⏐Ag
(c) Develop an equation that relates the potential of the cell in (b) to pIO 3 .
Ecell = E AgIO − ESCE

3
( (
= 0.354 − 0.0592log [IO3 − ] − 0.244 ) )
= 0.110 + 0.0592pIO3
Ecell − 0.110
pIO3 =
0.0592
(d) Calculate pIO3 if the cell in (b) has a potential of 0.306 V.
0.306 − 0.110
pIO3 = = 3.31
0.0592
19-17. Use the shorthand notation to describe a cell consisting of a saturated calomel reference
electrode and a silver indicator electrode for the measurement of
Solutions:
(a) pI.
SCE  I− (x M), AgI (sat’d)⏐Ag
(c) pPO4 .
SCE  PO43− (x M), Ag3PO4 (sat’d)⏐Ag
19-19. Calculate
Solutions:
(a) pI if the cell in Problem 19-17(a) has a potential of −196 mV.
−0.196 + 0.395
pI = = 3.36
0.0592
(c) pPO4 if the cell in Problem 19-17(c) has a potential of 0.211 V.
3 ( 0.211− 0.163 )
pPO4 = = 2.43
0.0592
4
19-20. The cell
SCE  Ag2CrO4 (sat’d), CrO42− (x M)⏐Ag

is used for the determination of pCrO4 . Calculate pCrO4 when the cell potential is 0.389 V.
Solution:
SCE  Ag2CrO4 (sat’d), CrO42− (x M)⏐Ag
Ag2CrO4 (s) + 2e−  2Ag(s ) + CrO4 2 − E o = 0.446 V
0.0592 0.0592
0.389 = 0.446 −
2
( )
log [CrO4 2− ] − 0.244 = 0.202 +
2
pCrO4
2 ( 0.389 − 0.202 )
pCrO4 =
0.0592
pCrO4 = 6.32
19-21. The cell
SCE  H+ (a = x )|glass electrode

has a potential of 0.2106 V when the solution in the right-hand compartment is a buffer
of pH 4.006. The following potentials are obtained when the buffer is replaced with
unknowns: (a) −0.2902 V and (b) +0.1241 V. Calculate the pH and the hydrogen ion
activity of each unknown. (c) Assuming an uncertainty of 0.002 V in the junction
potential, what is the range of hydrogen ion activities within which the true value might
be expected to lie?
Solution:
Substituting into Equation 19-22 gives
1 ( Ecell − C ) ( 0.2106 − C )
pH = − and 4.006 = −
0.0592 0.0592
C = ( 4.006 × 0.0592 ) + 0.2106 = 0.447755
(a) pH = −
( −0.2902 − 0.447755) = 12.47
0.0592
aH+ = antilog ( −12.4655 ) = 3.42 × 10−13 M
(b) pH = −
( 0.1241− 0.447755) = 5.47
0.0592
aH+ = antilog ( −5.4671) = 3.41 × 10−6 M
5
(c) For part (a)

If E = −0.2902 + 0.002 = −0.2882 V
pH = −
( −0.2882 − 0.447755) = 12.43
0.0592
aH+ = antilog ( −12.4317 ) = 3.70 × 10−13
If E = −0.2902 − 0.002 = −0.2922 V
pH = −
( −0.2922 − 0.447755) = 12.50
0.0592
aH+ = antilog ( −12.4992 ) = 3.17 × 10−13 M
Thus pH should be 12.43 to 12.50 and aH+ in the range of 3.17 to 3.70 × 10−13 M
Proceeding in the same way for (b), we obtain

pH in the range 5.43 to 5.50
aH+ in the range 3.16 × 10−6 to 3.69 × 10−6 M
19-22. A 0.4021-g sample of a purified organic acid was dissolved in water and titrated
potentiometrically. A plot of the data revealed a single end point after 18.62 mL of
0.1243 M NaOH had been introduced. Calculate the molecular mass of the acid.
Solution:
0.1243 mmol NaOH 1mmol HA
amount HA = × 18.62 mL NaOH × = 2.3145 mmol
mL mmol NaOH
0.4021g HA 1000 mmol 173.7 g HA
× =
2.3145 mmol HA mol mol
MHA = 173.7 g/mol
19-26. The Na+ concentration of a solution was determined by measurements with a sodium
ion-selective electrode. The electrode system developed a potential of −0.2462 V when
immersed in 10.0 mL of the solution of unknown concentration. After addition of 1.00 mL
of 2.00 × 10−2 M NaCl, the potential changed to −0.1994 V. Calculate the Na+
concentration of the original solution.
Solution:
 E′ − K 
( )
pNa = −log [Na+ ] = −  cell  where Ecell
′ = −0.2462 V
 0.0592 
After addition Ece
′′ ll = −0.1994 V
−log 
(
 10.00 × [Na+ ] + 1.00 × 2.00 × 10 −2  )
 = −  Ecell − K 
 ′′ 
 10.00 + 1.00   0.0592 
 
 E ′′ − K 
( ( ))
− log 0.9091[Na+ ] + 1.818 × 10 −3 = −  cell
 0.0592 

6
Subtracting this latter equation from that for the initial potential gives
 Ecell
′ − K   Ecell
′′ − K 
( ) ( (
− log [Na+ ] + log 0.9091[Na+ ] + 1.818 × 10 −3 )) = −  0.0592  +  0.0592 
   
 Ec′′ell − Ec′ell 
= 
 0.0592 
 [Na+ ]  −0.1994 + 0.2462
− log  = = 0.7905
(
 0.9091[Na+ ] + 1.818 × 10 −3 
  )0.0592
 [Na ]+ 
or, log   = −0.7905
(
 0.9091[Na+ ] + 1.818 × 10 −3 
  )
+
[Na ]
= antilog ( −0.7905 ) = 0.16198
(
0.9091[Na ] + 1.818 × 10 −3
+
)
+ +
[Na ] = 0.1473 [Na ] + 2.945 × 10−4
[Na+] = 3.453 × 10−4 M or rounding 3.5 × 10−4 M
7
© 2022, 978-0-357-45055-0, Chapter 20: Bulk Electrolysis: Electrogravimetry and Coulometry
Chapter 20
20-1. Briefly distinguish between
Answers:
(a) concentration polarization and kinetic polarization.
In concentration polarization, the current in an electrochemical cell is limited by the
rate at which reactants are brought to or removed from the surface of one or both
electrodes. In Kinetic polarization, the current is limited by the rate at which
electrons are transferred between the electrode surfaces and the reactant in
solution. For either type, the current is no longer linearly related to cell potential.
(c) diffusion and migration.

Diffusion is the movement of species under the influence of a concentration
gradient. Migration is the movement of an ion under the influence of an
electrostatic attractive or repulsive force.
(e) the electrolysis circuit and the control circuit for controlled-potential methods.
The electrolysis circuit consists of a working electrode and a counter electrode. The
control circuit regulates the applied potential such that the potential between the
working electrode and a reference electrode in the control circuit is constant and at
a desired level.
20-2. Briefly define
Answers:
(a) ohmic potential.
The ohmic potential, or IR drop, of a cell is the product of the current in the cell in
amperes and the electrical resistance of the cell in ohms.
(c) controlled-potential electrolysis.

In controlled-potential electrolysis, the potential applied to a cell is continuously
adjusted to maintain a constant potential between the working electrode and a
reference electrode.
1
(e) current efficiency.

Current efficiency is a measure of agreement between the number of faradays of
charge and the number of moles of reactant oxidized or reduced at a working
electrode.
20-3. Describe three mechanisms responsible for the transport of dissolved species to and
from an electrode surface.
Answer:
Diffusion arises from concentration differences between the electrode surface and the
bulk of solution. Migration results from electrostatic attraction or repulsion. Convection
results from stirring, vibration or temperature differences.
20-5. What experimental variables affect concentration polarization in an electrochemical cell?
Answer:
Variables that influence concentration polarization include temperature, stirring,
reactant concentrations, presence or absence of other electrolytes and electrode surface
areas.
20-7. Describe conditions that favor kinetic polarization in an electrochemical cell.
Answer:
Kinetic polarization is often encountered when the product of a reaction is a gas,
particularly when the electrode is a soft metal such as mercury, zinc, or copper. It is likely
to occur at low temperatures and high current densities.
20-9. How do electrogravimetric and coulometric methods differ from potentiometric

methods? Consider currents, voltages, and instrumentation in your answer.
Answer:
Potentiometric methods are carried out under zero-current conditions, and the effect of
the measurement on analyte concentration is typically undetectable. In contrast,
electrogravimetric and coulometric methods depend on the presence of a net current
and a net cell reaction (i.e., the analyte is quantitatively converted to a new oxidation
state). Unlike potentiometric methods where the cell potential is simply the difference
between two electrode potentials, two additional phenomena, IR drop and polarization,
must be considered in electrogravimetric and coulometric methods where current is
present. Finally, the final measurement in electrogravimetric and coulometric methods is
the mass of the product produced electrolytically, while in potentiometric methods it is
the cell potential.
2
20-11. Why is the working electrode normally isolated from the counter electrode in a
controlled-potential coulometric analysis?
Answer:
The species produced at the counter electrode are potential interferences by reacting
with the products at the working electrode. Isolation of one from the other is ordinarily
required.
20-13. Determine the number of ions undergoing electron transfer at the surface of an
electrode during each second that an electrochemical cell is operated at 0.0175 A
at 100% current efficiency and the participating ions are
Solution:
(b) divalent.
For a divalent ion
0.0175 C 1F 1mol e − 1 mol 6.02 × 1023 ions 5.5 × 1016 ions
× × × × =
s 96,485 C F 2 mol e −
mol s
20-14. Calculate the theoretical potential at 25°C needed to initiate the deposition of
Solutions:
(a) copper from a solution that is 0.250 M in Cu2+ and buffered to a pH of 3.00.
Oxygen is evolved at the anode at 1.00 atm.
0.0592  1 
Eright = 0.337 − log   = 0.319 V
2  0.250 
 
0.0592 1
Eleft = 1.229 − log   = 1.051V

4
( )
4
 1.00 × 1.00 × 10 −3 
 
Eapplied = Eright − Eleft = 0.319 − 1.051
= −0.732 V
(c) silver bromide on a silver anode from a solution that is 0.0964 M in Br − and
buffered to a pH of 3.70. Hydrogen is evolved at the cathode at 765 torr.
[H+ ] = antilog ( −3.70 ) = 1.995 × 10 −4

 765 
0.0592  
Eright = 0.000 − log  760  = −0.219 V
2
( )
2
 1.995 × 10 −4 
 
 
Eleft = 0.073 − 0.0592log ( 0.0964 ) = 0.133 V
Eapplied = Eright − Eleft = −0.219 − 0.133
= −0.352 V
3
20-15. Calculate the initial potential needed for a current of 0.065 A in the cell
Co|Co2 + (5.90 × 10 −3 M)  Zn2+ (2.95 × 10 −3 M)|Zn if this cell has a resistance of 4.50 Ω.
Solution:
0.0592  1 
Eright = −0.763 − log  −3 
= −0.838 V
2  2.95 × 10 
0.0592  1 
Eleft = −0.277 − log  −3 
= −0.343 V
2  5.90 × 10 
Ecell = −0.838 − ( −0.343 ) − 0.065 × 4.50
= −0.788 V
20-17. Copper is to be deposited from a solution that is 0.250 M in Cu(II) and is buffered to a pH
of 4.00. Oxygen is evolved from the anode at a partial pressure of 730 torr. The cell has a
resistance of 3.60 Ω , and the temperature is 25°C. Calculate
Solutions:
(a) the theoretical potential needed to initiate deposition of copper from this solution.
0.0592  1 
Eright = 0.337 − log   = 0.319 V
2  0.250 
 
0.0592  1 
Eleft = 1.229 − log   = 0.992 V
4 730 
( )
4
 1.00 × 10−4 ×
 
 760 
Ecell = Eright − Eleft = 0.319 − 0.992
= −0.673 V
(b) the IR drop associated with a current of 0.15 A in this cell.

IR = −0.15 × 3.60 = −0.54 V
(c) the initial potential, given that the overvoltage of oxygen is 0.50 V under these
conditions.
Recall that the overpotential in an electrolytic cell requires the application of a
larger or more negative potential. That is, 0.50 V must be subtracted from the cell
potential.
Eapplied = −0.673 − 0.54 − 0.50 = −1.71 V
4
(d) the potential of the cell when Cu2 +  is 7.00 × 10−6 , assuming that IR drop and O2
overvoltage remain unchanged.
0.0592  1 
Eright = 0.337 − log  −6 
= 0.184 V
2  7.00 × 10 
Eapplied = 0.184 − 0.992 − 0.54 − 0.50
= −1.85 V
20-19. A solution is 0.200 M in Co2+ and 0.0650 M in Cd2 + . Calculate
Solutions:
(a) the Co2+ concentration in the solution as the first cadmium starts to deposit.
Cd begins to form when
0.0592  1 
E = −0.403 − log   = −0.438 V
2  0 .0650 
The Co2+ concentration when Cd first begins to deposit is:
0.0592  1 
−0.438 = −0.277 − log  2+ 
2  [Co ] 
2 ( −0.438 + 0.277 )
(
log [Co2+ ] = ) 0.0592
= −5.439
[Co2+ ] = antilog ( −5.439 ) = 3.6 × 10−6 M
(b) the cathode potential needed to lower the Co2+ concentration to 1.00 × 10 −5 M.
0.0592  1 
Ecathode = −0.277 − log  −5 
= −0.425 V
2  1.00 × 10 
(c) based on (a) and (b) above, can Co2+ be quantitatively separated from Cd2+ ?
Referring to Example 22-2, quantitative separation is assumed to occur when the
[Co2+] falls to 10−4 of its original concentration or 2.0 × 10−5 M. Thus, if the cathode
is maintained between −0.425 V and −0.438 V, the quantitative separation of Co2+
from Cd2+ is possible in theory.
20-21. Electrogravimetric analysis with control of the cathode potential is proposed as a means
for separating Bi3+ and Sn2+ in a solution that is 0.250 M in each ion and buffered to pH
1.95.
Solutions:
(a) Calculate the theoretical cathode potential at the start of deposition of the more
easily reduced ion.
5
Bi deposits at a lower potential, that is

[H+ ] = antilog ( −1.95 ) = 1.12 × 10−2 M
 
0.0592 1
Ecathode = 0.320 − log  

3
( )
2
 0.250 1.12 × 10−2 
 
= 0.231 V
(b) Calculate the residual concentration of the more readily reduced species at the
outset of the deposition of the less easily reduced species.
Sn deposits when
0.0592  1 
Ecathode = −0.136 − log   = −0.154 V
2  0.250 
 
0.0592  1 
−0.154 = 0.320 − log  2 
3

+
(
 [BiO ] 1.12 × 10 − 2

 )
0.0592 0.0592
( )
2
= 0.320 + log 1.12 × 10 −2 + log ([BiO+ ])
3 3
3 ( −0.154 − 0.320 + 0.077 )
( )
log [BiO+ ] =
0.0592
= −20.12
[BiO+] = antilog(−20.12) = 7.6 × 10−21 M
(c) Propose a range (versus SCE), if such exists, within which the cathode potential
should be maintained. Consider a residual concentration less than 10−6 M as
constituting quantitative removal.
When [BiO+] = 10−6
 
0.0592 1
Ecathode = 0.320 − log   = 0.124 V

3
( )
2
 1.00 × 10 1.12 × 10 −2
−6

 
Sn begins to form when Ecathode = −0.154 V (see part (b))
range vs. SCE = 0.124 − 0.244 to −0.154 − 0.244 or −0.12 to −0.398 V
= −0.120 to −0.398 V
20-22. A solution is 0.200 M in each of two reducible cations, A and B. Removal of the more
reducible species (A) is deemed complete when [A] has been decreased to
1.00 × 10 −5 M. What minimum difference in standard electrode potentials will permit
the isolation of A without interference from B when
6
A Is B Is
(a) univalent univalent

(c) trivalent univalent
(e) divalent divalent
(g) univalent trivalent
(i) trivalent trivalent
Solution:
Deposition of A is complete when
0.0592  1  0.278
E A = E Ao − log  −5 
= E Ao −
nA  2.00 × 10  nA
Deposition of B begins when

0.0592  1  0.0414
EB = EBo − log  −1 
= EBo −
nB  2.00 × 10  nB
Boundary condition is that EA = EB. Thus,

0.278 0.0414
E Ao − = EBo − or
nA nB
0.278 0.0414
E Ao − EBo = −
nA nB
0.278 0.0414
(a) E Ao − EBo = − = 0.237 V
1 1
0.278 0.0414
(c) EAo − EBo = − = 0.0513 V
3 1
0.278 0.0414
(e) E Ao − EBo = − = 0.118 V
2 2
0.278 0.0414
(g) EAo − EBo = − = 0.264 V
1 3
0.278 0.0414
(i) EAo − EBo = − = 0.0789 V
3 3
7
20-23. Calculate the time needed for a constant current of 0.8510 A to deposit 0.250 g of Co(II)
as
Solutions:
(a) elemental cobalt on the surface of a cathode.
1 mol Co 2 mol e− 1F 96,485 C

0.250 g Co × × × × = 8.186 × 102 C
58.93 g mol Co mol e −
F
1A × s 1 1 min
8.186 × 102 C × × × = 16.0 min
C 0.851 A 60 s
(b) Co3O4 on an anode.
Assume 100% current efficiency for both gases.
3Co2+ + 4H2O  Co3O4 (s) + 8H+ + 2e− 3 ( 2 ) mol Co 2+

= 1 mol e−
1 mol Co 2 mol e− 1F 96,485 C

0.250 g Co × × × × = 2.727 × 102 C
58.93 g 3 mol Co mol e −
F
1A × s 1 1 min
2
2.727 × 10 C × × × = 5.34 min
C 0.851 A 60 s
20-25. A 0.1330-g sample of a purified organic acid was neutralized by the hydroxide ion
produced in 5 minutes and 24 s by a constant current of 300 mA. Calculate the
equivalent mass of the acid in grams.
Solution:
 60 s  1 C 1F 1 eq HA
 5 min × + 24 s  × 0.300 A × × × = 1.007 × 10 −3 eq HA
 min  A × s 96,485 C F
0.1330 g HA
= 132.0 g/eq
1.007 × 10 −3 eq HA
20-27. An excess of HgNH3 Y 2 − was introduced to 25.00 mL of well water. Express the hardness
of the water in terms of ppm CaCO3 if the EDTA needed for the titration was generated
at a mercury cathode (Equation 20-9) in 3.52 minutes by a constant current of 39.4 mA.
Assume 100% current efficiency.
Solution:
1 mol CaCO3 = 1 mol HgNH3Y2- = 2 mol e−
 60 s 1C 1 mol e− 1 mol CaCO3 100.09 g CaCO3 
 39.4 × 10 A × 3.52 min ×
−3
× × × × 
 min A × s 96, 485 C 2 mol e −
mol  × 106 ppm
1.00 g H2O
25.00 mL sample ×
mL H2 O
= 173 ppm CaCO3
8
20-29. The nitrobenzene in 300 mg of an organic mixture was reduced to phenylhydroxylamine

at a constant potential of −0.96 V (versus SCE) applied to a mercury cathode:
C6H5NO2 + 4H+ + 4e− → C6H5NHOH + H2O
The sample was dissolved in 100 mL of methanol. After electrolysis for 30 minutes, the
reaction was judged complete. An electronic coulometer in series with the cell indicated
that the reduction required 33.47 C. Calculate the percentage of C 6H5NO2 in the sample.
Solution:
1 mol C6H5NO2 = 4 mol e−
 1F 1 mol e− 1 mol C6H5NO2 123.11 g C6H5NO2 
 33.47 C × × × × 
 96,485 C F 4 mol e −
mol  × 100%
g
300 mg sample ×
1000 mg
= 3.56% C6H5NO2
20-34. Traces of aniline, C 6H5NH2 , in drinking water can be determined by reaction with an
excess of electrolytically generated Br2 :
The polarity of the working electrode is then reversed, and the excess Br2 is determined
by a coulometric titration involving the generation of Cu(I):
Br2 + 2Cu+ → 2Br − + 2Cu2 +
Suitable quantities of KBr and CuSO4 were added to a 25.0-mL sample containing
aniline. Calculate the number of micrograms of C 6H5NH2 in the sample from the data:
Working Electrode Functioning As Generation Time with Constant

Current of 1.51 mA, min
Anode 3.76
Cathode 0.270
Solution:
1 mol C6H5NH2 = 3 mol Br2 = 6 mol e−
 60 s 1.51× 10 −3 C 1F 
 ( 3.76 − 0.27 ) min × × × ×
 min s 96,485 C 
 = 5.462 × 10 mol C6H5NH2
−7
 1mol e− 1mol C6H5NH2
 × 
 F 6 mol e− 
 
93.128 g C H NH 6
10 μg
5.462 × 10−7 mol C6H5NH2 × 6 5 2
×
mol g
= 50.9 μg C6H5NH2
9
20-35. Quinone can be reduced to hydroquinone with an excess of electrolytically generated

Sn(II):
The polarity of the working electrode is then reversed, and the excess Sn(II) is oxidized
with Br2 generated in a coulometric titration:
Sn2+ + Br2 → Sn4 + + 2Br −
Appropriate quantities of SnCl4 and KBr were added to a 50.0-mL sample. Calculate the
mass of C 6H4 O2 in the sample from the data:
Working Electrode Functioning As Generation Time with Constant

Current of 1.062 mA, min
Cathode 8.34
Anode 0.691
Solution:
1 mol Sn4+ = 2 mol e− → 1 mol Sn2+ = 2 mol C6H4O2
 60 s 1.062 × 10 −3 C 1F 
 ( 8.34 − 0.691) min × × × 
 min s 96,485 C 
  = 2.526 × 10−6 mol C6H4 O2
1 mol e −
1mol C6H5NH2
 × × 
 F 2 mol e− 
 
108.10 g C H O
2.526 × 10 −6 mol C6H4 O2 × 6 4 2
mol
= 2.73 × 10−4 g C6H4 O2
10
© 2022, 978-0-357-45055-0, Chapter 21: Voltammetry
Chapter 21
Answers:
(a) voltammetry and amperometry.
Voltammetry is an analytical technique that is based on measuring the current that
develops at a small electrode as the applied potential is varied. Amperometry is a
technique in which the limiting current is measured at a constant potential.
(c) differential-pulse voltammetry and square-wave voltammetry.

Differential pulse and square wave voltammetry differ in the type of pulse sequence
used as shown in Figure 21-1b and 21-1c.
(e) a limiting current and a diffusion current.

In voltammetry, a limiting current is a current that is independent of applied
potential. Its magnitude is limited by the rate at which a reactant is brought to the
surface of the electrode by migration, convection, and/or diffusion. A diffusion
current is a limiting current when analyte transport is solely by diffusion.
(g) the standard electrode potential and the half-wave potential for a reversible
reaction at a working electrode.
The half-wave potential is closely related to the standard potential for a reversible
reaction. That is,
0.0592 k 
E1/2 = E Ao − log  A 
n  kB 
where kA and kB are constants that are proportional to the diffusion coefficients of
the analyte and product. When these are approximately the same, the half-wave
potential and the standard potential are essentially equal.
1
21-3. Why is a high supporting electrolyte concentration used in most electroanalytical

procedures?
Answer:
A high supporting electrolyte concentration is used in most electroanalytical procedures
to minimize the contribution of migration to concentration polarization. The supporting
electrolyte also reduces the cell resistance, which decreases the IR drop.
21-5. Why is it necessary to buffer solutions in organic voltammetry?
Answer:
Most organic electrode processes consume or produce hydrogen ions. Unless buffered
solutions are used, marked pH changes can occur at the electrode surface as the
reaction proceeds.
21-7. What is the purpose of the electrodeposition step in stripping analysis?
Answer:
The purpose of the electrodeposition step in stripping analysis is to preconcentrate the
analyte on the surface of the working electrode and to separate it from many interfering
species.
21-9. Suggest how Equation 21-13 could be used to determine the number of electrons n
involved in a reversible reaction at an electrode.
Solution:
i −0.0592
A plot of Eappl versus log should yield a straight line having a slope of . Thus,
il − i n
n is readily obtained from the slope.
21-12. It has been suggested that many polarograms can be obtained on a solution without
depleting the electroactive analyte. Suppose that in a polarographic experiment we
monitor the limiting current for 45 minutes in 60 mL of 0.08 MCu2+ . If the average
current during the time of the experiment is 6.0 μA, what fraction of the copper is
removed from the solution?
Solution:
Initally there are 60 mL × 0.08 mmol/mL = 4.8 mmol Cu2+ present.
Applying a current of 6.0 μA for 45 minutes represents a charge of
6.0 × 10−6 C/s × 45 min × 60 s/min = 0.0162 C
The number of moles of Cu2+ reduced by that amount of charge is:
nCu2+ = Q/nF = 0.0162 C/(2 × 96485 C/mol) = 8.4 × 10−8 mol or 8.4 × 10−5 mmol
The percentage removed is thus (8.4 × 10−5 mmol/ 4.8 mmol) × 100% = 1.7 × 10−3%
2
21-13. An unknown cadmium(II) solution was analyzed polarographically by the method of

standard additions. A 25.00-mL sample of the unknown solution produced a diffusion
current of 1.86 μA. Following addition of a 5.00-mL aliquot of 2.12 × 10−3 M Cd2+
standard solution to the unknown solution, a diffusion current of 5.27 μA was produced.
Calculate the concentration of Cd2+ in the unknown solution.
Solution:
i1 = kcu where i1 = 1.86 μA and cu is the concentration of the unknown.
i2 =
(
k 25.00 cu + 5.00 × 2.12 × 10−3 ) = 5.27 μA
25.00 + 5.00
From above, k = i1/cu. Substituting this into the second equation and solving for cu gives
cu = 1.77 × 10−4 M
3
© 2022, 978-0-357-45055-0, Chapter 22: Introduction to Spectrochemical Methods
Chapter 22
22-1. In a solution of pH 5.3, the indicator bromocresol purple exhibits a yellow color, but
when the pH is 6.0, the indicator solution changes to purple. Discuss why these colors
are observed in terms of the wavelength regions and colors absorbed and transmitted.
Answer:
The yellow color comes about because the solution absorbs blue light in the wavelength
region 435–480 nm and transmits its complementary color (yellow). The purple color
comes about because green radiation (500–560 nm) is absorbed and its complementary
color (purple) is transmitted.
22-2. What is the relationship between
Answer:
(a) absorbance and transmittance?
Absorbance, A, is the negative logarithm of transmittance T (A = − log T ).
22-3. Identify factors that cause the Beer’s law relationship to be nonlinear.
Answer:
Deviations from linearity can occur because of polychromatic radiation, unknown
chemical changes such as association or dissociation reactions, stray light, and molecular
or ionic interactions at high concentration.
22-6. Calculate the frequency in hertz of
Solutions:
ν = c/λ = 3.00 × 1010 cm s−1/λ(cm) = (3.00 × 1010/λ) s−1 = (3.00 × 1010/λ) Hz
(a) an X-ray beam with a wavelength of 2.65 Å.
ν = 3.00 × 1010 cm s−1/(2.65 Å × 10−8 cm/Å) = 1.13 × 1018 Hz
(c) the line at 694.3 nm produced by a ruby laser.

ν = 3.00 × 1010 cm s−1/(694.3 nm × 10−7 cm/nm) = 4.32 × 1014 Hz
(e) an infrared absorption peak at 9.6 μm.

ν = 3.00 × 1010 cm s−1/(9.6 μm × 10−4 cm/μm) = 3.12 × 1013 Hz
1
22-7. Calculate the wavelength in centimeters of
Solutions:
λ = c/ν = 3.00 × 1010 cm s−1/ν (s−1) = (3.00 × 1010/ν) cm
(a) an airport tower transmitting at 118.6 MHz.
λ = 3.00 × 1010 cm s−1/(118.6 MHz × 106 Hz/MHz) = 253.0 cm
(c) an NMR signal at 105 MHz.

λ = 3.00 × 1010 cm s−1/(105 MHz × 106 Hz/MHz) = 286 cm
22-9. A typical simple infrared spectrophotometer covers a wavelength range from 3 to 15 μm.
Express its range (a) in wavenumbers and (b) in hertz.
Solutions:
(a) ν = 1/(3 μm × 10−4 cm/μm) = 3.333 × 103 cm−1 to
1/(15 × 10−4 cm) = 6.67 × 102 cm−1
(b) ν = 3.00 × 1010 cm s−1 × 3.333 × 103 cm−1 = 1.00 × 1014 Hz to

3.00 × 1010 × 6.67 × 102 = 2.00 × 1013 Hz
22-11. Calculate the wavelength and the energy in joules associated with a signal at 220 MHz.
Solution:
λ = c/ν = (3.00 × 1010 cm s−1)/(220 × 106 s−1) = 136 cm or 1.36 m
E = hν = 6.63 × 10−34 J s × 220 × 106 s−1 = 1.46 × 10−25 J
22-12. Calculate the wavelength of
Solution:
(a) the sodium line at 589 nm in an aqueous solution with a refractive index of 1.35.
λ = 589 nm/1.35 = 436 nm
22-13. What are the units for absorptivity when the path length is given in centimeters and the
concentration is expressed in
Solutions:
(a) parts per million?
ppm−1 cm−1
(c) mass-volume percent?

%−1 cm−1
22-14. Express the following absorbances in terms of percent transmittance.
Solutions:
(a) 0.0356
%T = 100 × antilog(−0.0356) = 92.1%
Proceeding similarly, we obtain
(c) 0.379
%T = 41.8
(e) 0.485
%T = 32.7
22-15. Convert the accompanying transmittance data to absorbances.
Solutions:
(a) 27.2%
A = −log T = −log(27.2%/100%) = 0.565
Proceeding similarly,
(c) 30.6%
A = 0.514
(e) 0.093
A = 1.032
22-18. Evaluate the missing quantities in the accompanying table. Where needed, use 200 for
the molar mass of the analyte.
ε a b c
A %T L mol−1 cm−1 cm−1 ppm−1 cm M ppm
(a) 0.172 4.23 × 103 1.00
(c) 0.520 7.95 × 103 1.00
(e) 3.73 × 103 0.100 1.71× 10−3
(g) 0.798 1.50 33.6
(i) 5.23 9.78 × 103 5.24
Solutions:
(a) %T = antilog(−0.172) × 100% = 67.3%
c = A/εb = (0.172)/(4.23 × 103 × 1.00) = 4.07 × 10−5 M
mol 200 g 1L
c = 4.07 × 10−5 × × × 106 ppm = 8.13 ppm
L mol 1000 g
a = A/bc = 0.172/(1.00 × 8.13) = 0.0211 cm−1 ppm−1
Using similar conversions and calculations, we can evaluate the missing quantities
ε a b c
A %T L mol−1 cm−1 cm−1 ppm−1 cm M Ppm
(a) 0.172 67.3 4.23 × 10 3
0.0211 1.00 4.07 × 10 −5
8.13
(c) 0.520 30.2 7.95 × 10 3
0.0397 1.00 6.54 × 10 −5
13.1
(e) 0.638 23.0 3.73 × 10 3
0.0187 0.100 1.71 × 10 −3
342
(g) 0.798 15.9 3.17 × 103 0.0158 1.50 1.68 × 10−4 33.6
(i) 1.28 5.23 9.78 × 103 0.0489 5.00 2.62 × 10−5 5.24
22-21. At 580 nm, the wavelength of its maximum absorption, the complex Fe(SCN)2+ has a
molar absorptivity of 7.00 × 103 L cm−1 mol−1. Calculate
Solutions:
(a) the absorbance of a 3.40 × 10−5 M solution of the complex at 580 nm in a 1.00-cm
cell.
A = 7.00 × 103 L mol−1 cm−1 × 1.00 cm × 3.40 × 10−5 mol L−1 = 0.238
(b) the absorbance of a solution in which the concentration of the complex is twice
that in (a).
A = 7.00 × 103 × 1.00 × 2 × 3.40 × 10−5 = 0.476
(c) the transmittance of the solutions described in (a) and (b).

For part (a), T = antilog(−0.238) = 0.578
For part (b), T = antilog(−0.476) = 0.334
(d) the absorbance of a solution that has half the transmittance of that described in (a).
A = −log(T) = −log(0.578/2) = 0.539
22-23. A solution containing the complex formed between Bi(III) and thiourea has a molar
absorptivity of 9.32 × 103 L cm−1 mol−1 at 470 nm.
Solutions:
(a) What is the absorbance of a 5.67 × 10−5 M solution of the complex at 470 nm in a
1.00-cm cell?
A = 9.32 × 103 L mol−1 cm−1 × 1.00 cm × 5.67 × 10−5 mol L−1 = 0.528
(b) What is the percent transmittance of the solution described in (a)?

%T = 100 × antilog(−0.528) = 29.6%
(c) What is the molar concentration of the complex in a solution that has the
absorbance described in (a) when measured at 470 nm in a 2.50-cm cell?
c = A/εb = 0.528/(9.32 × 103 L mol−1 cm−1 × 2.50 cm) = 2.27 × 10−5 M
22-25. A solution with a “true” absorbance  A = −log ( P0 /P )  of 2.10 was placed in a

spectrophotometer with a stray light percentage ( Ps /P0 ) of 0.75. What absorbance A′
would be measured? What percentage error would result?
Solution:
2.10 = −log (P/P0) P/P0 = 0.0079433 P = 0.007943 P0
Ps/P0 = 0.0075 Ps = 0.0075 P0
 P + Ps   P0 + 0.0075P0   1.0075P0 
A′ =  0  = log   = log   = log(65.2139) = 1.81
 P + Ps   0.007943P0 + 0.0075P0   0.015443P0 
Error = [(1.81 − 2.10)/2.10] × %100 = −13.6%
© 2022, 978-0-357-45055-0, Chapter 23: Instruments for Optical Spectrometry
Chapter 23
23-1. Describe the differences between the following pairs of terms, and list any particular
advantages possessed by one over the other:
Answers:
(a) solid-state photodiodes and phototubes as detectors for electromagnetic radiation.
Phototubes consist of a single photoemissive surface (cathode) and an anode in an
evacuated envelope. They exhibit low dark current, but have no inherent
amplification. Solid-state photodiodes are semiconductor pn-junction devices that
respond to incident light by forming electron-hole pairs. They are more sensitive
than phototubes but less sensitive than photomultiplier tubes.
(c) filters and monochromators as wavelength selectors.

Filters isolate a single band of wavelengths. They provide low resolution wavelength
selection suitable for quantitative work. Monochromators produce high resolution
for qualitative and quantitative work. With monochromators, the wavelength can
be varied continuously, whereas this is not possible with filters.
23-3. Why do quantitative and qualitative analyses often require different monochromator slit
widths?
Answer:
Quantitative analyses can tolerate rather wide slits since measurements are usually
carried out at a wavelength maximum where the slope of the spectrum dA/dλ is
relatively constant. On the other hand, qualitative analyses require narrow slits so that
any fine structure in the spectrum will be resolved. This can allow differentiation of one
compound from another.
23-5. Why is iodine sometimes introduced into a tungsten lamp?
Answer:
Tungsten/halogen lamps contain a small amount of iodine in the evacuated quartz
envelope that contains the tungsten filament. The iodine prolongs the life of the lamp
and permits it to operate at a higher temperature. The iodine combines with gaseous
tungsten that sublimes from the filament and causes the metal to be redeposited, thus
adding to the life of the lamp.
1
advantages of one over the other:
Answers:
(a) spectrophotometers and photometers.
Spectrophotometers have monochromators for multiple wavelength operation and
for procuring spectra while photometers utilize filters for fixed wavelength
operation. While offering the advantage of multiple wavelength operation,
spectrophotometers are substantially more complex and more expensive than
photometers.
(c) monochromators and polychromators.

Both a monochromator and a polychromator use a diffraction grating to disperse the
spectrum, but a monochromator contains only one exit slit and detector while a
polychromator contains multiple exit slits and detectors. A monochromator can be
used to monitor one wavelength at a time while a polychromator can monitor
several discrete wavelengths simultaneously.
23-7. The Wien displacement law states that the wavelength maximum in micrometers for
blackbody radiation is
λmaxT = 2.90 × 103
where T is the temperature in kelvins. Calculate the wavelength maximum for a

blackbody that has been heated to (a) 4000 K, (c) 2000 K.
Solutions:
(a) λmax = 2.90 × 103 / T = 2.90 × 103 / 4000 = 0.73 μm
(c) λmax = 2.90 × 103 / 2000 = 1.45 μm
23-9. The relationships described in Problems 23-7 and 23-8 may be of help in solving the
following.
Solutions:
(a) Calculate the wavelength of maximum emission of a tungsten-filament bulb
operated at 2870 K and at 3000 K.
λmax = 2.90 × 103/2870 = 1.01 μm (1010 nm)
λmax = 2.90 × 103/3000 = 0.967 μm (967 nm)
(b) Calculate the total energy output of the bulb in W/cm2 .

Et = 5.69 × 10−8 (2870)4 × (1 m/100 cm)2 = 386 W/cm2
Et = 5.69 × 10−8 (3000)4 × (1 m/100 cm)2 = 461 W/cm2
23-11. What is the purpose of (a) the 0% T adjustment and (b) the 100% T adjustment of a
spectrophotometer?
Answers:
(a) The 0% transmittance is measured with no light reaching the detector and is a
measure of the dark current or dark signal.
(b) The 100% transmittance adjustment is made with a blank in the light path and
measures the unattenuated source. It compensates for any absorption or
reflection losses in the cell and optics.
23-13. What are the major advantages of Fourier transform IR instruments over dispersive IR
instruments?
Answer:
Fourier transform IR spectrometers have the advantages over dispersive instruments of
higher speed and sensitivity, better light-gathering power, more accurate and precise
wavelength settings, simpler mechanical design, and elimination of stray light and IR
emission.
23-14. A photometer with a linear response to radiation gave a reading of 625 mV with a blank
in the light path and 149 mV when the blank was replaced by an absorbing solution.
Calculate
Solutions:
(a) the percent transmittance and absorbance of the absorbing solution.
%T = (149/625) × 100% = 23.84%
A = –log(23.84%/100) = 0.623
(c) the percent transmittance to be expected if the light path through the original
solution is doubled.
Since A is proportional to light path, at twice the light path A = 2 × 0.623 = 1.246
T = antilog(–A) = antilog(–1.246) = 0.057; %T = 5.7
23-15. A portable photometer with a linear response to radiation registered a photocurrent of

75.9 μA with a blank solution in the light path. Replacement of the blank with an
absorbing solution yielded a response of 23.5 μA. Calculate
Solutions:
(b) the absorbance of the sample solution.
A = –log(30.96%/100) = 0.509
(d) the transmittance to be expected for a solution that has twice the concentration of
the sample solution.
A = 2 × 0.509 = 1.018
T = antilog(–A) = antilog(–1.018) = 0.096
23-17. What are the differences between a photon detector and a thermal detector?
Answer:
A photon detector produces a current or voltage as a result of the emission of electrons
from a photosensitive surface when struck by photons. A thermal detector consists of a
darkened surface to absorb infrared radiation and produce a temperature increase. A
thermal transducer produces an electrical signal whose magnitude is related to the
temperature and thus the intensity of the infrared radiation.
23-19. Describe how an absorption photometer and a fluorescence photometer differ from
each other.
Answer:
Basically, an absorption photometer and a fluorescence photometer consist of the same
components. The basic difference is in the location of the detector and in the source
intensity. An intense source is used in fluorescence so as to produce measurable
emission. The detector in a fluorometer is positioned at an angle of 90o to the direction
of the beam from the source so that emission is detected rather than transmisson. In
addition, a filter is often positioned in front of the detector to remove radiation from the
excitation beam that may result from scattering or other nonfluorescence processes. In
a transmission photometer, the detector is positioned in a line with the source, the filter,
and the detector.
23-21. Define
Answers:
(a) transducer.
Transducer indicates the type of detector that converts quantities, such as light
intensity, pH, mass, and temperature, into electrical signals that can be
subsequently amplified, manipulated, and finally converted into numbers
proportional to the magnitude of the original quantity.
(c) n-type semiconductor.

A semiconductor containing unbonded electrons (e.g. produced by doping silicon
with a Group V element) is termed an n-type semiconductor.
(e) depletion layer.

A depletion layer results when a reverse bias is applied to a pn-junction type device.
Majority carriers are drawn away from the junction leaving a nonconductive
depletion layer.
© 2022, 978-0-357-45055-0, Chapter 24: Molecular Absorption Spectrometry
Chapter 24
advantages of one over the other:
Answers:
(a) spectrophotometers and photometers.
Spectrophotometers use a grating or a prism to provide narrow bands of radiation while
photometers use filters for this purpose. The advantages of spectrophotometers are
greater versatility and the ability to obtain entire spectra. The advantages of
photometers are simplicity, ruggedness, higher light throughput and low cost.
(c) conventional and diode-array spectrophotometers.

Diode-array spectrophotometers detect the entire spectral range essentially
simultaneously and can produce a spectrum in less than a second. Conventional
spectrophotometers require several minutes to scan the spectrum. Accordingly,
diode-array instruments can be used to monitor processes that occur on fast time
scales. Their resolution is usually lower than that of a conventional
spectrophotometer.
24-3. What experimental variables must be controlled to assure reproducible absorbance

data?
Answer:
Electrolyte concentration, pH, temperature, nature of solvent, and interfering
substances.
24-5. The molar absorptivity for the complex formed between bismuth(III) and thiourea is
9.32 × 103 L cm−1 mol−1 at 470 nm. Calculate the range of permissible concentrations for
the complex if the absorbance is to be no less than 0.10 nor greater than 0.90 when the
measurements are made in 1.00-cm cells.
Solution:
A = εbc
cmin = A/εb = 0.10/(9.32 × 103 × 1.00) = 1.1 × 10−5 M
cmax = A/εb = 0.90/(9.32 × 103 × 1.00) = 9.7 × 10−5 M
1
24-7. The logarithm of the molar absorptivity for acetone in ethanol is 2.75 at 366 nm.
Calculate the range of acetone concentrations that can be used if the absorbance is to
be greater than 0.100 and less than 2.000 with a 1.50-cm cell.
Solution:
log ε = 2.75 ε = 5.6 × 102
cmin = A/εb = 0.100/(5.6 × 102 × 1.50) = 1.2 × 10−4 M
cmax = A/εb = 2.000/(5.6 × 102 × 1.50) = 2.4 × 10−3 M
24-9. A photometer with a linear response to radiation gave a reading of 690 mV with a blank
in the light path and 169 mV when the blank was replaced by an absorbing solution.
Calculate
Solutions:
(a) the transmittance and absorbance of the absorbing solution.
T = 169 mV/690 mV = 0.245
A = −log(0.245) = 0.611
(c) the transmittance to be expected if the light path through the original solution is
doubled.
Since A is proportional to light path, at twice the light path A = 2 × 0.611 = 1.222
T = antilog(−A) = antilog(−1.222) = 0.060
24-10. A portable photometer with a linear response to radiation registered 75.5 μA with a
blank solution in the light path. Replacement of the blank with an absorbing solution
yielded a response of 23.7 μA. Calculate
Solutions:
(b) the absorbance of the sample solution.

A = −log(31.4%/100) = 0.503
(d) the transmittance to be expected for a solution that has twice the concentration of
the sample solution.
A = 2 × 0.503 = 1.006
T = antilog(−A) = antilog(−1.006) = 0.099
24-13. Ethylenediaminetetraacetic acid displaces bismuth(III) from its thiourea complex:
Bi ( tu)6
3+
+ H2 Y 2 − → BiY − + 6tu + 2H+
where tu is the thiourea molecule, (NH2 )2 CS. Predict the shape of a photometric titration
curve based on this process, given that the Bi(III)/thiourea complex is the only species in
the system that absorbs at 465 nm, the wavelength selected for the titration.
Solution:
Absorbance
End Point
Volume EDTA
The absorbance should decrease approximately linearly with titrant volume until the end
point. After the end point the absorbance becomes independent of titrant volume.
Iron(III) forms a complex with thiocyanate ion that has the formula Fe ( SCN) . The
2+
24-16.
complex has an absorption maximum at 580 nm. A specimen of well water was assayed
according to the following scheme.
Calculate the concentration of iron in parts per million.

Solution:
Applying the equation we developed in Solution 26-15 we write
0.231 × 2.75 × 5.00
cx = = 0.200 ppm Fe
50.0(0.549 − 0.231)
24-18. Molar absorptivity data for the cobalt and nickel complexes with 2,3-quinoxalinedithiol are
εCo = 36,400 and εNi = 5520 at 510 nm and εCo = 1240 and εNi = 17,500 at 656 nm. A 0.425-g
sample was dissolved and diluted to 50.0 mL. A 25.0-mL aliquot was treated to eliminate
interferences; after addition of 2,3-quinoxalinedithiol, the volume was adjusted to 50.0 mL.
This solution had an absorbance of 0.446 at 510 nm and 0.326 at 656 nm in a 1.00-cm cell.
Calculate the concentration in parts per million of cobalt and nickel in the sample.
Solution:
A510 = 0.446 = 36400 × 1.00 × cCo + 5520 × 1.00 × cNi
A656 = 0.326 = 1240 × 1.00 × cCo + 17500 × 1.00 × cNi
cCo = 9.530 × 10−6 M cNi = 1.795 × 10−5 M
mmol 50.0 mL 0.05893 g Co
50.0 mL × 9.530 × 10−6 × ×
cCo = mL 25.0 mL mmol × 106 ppm = 132 ppm
0.425 g
mmol 50.0 mL 0.05869 g Ni
50.0 mL × 1.795 × 10−5 × ×
cNi = mL 25.0 mL mmol × 106 ppm = 248 ppm
0.425 g
24-20. Calculate the absorbance (1.00-cm cells) at 450 nm of a solution in which the total molar
concentration of the indicator described in Problem 24-19 is 8.00 × 10 −5 M and the pH is
(a) 4.92, (c) 5.93.
Solutions:
[H3O+ ]
α0 = α1 = 1 − α0
[H3O+ ] + KHIn
A450 = εHIn × 1.00 × [HIn] + εIn × 1.00 × [In−]
= εHInα0cIn + εInα1cIn
= (εHInα0 + εInα1)cIn
where cIn is the analytical concentration of the indicator (cIn = [HIn] + [In−]).
We may assume at pH 1.00 all of the indicator is present as HIn; at pH 13.0 it is all
present as In−. Therefore, from the data in Problem 26-19 we may write
A450 0.658
εHIn = = = 8.22 × 103 L mol−1 cm−1
bcHIn 1.00 × 8.00 × 10 −5
A450 0.076
εIn = = = 9.5 × 102 L mol−1 cm−1
bcIn 1.00 × 8.00 × 10 −5
(a) At pH = 4.92, [H3O+] = 1.20 × 10−5 M
1.20 × 10−5
α0 = = 0.714
1.20 × 10 −5 + 4.80 × 10−6
α1 = 1.000 − 0.714 = 0.286
A450 = (8.22 × 103 × 0.714 + 9.5 × 102 × 0.286) × 8.00 × 10−5 = 0.492
pH [H3O+] α0 α1 A450
(a) 4.92 1.20 × 10 −5
0.714 0.286 0.492
(c) 5.93 1.18 × 10 −6
0.197 0.803 0.190
24-21. What is the absorbance at 595 nm (1.00-cm cells) of a solution that is 1.25 × 10−4 M in the
indicator of Problem 24-19 and has a pH of (a) 5.30, (b) 5.70, and (c) 6.10?
Solutions:
The approach is identical to that of Solution 24-20. At 595 nm and
A595 0.032
at pH = 1.00, εHIn = = = 4.0 × 102 L mol−1 cm−1
bcHIn 1.00 × 8.00 × 10−5
A595 0.361
at pH = 13.00, εIn = = = 4.51 × 103 L mol−1 cm−1
bcIn 1.00 × 8.00 × 10 −5
(a) At pH = 5.30 and with 1.00-cm cells, [H3O+] = 5.01 × 10−6 M and
[H3O+ ] 5.01 × 10−6
α0 = = = 0.511
[H3O+ ] + KHIn 5.01 × 10−6 + 4.80 × 10−6
α1 = 1 − α0 = 0.489
A595 = (εHInα0 + εInα1)cIn
A595 = (4.0 × 102 × 0.511 + 4.51 × 103 × 0.489) × 1.25 × 10−4 = 0.301
Similarly for parts (b) and (c)
pH [H3O+] α0 α1 A595
(a) 5.30 5.01 × 10 −6
0.511 0.489 0.301
(b) 7.50 2.00 × 10 −6
0.294 0.706 0.413
(c) 6.10 7.94 × 10−7 0.142 0.858 0.491
24-22. Several buffer solutions were made 1.00 × 10−4 M in the indicator of Problem 24-19.
Absorbance data (1.00-cm cells) are
Solution A450 A595
A 0.344 0.310
C 0.653 0.136
Calculate the pH of each solution.

Solutions:
In these solutions the concentrations of the two absorbers HIn and In− must be
determined by the analysis of mixtures, so
A450 = ε′HInb[HIn] + ε′Inb[In−]
A595 = ε″HInb[HIn] + ε″Inb[In−]
From the solutions to Problems 24-20 and 24-21
ε′HIn = 8.22 × 103 ε′In = 9.5 × 102 ε″HIn = 4.0 × 102 ε″In = 4.51 × 103
Thus, A450 = 0.344 = (8.22 × 103)[HIn] + (9.5 × 102)[In−]
A595 = 0.310 = (4.0 × 102)[HIn] + (4.51 × 103)[In−]
Solving these equations gives
[HIn] = 3.42 × 10−5 M and [In−] = 6.57 × 10−5 M
[H3O+ ][In− ]
KHIn =
[HIn]
[HIn] (4.80 × 10−6 )(3.42 × 10−5 )
[H3O+] = KHIn = = 2.50 × 10−6 M
[In− ] 6.57 × 10−5
pH = −log[H3O+] = −log(2.50 × 10−6) = 5.60
The results for all solutions are shown in the table that follows.
Solution [HIn] [In−] pH

A 3.42 × 10−5 6.57 × 10−5 5.60
C 7.70 × 10 −5
2.33 × 10 −5
4.80
24-25. Use the data in Problem 24-24 to calculate the molar concentration of P and Q in each of
the following solutions:
A440 A620
(a) 0.357 0.803
(c) 0.248 0.333
(e) 0.480 0.825
Solutions:
A440 = ε P′ bcP + ε Q′ bcQ b = 1.00 cm
A620 = ε P′′bcP + ε Q′′ bcQ
A440 − ε Q′ cQ
cP =
ε P′
Substituting for cP in the second equation gives

A − ε Q′ cQ 
A620 = ε P′′  440  + ε Q′′cQ
 ε P′ 
We then solve for cQ and cP as in the spreadsheet
24-26. A standard solution was put through appropriate dilutions to give the concentrations of iron
shown in the accompanying table. The iron(II)-1,10,phenanthroline complex was then
formed in 25.0-mL aliquots of these solutions, following which each was diluted to 50.0 mL
(see Figure 24-7). The absorbances in the table (1.00-cm cells) were recorded at 510 nm.
Fe(II) Concentration in
Original Solution, ppm A510
4.00 0.160
10.0 0.390
16.0 0.630
24.0 0.950
32.0 1.260
40.0 1.580
(b) Use the method of least squares to find an equation relating absorbance and the
concentration of iron(II).
(c) Calculate the standard deviation of the slope and intercept.

Solutions:
24-28. The sodium salt of 2-quinizarinsulfonic acid (NaQ) forms a complex with Al31 that
absorbs strongly at 560 nm. The data collected on this system are shown in the
accompanying table. (a) Find the formula of the complex from the data. In all solutions,
cAl = 3.7 × 1025 M , and all measurements were made in 1.00-cm cells. (b) Find the molar
absorptivity of the complex.
c Q, M A560
1.00 × 10 −5 0.131
2.00 × 10 −5 0.265
3.00 × 10 −5 0.396
4.00 × 10 −5 0.468
5.00 × 10 −5 0.487
6.00 × 10 −5 0.498
8.00 × 10 −5 0.499
1.00 × 10 −4 0.500
Solutions:
Plotting the data in the problem gives
0.7
y = 13250x - 0.001
0.6 R² = 1
0.5
Absorbance
0.4 y = 50x + 0.495

R² = 1
0.3
0.2
0.1
0
0.00E+00 2.00E-05 4.00E-05 6.00E-05 8.00E-05 1.00E-04 1.20E-04
cQ, M
Solving for the crossing point by using the 2 best fit equations gives, cQ = 3.76 × 10−5 M.
(a) Since cAl = 3.7 × 10−5 M and no more complex forms after cQ = 3.76 × 10−5 M, the
complex must be 1:1, or AlQ2+.
(b) ε for AlQ2+ = (0.500)/(3.7 × 10−5) = 1.4 × 104 L mol−1 cm−1
24-30. The accompanying absorption data were recorded at 390 nm in 1.00-cm cells for a
continuous-variations study of the colored product formed between Cd21 and the
complexing reagent R.
Reagent Volumes, mL
Solution cCd = 1.25 × 10−4 M cR = 1.25 × 10−4 M A390
0 10.00 0.00 0.000

1 9.00 1.00 0.174
2 8.00 2.00 0.353
3 7.00 3.00 0.530
4 6.00 4.00 0.672
5 5.00 5.00 0.723
6 4.00 6.00 0.673
7 3.00 7.00 0.537
8 2.00 8.00 0.358
9 1.00 9.00 0.180
10 0.00 10.00 0.000
Solutions:
(a) Find the ligand-to-metal ratio in the product.

The two lines intercept at VM/(VM + VL) = 0.5 (Cell B19). The Cd2+ to R ratio is 1:1.
(b) Calculate an average value for the molar absorptivity of the complex and its
uncertainty. Assume that in the linear portions of the plot the metal is completely
complexed.
The molar absorptivities can be obtained from solutions 1-3 where the reagent is
limiting and solutions 7-9 where the metal is limiting. Rounding the results in Cells
B32 and B33 the average ε = 1400 ± 200 L mol−1 cm−1
(c) Calculate K f for the complex using the stoichiometric ratio determined in (a) and
the absorption data at the point of intersection of the two extrapolated lines.
The absorbance at the volume ratio where the lines intersect is A = 0.723. Thus,
[CdR] = (0.723)/(14202) = 5.09 × 10−5 M
[Cd2+] = [(5.00 mL)(1.25 × 10−4 mmol/mL) − (10.00 mL)(5.09 × 10−5 mmol/mL)]/(10.00 mL)
= 1.16 × 10−5 M
[R] = [Cd2+] = 1.16 × 10−5 M
Kf =
[CdR]
=
(5.09 × 10 )−5
= 3.78 × 105
[Cd2 + ][R] (1.16 × 10 )
2
−5
24-33. Estimate the frequencies of the absorption maxima in the IR spectrum of methylene
chloride shown in Figure 24F-2. From these frequencies, assign molecular vibrations of
methylene chloride to each of the bands. Notice that some of the group frequencies that
you will need are not listed in Table 24-5, so you will have to look elsewhere.
Solution:
From Figure 24F-2, the frequencies of the band maxima are estimated to be:
(1) 740 cm−1 C―Cl stretch
(2) 1270 cm−1 CH2 wagging
(3) 2900 cm−1 Aliphatic C―H stretch.
© 2022, 978-0-357-45055-0, Chapter 25: Molecular Fluorescence Spectroscopy
Chapter 25
Answers:
(a) fluorescence.
Fluorescence is a photoluminescence process in which atoms or molecules are
excited by absorption of electromagnetic radiation and then relax to the ground
state, giving up their excess energy as photons. The transition is from the lowest
lying excited singlet state to the ground singlet state.
(c) internal conversion.

Internal conversion is the nonradiative relaxation of a molecule from a low energy
vibrational level of an excited electronic state to a high energy vibrational level of a
lower electronic state.
(e) Stokes shift.

Answer:
The Stokes shift is the difference in wavelength between the radiation used to excite
fluorescence and the wavelength of the emitted radiation.
(g) inner-filter effect.

An inner filter effect is a result of excessive absorption of the incident beam (primary
absorption) or absorption of the emitted beam (secondary absorption).
1
25-3. Which compound in each of the following pairs would you expect to have a greater
fluorescence quantum yield? Explain.
Answers:
(a)
Fluorescein because of its greater structural rigidity due to the bridging ―O―
groups.
25-5. Describe the characteristics of organic compounds that fluoresce.
Answer:
Organic compounds containing aromatic rings often exhibit fluorescence. Rigid
molecules or multiple ring systems tend to have large quantum yields of fluorescence
while flexible molecules generally have lower quantum yields.
25-7. Describe the components of a filter fluorometer and a spectrofluorometer.
Answer:
See Figure 25-8. A filter fluorometer usually consists of a light source, a filter for selecting the
excitation wavelength, a sample container, an emission filter and a transducer/readout
device. A spectrofluorometer has two monochromators that are the wavelength selectors.
25-9. Why are fluorometers often more useful than spectrofluorometers for quantitative
analysis?
Answer:
Fluorometers are more sensitive because filters allow more excitation radiation to reach
the sample and more emitted radiation to reach the transducer. Thus, a fluorometer can
provide lower limits of detection than a spectrofluorometer. In addition, fluorometers
are substantially less expensive and more rugged than spectrofluorometer, making
them particularly well suited for routine quantitation and remote analysis applications.
25-10. The reduced form of nicotinamide adenine dinucleotide (NADH) is an important and
highly fluorescent coenzyme. It has an absorption maximum of 340 nm and an emission
maximum at 465 nm. Standard solutions of NADH gave the following fluorescence
intensities:
Concn NADH, μmol/L Relative Intensity
0.100 2.24
0.200 4.52
0.300 6.63
0.400 9.01
0.500 10.94
0.600 13.71
0.700 15.49
0.800 17.91
(b) Find the least-squares slope and intercept for the plot in (a).
(d) An unknown exhibits a relative fluorescence intensity of 11.34. Use the

spreadsheet to calculate the concentration of NADH.
(e) Calculate the relative standard deviation for the result in part (d).
Solutions:
(b) F = 22.3cNADH + 0.0004

(d) Conc. unknown = 0.510 μm NADH
(e) RSD for c = 0.016
25-12. Quinine in a 1.664-g antimalarial tablet was dissolved in sufficient 0.10 M HCl to give 500
mL of solution. A 15.00-mL aliquot was then diluted to 100.0 mL with the acid. The
fluorescence intensity for the diluted sample at 347.5 nm provided a reading of 288 on
an arbitrary scale. A standard 100 ppm quinine solution registered 180 when measured
under conditions identical to those for the diluted sample. Calculate the mass of quinine
in milligrams in the tablet.
Solution:
cQ = 100 ppm × 288/180 = 160 ppm
100 mL 1 mg quinine 1 g solution
160 ppm × × × × 500 mL = 533 mg quinine
15 mL 1 × 10 g solution
3
1 mL
© 2022, 978-0-357-45055-0, Chapter 26: Atomic Spectroscopy
Chapter 26
26-1. Describe the basic differences among atomic emission, atomic absorption, and atomic
fluorescence spectroscopy.
Answer:
In atomic emission spectroscopy the radiation source is the sample itself. The energy for
excitation of analyte atoms is supplied by a plasma, a flame, an oven, or an electric arc or
spark. The signal is the measured intensity of the source at the wavelength of interest. In
atomic absorption spectroscopy the radiation source is usually a line source such as a
hollow cathode lamp, and the signal is the absorbance. The latter is calculated from the
radiant power of the source and the resulting power after the radiation has passed
through the atomized sample. In atomic fluorescence spectroscopy, an external radiation
source is used, and the fluorescence emitted, usually at right angles to the source, is
measured. The signal is the intensity of the fluorescence emitted.
26-2. Define
Answers:
(a) atomization.
Atomization is a process in which a sample, often in solution, is volatilized and
decomposed to form an atomic vapor.
(c) Doppler broadening.

Doppler broadening is an increase in the width of the atomic lines caused by the
Doppler effect in which atoms moving toward a detector absorb or emit
wavelengths that are slightly shorter than those absorbed or emitted by atoms
moving at right angles to the detector. The reverse effect is observed for atoms
moving away from the detector.
(e) plasma.
A plasma is a conducting gas that contains a large concentration of ions and/or
electrons.
1
(g) hollow-cathode lamp.

A hollow cathode lamp consists of a tungsten wire anode and a cylindrical cathode
sealed in a glass tube that contains argon at a pressure of 1 to 5 torr. The cathode
is constructed from or supports the element whose emission spectrum is desired.
(i) additive interference.

An additive interference, also called a blank interference, produces an effect that is
independent of the analyte concentration. It could be eliminated with a perfect
blank solution.
(k) chemical interference.

A chemical interference in atomic spectroscopy is encountered when a species
interacts with the analyte in such a way as to alter the spectral emission or
absorption characteristics of the analyte.
(m) protective agent.

A protective agent prevents interference by forming a stable, but volatile, compound
with the analyte. It protects the analyte from forming non-volatile, but less stable
interfering compounds.
26-3. Why is atomic emission more sensitive to flame instability than atomic absorption?
Answer:
In atomic emission spectroscopy, the analytical signal is produced by the relatively small
number of excited atoms or ions, whereas in atomic absorption the signal results from
absorption by the much larger number of unexcited species. Any small change in flame
conditions dramatically influences the number of excited species, whereas such changes
have a much smaller effect on the number of unexcited species.
26-5. Why is source modulation used in atomic absorption spectroscopy?
Answer:
In atomic absorption spectroscopy the source radiation is modulated to create an ac
signal at the detector. The detector is made to reject the dc signal from the flame and
measure the modulated signal from the source. In this way, background emission from
the flame and atomic emission from the analyte is discriminated against and prevented
from causing an interference effect.
26-7. Why are the lines from a hollow-cathode lamp generally narrower than the lines emitted
by atoms in a flame?
Answer:
The temperature and pressure in a hollow cathode lamp are much less than those in an
ordinary flame. As a result, Doppler and collisional broadening effects are much less,
and narrower lines results.
26-9. Name four characteristics of inductively coupled plasmas that make them suitable for
atomic emission spectrometry.
Answer:
The temperatures are high which favors the formation of atoms and ions. Sample
residence times are long so that desolvation and vaporization are essentially complete.
The atoms and ions are formed in a nearly chemically inert environment. The high and
relatively constant electron concentration leads to fewer ionization interferences.
26-11. Discuss the differences that result in ICP atomic emission when the plasma is viewed
axially rather than radially.
Answer:
The radial geometry provides better stability and precision while the axial geometry can
achieve lower detection limits. Many ICP emission systems allow both geometries.
26-13. A 5.00-mL sample of blood was treated with trichloroacetic acid to precipitate proteins.
After centrifugation, the resulting solution was brought to pH 3 and extracted with two
5-mL portions of methyl isobutyl ketone containing the lead-complexing agent APCD.
The extract was aspirated directly into an air/acetylene flame and yielded an absorbance
of 0.502 at 283.3 nm. Five-milliliter aliquots of standard solutions containing 0.400 and
0.600 ppm of lead were treated in the same way and yielded absorbances of 0.396 and
0.599. Find the concentration of lead in the sample in ppm assuming that Beer’s law is
followed.
Solution:
By linear interpolation
(0.600 − 0.400)
0.400 + ( 0.502 – 0.396 ) = 0.504 ppm Pb
(0.599 − 0.396)
26-15. The copper in an aqueous sample was determined by atomic absorption flame
spectrometry. First, 10.0 mL of the unknown were pipetted into each of five 50.0-mL
volumetric flasks. Various volumes of a standard containing 12.2 ppm Cu were added to
the flasks, and the solutions were then diluted to volume.
Unknown, mL Standard, mL Absorbance
10.0 0.0 0.201
10.0 10.0 0.292
10.0 20.0 0.378
10.0 30.0 0.467
10.0 40.0 0.554
Solutions:
(b) Derive an expression relating absorbance to the concentrations of standard and

unknown ( cs and c x ) and the volumes of the standards and unknown (Vs and Vx )
as well as the volume to which the solutions were diluted (Vt ) .
ε bVs cs ε bVx c x
As = + = kVs cs + kVx c x
Vt Vt
(c) Derive expressions for the slope and the intercept of the straight line obtained in
(a) in terms of the variables listed in (b).
For the plot of As versus Vs, As = mVs + b where m = kcs and b = kVxcx
(e) Determine values for m and b by the method of least squares.
From the values in the spreadsheet: m = 0.00881 and b = 0.2022
(g) Calculate the copper concentration in ppm Cu in the sample using the relationship
given in (d).
From the values in the spreadsheet: cCu = 28.0 (±0.2) ppm
© 2022, 978-0-357-45055-0, Chapter 27: Mass Spectrometry
Chapter 27
27-1. Define
Answers:
(a) Dalton.
The Dalton is one unified atomic mass unit and equal to 1/12 the mass of a neutral
12
6
C atom.
(c) mass number.

The mass number is the atomic or molecular mass expressed without units.
(e) time-of-flight analyzer.

In a time-of-flight analyzer ions with nearly the same kinetic energy traverse a field-
free region. The time required for an ion to reach a detector at the end of the field-
free region is inversely proportional to the mass of the ion.
27-3. What function does the ICP torch serve in mass spectrometry?
Answer:
The ICP torch serves both as an atomizer and ionizer.
27-5. What types of interferences are encountered in ICPMS?
Answer:
Interferences fall into two categories: spectroscopic interferences and matrix
interferences. In a spectroscopic interference, the interfering species has the same
mass-to-charge ratio as the analyte. Matrix effects occur at high concentrations where
interfering species can interact chemically or physically to change the analyte signal.
27-7. Why are detection limits for ICPMS often lower with double-focusing mass
spectrometers than with quadrupole mass spectrometers?
Answer:
The higher resolution of the double focusing spectrometer allows the ions of interest to
be better separated from background ions than with a relative low resolution
quadrupole spectrometer. The higher signal-to-background ratio of the double focusing
instrument leads to lower detection limits than with the quadrupole instrument.
1
© 2022, 978-0-357-45055-0, Chapter 27: Mass Spectrometry
27-9. Why are fragments often produced with electron ionization?
Answer:
The high energy of the beam of electrons used in EI sources is enough to break some
chemical bonds and produce fragment ions. Such fragment ions can be useful in
qualitative identification of molecular species.
27-11. What is the difference between a precursor ion and a product ion in tandem mass
spectrometry?
Answer:
The ion selected by the first analyzer is called the precursor ion. It then undergoes
thermal decomposition, reaction with a collision gas, or photodecomposition to form
product ions that are analyzed by a second mass analyzer.
© 2022, 978-0-357-45055-0, Chapter 28: Kinetic Methods of Analysis
Chapter 28
28-1. Define the following terms as they are used in kinetic methods of analysis.
Answers:
(a) Order of a reaction
The order of a reaction is the numerical sum of the exponents of the concentration
terms in the rate law for the reaction.
(c) Enzyme
Enzymes are high molecular weight organic molecules that catalyze reactions of
biological importance.
(e) Michaelis constant

The Michaelis constant Km is an equilibrium-like constant for the dissociation of the
enzyme-substrate complex. It is defined by the equation Km = (k−1 + k2)/k1, where k1
and k−1 are the rate constants for the forward and reverse reactions in the
formation of the enzyme-substrate complex. The term k2 is the rate constant for
the dissociation of the complex to give products.
(g) Integral method

Integral methods use integrated forms of the rate equations to calculate
concentrations from kinetic data.
28-3. List three advantages of kinetic methods. Can you think of two possible limitations of
kinetic methods when compared to equilibrium methods?
Answer:
Advantages would include (1) measurements are made relatively early in the reaction
before side reactions can occur; (2) measurements do not depend upon the
determination of absolute concentration but rather depend upon differences in
concentration; (3) selectivity is often enhanced in reaction-rate methods, particularly in
enzyme-based methods. Also kinetic methods can often be done more rapidly than
waiting for equilibrium conditions. Limitations include (1) lower sensitivity, since reaction
is not allowed to proceed to equilibrium; (2) greater dependence on conditions such as
temperature, ionic strength, pH and concentration of reagents; (3) lower precision since
the analytical signal is lower.
1
28-5. Derive an expression for the half-life of the reactant in a first-order process in terms of
the rate constant k.
Solution:
[A ]t
[A]t = [A]0e−kt ln = −kt
[A]0
[A]0 /2
For t = t1/2, [A]t = [A]0/2 ln = ln (1/2) = −kt1/2
[A]0
ln 2 = kt1/2
t1/2 = ln 2/k = 0.693/k
28-6. Find the natural lifetime in seconds for first-order reactions corresponding to
Solutions:
(a) k = 0.497 s−1.
τ = 1/k = 1/0.497 s−1 = 2.01 s
(c) [A]0 = 3.16 M, and [A]t = 0.496 M at t = 3876 s.

[A]0
ln = kt τ = 1/k = t/ln([A]0/[A]t) = 3876 s/ln(3.16/0.496) = 2.093 × 103 s
[A]t
(e) half-life, t1/2, = 26.5 years.

365 d 24 h 60 min 60 s
t1/2 = 26.5 yr × × × × = 8.36 × 108 s
1 yr 1d 1h 1 min
τ = 1/k = t1/2/0.693 = 8.36 × 108 s/0.693 = 1.2 × 109 s
28-7. Find the first-order rate constant for a reaction that is 75.0% complete in
Solutions:
(a) 0.0100 s.
[A]t 1 [A]t
ln = −kt k = − ln
[A]0 t [A]0
1
k= − ln(0.75) = 28.8 s−1
0.0100
(c) 1.00 s.
k = 0.288 s−1
(e) 26.8 μs.

k = 1.07 × 104 s−1
28-8. Find the number of half-lives required to reach the following levels of completion:
Solutions:
1 [A]
− ln
t k [A]0
Let m = no. half-lives = =
t1/2 1 [A] /2
− ln 0
k [A]0
ln[A]/[A]0
m= = −1.4427 ln([A]/[A]0)
ln1/2
(a) 10%
m = −1.4427 ln 0.90 = 0.152
(c) 90%.
m = −1.4427 ln 0.10 = 3.3
(e) 99.9%.
m = −1.4427 ln 0.001 = 10
28-10. Find the relative error associated with the assumption that k′ is invariant during the
course of a pseudo-first-order reaction under the following conditions:
Extent of Reaction, % Excess of Reagent
(a) 1 5×
(c) 1 50×
(e) 5 5×
(g) 5 100×
(i) 63.2 10×
(k) 63.2 100×
Solutions:
(a) [R]0 = 5.00[A]0 where 5.00 is the ratio of the initial reagent concentration to the
initial concentration of the analyte.
At 1% reaction, [A] = 0.99[A]0

[R]1% = [R] − 0.01[A]0 = 5.00[A]0 − 0.01[A]0 = 4.99[A]0
Rateassumed = k[R][A] = k(5.00[A]0 × 0.99[A]0)

Ratetrue = k(4.99[A]0 × 0.99[A]0)
k (5.00[A]0 × 0.99[A]0) − k (4.99[A]0 × 0.99[A]0 )
relative error =
k(4.99[A]0 × 0.99[A]0 )
(5.00 × 0.99) − (4.99 × 0.99)

= = 0.00200
(4.99 × 0.99)
(c) (50.00 − 49.99)/49.99 = 0.000200 or 0.02%

(e) (5.00 − 4.95)/4.95 = 0.0101 or 1.0%
(g) (100.00 − 99.95)/99.95 = 0.0005002 or 0.05%
(i) (10.000 − 9.368)/9.368 = 0.06746 or 6.7%
(k) (100.00 − 99.368)/99.368 = 0.00636 or 0.64%
28-12. Equation 28-19 can be rearranged to produce the equation
1 Km 1
= +
d[P]/dt v max [S] v max
where vmax = k2 [E]0 , the maximum velocity when [S] is large.
Solutions:
(a) Suggest a way to use this equation in the construction of a calibration (working)
curve for the enzymatic determination of substrate.
Plot 1/Rate versus 1/[S] for known [S] to give a linear calibration curve. Measure
rate for unknown [S], calculate 1/Rate and 1/[S]unknown from the working curve and
find [S]unknown.
(b) Describe how the resulting working curve can be used to find Km and vmax .
The intercept of the calibration curve is 1/vmax and the slope is Km/vmax. Use the
intercept to calculate Km = slope/intercept, and vmax = 1/intercept.
28-13. Copper(II) forms a 1:1 complex with the organic complexing agent R in acidic medium.
The formation of the complex can be monitored by spectrophotometry at 480 nm. Use
the following data collected under pseudo-first-order conditions to construct a
calibration curve of rate versus concentration of R. Find the concentration of copper(II) in
an unknown whose rate under the same conditions was 6.2 × 10−3 A s−1. Also find the
standard deviation of the concentration.
cCu2+ , ppm Rate, A s−1
3.0 3.6 × 10−3
5.0 5.4 × 10−3
7.0 7.9 × 10−3
9.0 1.03 × 10−2
Solution:
We report the concentration of the unknown as 5.5 ± 0.2 ppm
28-15. The enzyme monoamine oxidase catalyzes the oxidation of amines to aldehydes. For
tryptamine, Km for the enzyme is 4.0 × 10−4 M, and vmax = k2[E]0 = 1.6 × 10−3 μM/min at pH
8. Find the concentration of a solution of tryptamine that reacts at a rate of 0.18 μM/min
in the presence of monoamine oxidase under the preceding conditions. Assume that
[tryptamine] << Km .
Solution:
k2 [E]0 [tryp]t
Rate = R =
[tryp]t + Km
Assume Km >> [tryp]t

vmax [tryp]t
R= and [tryp]t = RKm/vmax
Km
[tryp]t = (0.18 μM/min)(4.0 × 10−4 M)/(1.6 × 10−3 μM/min) = 0.045 M
28-17. Calculate the product concentrations versus time for a pseudo-first-order reaction with
k′ = 0.015 s−1 and [A]0 = 0.005 M . Use times of 0.000 s, 0.001 s, 0.01 s, 0.1 s, 0.2 s 0.5 s, 1.0
s, 2.0 s, 5.0 s, 10.0 s, 20.0 s, 50.0 s, 100.0 s, 200.0 s, 500.0 s, and 1000.0 s. From the two
earliest time values, find the “true” initial rate of the reaction. Determine approximately
what percentage completion of the reaction occurs before the initial rate drops to (a)
99% and (b) 95% of the true value.
Solutions:
(a) The initial rate drops to 0.99Ri between times 1.3 and 1.4 s, which is ≈ 2% of the
reaction.
(b) Between 6.0 and 7.0 s so a little over 9% of the reaction is completed.
© 2022, 978-0-357-45055-0, Chapter 29: Introduction to Analytical Separations
Chapter 29
29-1. What is a collector ion, and how is it used?
Answer:
A collector ion is an ion added to a solution that forms a precipitate with the reagent
which carries the desired minor species out of solution.
29-3. What two events accompany the separation process?
Answer:
The two events are transport of material and a spatial redistibrution of the components.
29-5. Define
Answers:
(a) elution.
Elution is a process in which species are washed through a chromatographic
column by additions of fresh mobile phase.
(c) stationary phase.

The stationary phase in chromatography is a solid or liquid phase that is fixed in
place. The mobile phase then passes over or through the stationary phase.
(e) retention time.

The retention time for an analyte is the time interval between its injection onto a
column and its appearance at the detector at the other end of the column.
(g) selectivity factor.

The selectivity factor α of a column toward two species is given by the equation α =
KB/KA, where KB is the distribution constant for the more strongly retained species B
and KA is the constant for the less strongly held or more rapidly eluting species A.
1
29-7. List the variables that lead to band broadening in chromatography.
Answer:
The variables that lead to band broadening include (1) large particle diameters for
stationary phases; (2) large column diameters; (3) high temperatures (important only in
gas chromatography); (4) for liquid stationary phases, thick layers of the immobilized
liquid; and (5) very rapid or very slow flow rates.
29-9. Describe a method for determining the number of plates in a column.
Answer:
Determine the retention time tR for a solute and the width of the solute peak at its base,
W. The number of plates N is then N = 16(tR/W)2.
29-11. The distribution constant for X between n-hexane and water is 8.9. Calculate the
concentration of X remaining in the aqueous phase after 50.0 mL of 0.200 M X is treated
by extraction with the following quantities of n-hexane:
Solutions:
i
 Vaq 
[X]i =   [X]0
 Vorg K + Vaq 
 
(a) one 40.0-mL portion.
 50.0 
[X]1 =   ( 0.200 ) = 0.0246 M
 40.0 × 8.9 + 50.0 
(b) two 20.0-mL portions.

2
 50.0 
[X]2 =   ( 0.200 ) = 9.62 × 10 M
−3
 20.0 × 8.9 + 50.0 
(c) four 10.0-mL portions.

4
 50.0 
[X]4 =   ( 0.200 ) = 3.35 × 10 M
−3
 10.0 × 8.9 + 50.0 
(d) eight 5.00-mL portions.

8
 50.0 
[X]8 =   ( 0.200 ) = 1.23 × 10 M
−3
 5.0 × 8.9 + 50.0 
29-13. What volume of n-hexane is required to decrease the concentration of X in Problem 29-
11 to 1.00 × 10−4 M if 25.0 mL of 0.0500 M X is extracted with
Solutions:
i
 Vaq  log ([A]i /[A]0 )
[A]i =   [A]0 i=
 Vorg K + Vaq   Vaq 
  log  
 Vorg K + Vaq 
 
(a) 25.0-mL portions?
 1.00 × 10 −4 
log  
i=  0.0500  = 2.7 extractions. So 3 extractions are needed.
 25.0 
log  
 25.0 × 8.9 + 25.0 
The total volume would be 75 mL with 3 extractions.
(b) 10.0-mL portions?
As in part (a), i = 4.09 extractions, so 5 extractions are needed.
The total volume would be 5 × 10 mL = 50 mL
(c) 2.0-mL portions?
i = 11.6 so 12 extractions are needed
The total volume would be 12 × 2 mL = 24 mL
29-15. What is the minimum distribution coefficient that permits removal of 99% of a solute
from 50.0 mL of water with
Solutions:
If 99% of the solute is removed then 1% of solute remains and [A]i/[A]0 = 0.01.
(a) two 25.0-mL extractions with toluene?
2
[A]i  50.0 
=  = 0.01
[A]0  25.0K + 50.0 
(0.01)1/2(25.0K + 50.0) = 50.0
2.5K + 5.0 = 50.0
K = (50.0 − 5.0)/2.5 = 18.0
(b) five 10.0-mL extractions with toluene?
5
[A]i  50.0 
=  = 0.01
[A]0  10.0K + 50.0 
(0.01)1/5(10.0K + 50.0) = 50.0
3.98K + 19.9 = 50.0
K = (50.0 − 19.9)/3.98 = 7.56
29-16. If 30.0 mL of water that is 0.0500 M in Q is to be extracted with four 10.0-mL portions of
an immiscible organic solvent, what is the minimum distribution coefficient that allows
transfer of all but the following percentages of the solute to the organic layer:
Solution:
(a) 1.00 × 10−4.
If 1.00 × 10−4 % of the solute remains, [A]i/[A]0 = 1.00 × 10−6.
4
[A]i  30.0 
=  = 1.00 × 10
−6
[A]0  10.0K + 30.0 
(1 × 10−6)1/4(10.0K + 30.0) = 30.0
0.316K + 0.949 = 30.0
K = (30.0 − 0.949)/0.31 = 91.9
29-17. A 0.150 M aqueous solution of the weak organic acid HA was prepared from the pure
compound, and three 50.0-mL aliquots were transferred to 100.0-mL volumetric flasks.
Solution 1 was diluted to 100.0 mL with 1.0 M HClO4, solution 2 was diluted to the mark
with 1.0 M NaOH, and solution 3 was diluted to the mark with water. A 25.0-mL aliquot of
each was extracted with 25.0 mL of n-hexane. The extract from solution 2 contained no
detectable trace of A-containing species, indicating that A 2 is not soluble in the organic
solvent. The extract from solution 1 contained no ClO4 − or HClO4 but was found to be
0.0454 M in HA (by extraction with standard NaOH and back-titration with standard HCl).
The extract from solution 3 was found to be 0.0225 M in HA. Assume that HA does not
associate or dissociate in the organic solvent, and calculate
Solutions:
(a) the distribution ratio for HA between the two solvents.
Recognizing that in each of the solutions [HA] = 0.0750 due to dilution, from the
data for solution 1,
[HA]org = 0.0454 M
25.0(0.0750) − 25.0(0.0454)
[HA]aq = = 0.0296 M
25.0
K = [HA]org/[HA]aq = 0.0454/0.0296 = 1.53
(b) the concentration of the species HA and A − in aqueous solution 3 after extraction.
For solution 3, after extraction
[HA]aq = [HA]org/K = 0.0225/1.53 = 0.0147 M
[A−] = (mols HAtot − mols HAaq − mols HAorg)/(25.0 mL)
(25.0)(0.0750) − (25.0)(0.0147) − (25.0)(0.0225)
[A−] = = 0.0378 M
25.0
(c) the dissociation constant of HA in water.
Since [H+] = [A−], Ka = (0.0378)2/(0.0147) = 0.0972
29-19. The total cation content of natural water is often determined by exchanging the cations
for hydrogen ions on a strong-acid ion-exchange resin. A 25.0-mL sample of a natural
water was diluted to 100 mL with distilled water, and 2.0 g of a cation-exchange resin
was added. After stirring, the mixture was filtered and the solid remaining on the filter
paper was washed with three 15.0-mL portions of water. The filtrate and washings
required 15.3 mL of 0.0202 M NaOH to give a bromocresol green end point.
Solutions:
(a) Calculate the number of millimoles of cation present in exactly 1.00 L of sample.
amount H+ resulting from exchange = 15.3 mL × 0.0202 mmol/mL = 0.3091 mmol
mmols H+ = mmol cation = 0.3091 in 0.0250 L sample
0.3091 mmol cation/0.0250 L = 12.36 mmol cation/L
(b) Report the results in terms of milligrams of CaCO3 per liter.
12.36 mmol cation 1 mmol CaCO3 100.087 mg CaCO3

× × = 619 mg CaCO3/L
L 2 mmol cation mmol CaCO3
29-21. An aqueous solution containing MgCl2 and HCl was analyzed by first titrating a 25.00-mL
aliquot to a bromocresol green end point with 17.53 mL of 0.02932 M NaOH. A 10.00-mL
aliquot was then diluted to 50.00 mL with distilled water and passed through a strong-
acid ion-exchange resin. The eluate and washings required 35.94 mL of the NaOH
solution to reach the same end point. Report the molar concentrations of HCl and MgCl2
in the sample.
Solution:
0.02932 mmol NaOH 1 mmol HCl 1
[HCl] = 17.53 mL × × ×
mL 1 mmol NaOH 25.00 mL
= 0.02056 mmol/mL
amount H3O+/mL from exchange = 35.94 mL × 0.02932 mmol/mL/10.00 mL = 0.10538
= (no. mmol HCl + 2 × no. mmol MgCl2)/mL
mmol MgCl2/mL = (0.10536 − 0.02056)/2 = 0.0424
The solution is thus 0.02056 M in HCl and 0.0424 M in MgCl2.
29-23. A packed column in gas chromatography had an inside diameter of 5.0 mm. The
measured volumetric flow rate at the column outlet was 48.0 mL/min. If the column
porosity was 0.43, what was the linear flow velocity in cm/s?
Solution:
From Equation 29-13,
48 cm3 /min  1 min 

u0 = F/επ r2 = F/επ (d/2)2 =   = 9.5 cm/s
 0.50 cm   60 s 
2
0.43 × 3.1415 ×  
 2 
29-25. From the data in Problem 29-24, calculate for A, B, C, and D
Solutions:
(a) the retention factor.
k = (tR − tM)/tM
For A, kA = (5.4 − 3.1)/3.1 = 0.742 = 0.74
For B, kB = (13.3 − 3.1)/3.1 = 3.29 = 3.3
For C, kC = (14.1 − 3.1)/3.1 = 3.55 = 3.5
For D, kD = (21.6 − 3.1)/3.1 = 5.97 = 6.0
(b) the distribution constant.

K = k VM/VS
For A, KA = 0.742 × 1.37/0.164 = 6.2
For compound B, KB = 3.29 × 1.37/0.164 = 27
For compound C, KC = 3.55 × 1.37/0.164 = 30
For compound D, KD = 5.97 × 1.37/0.164 = 50
29-30. If a resolution of 1.75 is desired in separating methylcyclohexane and

methylcyclohexene in Problem 29-28,
(a) how many plates are required?

(b) how long must the column be if the same packing is used?
(c) what is the retention time for methylcyclohexene on the column of part b?
Solutions:
29-32. From distribution studies, species M and N are known to have water/hexane distribution
constants of 5.99 and 6.16 (K = [X]H O / [X]hex ), where X = M or N. The two species are to be
2
separated by elution with hexane in a column packed with silica gel containing adsorbed
water. The ratio VS/VM for the packing is 0.425.
(a) Calculate the retention factor for each solute.

(b) Calculate the selectivity factor.
(c) How many plates are needed to provide a resolution of 1.5?
(d) How long a column is needed if the plate height of the packing is 1.5 × 10−3 cm?
(e) If the flow rate is 6.75 cm/min, how long will it take to elute the two species?
Solutions:
© 2022, 978-0-357-45055-0, Chapter 30: Gas Chromatography
Chapter 30
30-1. How do gas-liquid and gas-solid chromatography differ?
Answer:
In gas-liquid chromatography, the stationary phase is a liquid that is immobilized on a
solid. Retention of sample constituents involves equilibria between a gaseous and a
liquid phase. In gas-solid chromatography, the stationary phase is a solid surface that
retains analytes by physical adsorption. Here separation involves adsorption equilibria.
30-3. What kind of mixtures are separated by gas-solid chromatography?
Answer:
Gas-solid chromatography is used primarily for separating low molecular weight gaseous
species, such as carbon dioxide, carbon monoxide and oxides of nitrogen.
30-5. Describe a chromatogram, and explain what type of information it contains.
Answer:
A chromatogram is a plot of detector response versus time. Retention of analytes
depends on their boiling points and on interactions with the stationary phase. The peak
position (retention time) can reveal the identity of the compound eluting. The peak area
is related to the concentration of the compound.
30-7. Describe the physical differences between capillary and packed columns. What are the
advantages and disadvantages of each?
Answer:
In open tubular or capillary columns, the stationary phase is held on the inner surface of a
capillary, whereas in packed columns, the stationary phase is supported on particles that
are contained in a glass or metal tube. Open tubular columns contain an enormous
number of plates that permit rapid separations of closely related species. They suffer
from small sample capacities.
1
30-9. What variables must be controlled if satisfactory quantitative data are to be obtained
from chromatograms?
Answer:
Sample injection volume, carrier gas flow rate and column condition are among the
parameters which must be controlled for highest precision quantitative GC. The use of
an internal standard can minimize the impact of variations in these parameters.
30-11. What are the principal advantages and the principal limitations of each of the detectors
listed in Problem 30-10?
Answers:
(a) Advantages of thermal conductivity: general applicability, large linear range,
simplicity, nondestructive.
Disadvantage: low sensitivity.
(b) Advantages of flame ionization: high sensitivity, large linear range, low noise,
ruggedness, ease of use, and response that is largely independent of flow rate.
Disadvantage: destructive.
(c) Advantages of electron capture: high sensitivity selectivity towards halogen-
containing compounds and several others, nondestructive.
Disadvantage: small linear range.
(d) Advantages of thermionic detector: high sensitivity for compounds containing
nitrogen and phosphorus, good linear range.
Disadvantages: destructive, not applicable for many analytes.
(e) Advantages of photoionization: versatility, nondestructive, large linear range.
Disadvantages: not widely available, expensive.
30-13. What are megabore open tubular columns? Why are they used?
Answer:
Megabore columns are open tubular columns that have a greater inside diameter (530
μm) than typical open tubular columns (150 to 320 μm). Megabore columns can tolerate
sample sizes similar to those for packed columns, but with significantly improved
performance characteristics. Thus, megabore columns can be used for preparative scale
GC purification of mixtures where the compound of interest is to be collected and
further analyzed using other analytical techniques.
30-15. Why are gas chromatographic stationary phases often bonded and cross-linked? What
do these terms mean?
Answer:
Currently, liquid stationary phases are generally bonded and/or cross-linked in order to
provide thermal stability and a more permanent stationary phase that will not leach off
the column. Bonding involves attaching a monomolecular layer of the stationary phase
to the packing surface by means of chemical bonds. Cross linking involves treating the
stationary phase while it is in the column with a chemical reagent that creates cross links
between the molecules making up the stationary phase.
30-17. What are the advantages of fused-silica capillary columns compared with glass or metal
columns?
Answer:
Fused silica columns have greater physical strength and flexibility than glass open
tubular columns and are less reactive toward analytes than either glass or metal
columns.
30-19. List the variables that lead to (a) band broadening and (b) band separation in gas-liquid
chromatography.
Answers:
(a) Band broadening arises from very high or very low flow rates, large particles
making up packing, thick layers of stationary phase, low temperature, and slow
injection rates.
(b) Band separation is enhanced by maintaining conditions so that k lies in the range
of 1 to 10, using small particles for packing, limiting the amount of stationary
phase so that particle coatings are thin, and injecting the sample rapidly.
30-21. Peak areas and relative detector responses are to be used to determine the
concentration of the five species in a sample. The area normalization method described
in Problem 30-20 is to be used. The relative areas for the five gas chromatographic peaks
are given in the accompanying table. Also shown are the relative responses of the
detector. Calculate the percentage of each component in the mixture.
Compound Relative Peak Area Relative Detector Response
A 32.5 0.70
B 20.7 0.72
C 60.1 0.75
D 30.2 0.73
E 18.3 0.78
Solution:
© 2022, 978-0-357-45055-0, Chapter 31: High-Performance Liquid Chromatography
Chapter 31
31-1. List the types of substances to which each of the following chromatographic methods is
most applicable:
Answers:
(a) gas-liquid.
Substances that are somewhat volatile and are thermally stable.
(c) ion.
Substances that are ionic.
(e) gel permeation.

High molecular weight compounds that are soluble in nonpolar solvents.
(g) chiral.
Chiral compounds (enantiomers).
31-2. Define
Answers:
(a) isocratic elution.
In an isocratic elution, the solvent composition is held constant throughout the
elution.
(c) normal-phase packing.

In a normal-phase packing, the stationary phase is quite polar and the mobile phase
is relatively nonpolar.
(e) bonded-phase packing.

In a bonded-phase packing, the stationary phase liquid is held in place by chemically
bonding it to the solid support.
(g) ion-pair chromatography.

In ion-pair chromatography a large organic counter-ion is added to the mobile phase
as an ion-pairing reagent. Separation is achieved either through partitioning of the
1
neutral ion-pair or as a result of electrostatic interactions between the ions in

solution and charges on the stationary phase resulting from adsorption of the
organic counter-ion.
(i) gel filtration.

Gel filtration is a type of size-exclusion chromatography in which the packings are
hydrophilic, and eluents are aqueous. It is used for separating high molecular
weight polar compounds.
31-3. Indicate the order in which the following compounds would be eluted from an HPLC
column containing a reversed-phase packing:
Answer:
(a) benzene, diethyl ether, n-hexane.
diethyl ether, benzene, n-hexane.
31-4. Indicate the order of elution of the following compounds from a normal-phase packed
HPLC column:
Answer:
(a) ethyl acetate, acetic acid, dimethylamine.
ethyl acetate, dimethylamine, acetic acid.
31-5. Describe the fundamental difference between adsorption and partition chromatography.
Answer:
In adsorption chromatography, separations are based on adsorption equilibria between
the components of the sample and a solid surface. In partition chromatography,
separations are based on distribution equilibria between two immiscible liquids.
31-7. Describe the difference between gel-filtration and gel-permeation chromatography.
Answer:
Gel filtration is a type of size-exclusion chromatography in which the packings are
hydrophilic and eluents are aqueous. It is used for separating high molecular weight
polar compounds. Gel permeation chromatography is a type of size-exclusion
chromatography in which the packings are hydrophobic and the eluents are
nonaqueous. It is used for separating high molecular weight nonpolar species.
31-9. What is the major difference between isocratic elution and gradient elution? For what
types of compounds are these two elution methods most suited?
Answer:
In an isocratic elution, the solvent composition is held constant throughout the elution.
Isocratic elution works well for many types of samples and is simplest to implement. In a
gradient elution, two or more solvents are employed and the composition of the eluent is
changed continuously or in steps as the separation proceeds. Gradient elution is best

used for samples in which there are some compounds separated well and others with
inordinately long retention times.
31-11. Describe the differences between single-column and suppressor-column ion

chromatography.
Answer:
In suppressor-column ion chromatography the chromatographic column is followed by a
column whose purpose is to convert the ions used for elution to molecular species that
are largely nonionic and thus do not interfere with conductometric detection of the
analyte species. In single-column ion chromatography, low capacity ion exchangers are
used so that the concentrations of ions in the eluting solution can be kept low. Detection
then is based on the small differences in conductivity caused by the presence of eluted
sample components.
31-13. Which of the GC detectors in Table 30-1 are suitable for HPLC? Why are some of these
unsuitable for HPLC?
Answer:
Comparison of Table 31-1 with Table 30-1 suggests that the GC detectors that are
suitable for HPLC are the mass spectrometer, FTIR and possible photoionization. Many
of the GC detectors are unsuitable for HPLC because they require the eluting analyte
components to be in the gas-phase.
31-15. Although temperature does not have nearly the effect on HPLC separations that it has
on GC separations, it nonetheless can play an important role. Discuss how and why
temperature might or might not influence the following separations:
Answers:
A number of factors that influence separation are clearly temperature dependent
including distribution constants and diffusion rates. In addition, temperature changes
can influence selectivity if components A and B are influenced differently by changes in
temperature. Because resolution depends on all these factors, resolution will also be
temperature dependent.
(a) a reversed-phase chromatographic separation of a steroid mixture.

For a reversed phase chromatographic separation of a steroid mixture, selectivity
and, as a consequence, separation could be influenced by temperature dependent
changes in distribution coefficients.
(b) an adsorption chromatographic separation of a mixture of closely related isomers.

For an adsorption chromatographic separation of a mixture of isomers, selectivity
and, as a consequence, separation could be influenced by temperature dependent
changes in distribution coefficients.
© 2022, 978-0-357-45055-0, Chapter 32: Miscellaneous Separation Methods
Chapter 32
32-1. List the types of substances to which each of the following separation methods is most
applicable:
Answers:
(a) supercritical fluid chromatography.
Nonvolatile or thermally unstable species that contain no chromophoric groups.
(c) capillary zone electrophoresis.

Inorganic anions and cations, amino acids, catecholamines, drugs, vitamins,
carbohydrates, peptides, proteins, nucleic acids, nucleotides, and polynucleotides.
(e) flow FFF.

Proteins, synthetic polymers, and colloidal particles.
32-2. Define:
Answers:
(a) supercritical fluid.
A supercritical fluid is a substance that is maintained above its critical temperature
so that it cannot be condensed into a liquid no matter how great the pressure.
(c) two-dimensional thin-layer chromatography.

In two-dimensional thin layer chromatography, development is carried out with two
solvents that are applied successively at right angles to one another.
(e) critical micelle concentration.

The critical micelle concentration is the level above which surfactant molecules begin
to form spherical aggregates made up to 40 to 100 ions with their hydrocarbon
tails in the interior of the aggregate and their charged ends exposed to water on
the outside.
1
32-3. What properties of a supercritical fluid are important in chromatography?
Answer:
The properties of a supercritical fluid that are important in chromatography include its
density, its viscosity, and the rates at which solutes diffuse in it. The magnitude of each
of these lies intermediate between a typical gas and a typical liquid.
32-5. How do instruments for supercritical fluid chromatography differ from those for (a)
HPLC and (b) GC?
Answers:
(a) Instruments for supercritical-fluid chromatography are very similar to those for
HPLC except that in SFC there are provisions for controlling and measuring the
column pressure.
(b) SFC instruments differ substantially from those used for GC in that SFC
instruments must be capable of operating at much higher mobile phase pressures
than are typically encountered in GC.
32-7. What important property of supercritical fluids is related to their densities?
Answer:
Their ability to dissolve large nonvolatile molecules, such as large n-alkanes and
polycyclic aromatic hydrocarbons.
32-9. For supercritical carbon dioxide, predict the effect that the following changes will have
on the elution time in an SFC experiment.
Answers:
(a) Increase the flow rate (at constant temperature and pressure).
An increase in flow rate results in a decrease in retention time.
(b) Increase the pressure (at constant temperature and flow rate).
An increase in pressure results in a decrease in retention time.
(c) Increase the temperature (at constant pressure and flow rate).
An increase in temperature results in a decrease in density of supercritical fluids
and thus an increase in retention time.
32-11. What is electroosmotic flow? Why does it occur?
Answer:
Electroosmotic flow is the migration of the solvent towards the cathode in an
electrophoretic separation. This flow is due to the electrical double layer that develops at
the silica/solution interface. At pH values higher than 3 the inside wall of the silica
capillary becomes negatively charged leading to a build-up of buffer cations in the
electrical double layer adjacent to the wall. The cations in this double layer are attracted
to the cathode and, since they are solvated they drag the bulk solvent along with them.
32-13. What is the principle of separation by capillary zone electrophoresis?
Answer:
Under the influence of an electric field, mobile ions in solution are attracted or repelled
by the negative potential of one of the electrodes. The rate of movement toward or away
from a negative electrode is dependent on the net charge on the analyte and the size
and shape of analyte molecules. These properties vary from species to species. Hence,
the rate at which molecules migrate under the influence of the electric field vary, and the
time it takes them to traverse the capillary varies, making separations possible.
32-15. The cationic analyte of Problem 32-14 was separated by capillary zone electrophoresis in
a 50-cm capillary at 20 kV. Under the separation conditions, the electroosmotic flow rate
was 0.65 mm s21 toward the cathode. If the detector were placed 40 cm from
the injection end of the capillary, how long does it take in minutes for the analyte cation
to reach the detector after the field is applied?
Solution:
The electrophoretic mobility is given by
μeV 6.97 × 10 −4 cm2 s −1 V −1 × 20000 V
v= = = 0.2788 cm s −1
L 50
The electroosmotic flow rate is given as 0.65 mm s−1 = 0.065 cm s−1
Thus, the total flow rate = 0.2788 + 0.065 = 0.3438 cm s−1, and
t = [(40.0 cm)/0.3438 cm s−1)] × (1 min/60 s) = 1.9 min
32-17. Describe a major advantage of micellar electrokinetic capillary chromatography over

conventional liquid chromatography.
Answer:
Higher column efficiencies and the ease with which pseudostationary phase can be
altered.
32-19. Three large proteins are ionized at the pH at which an electrical FFF separation is carried
out. If the ions are designated A 2 + , B + , and C 3 + , predict the order of elution.
Answer:
B+ followed by A2+ followed by C3+.

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Student Solution Manual: Skoog et al., Fundamentals of Analytical Chemistry, 10e,

(c) millimolar mass.

(c) 9.31 × 107 μmol.

(e) 3.96 × 106 nm.

2-5. Why is 1 g no longer exactly 1 mole of unified atomic mass units?

2-7. Find the number of Na+ ions in 2.75 g of Na3PO4?

2-9. Find the amount of the indicated element (in moles) in

2 mol B mol B2O3

(b) 195.7 mg of Na2B4O7 ⋅ 10H2O.

(c) 4.96 g of Mn3O4.

(d) 333 mg of CaC2O4.

g mol CaC2O4 2 mol C

2-11. Find the number of millimoles of solute in

0.0449 mol KMnO4 1000 mmol

(b) 750 mL of 5 .35 × 1023 M KSCN.

5.35 × 10 −3 M KSCN 1000 mmol L

(c) 3.50 L of a solution that contains 6.23 ppm of CuSO4 .

6.23 mg CuSO4 g mol CuSO4 1000 mmol

(d) 250 mL of 0.414 mM KCl.

2-13. What is the mass in milligrams of

(b) 245 mmol of MgO?

(c) 12.5 mol of NH4NO3 ?

(d) 4.95 mol of (NH4 )2 e (NO3 )6 ( 548.23 g/mol) ?

548.23 g (NH4 )2 Ce(NO 3 )6 1000 mg

2-15. What is the mass in milligrams of solute in

(b) 1.92 L of 3.76 × 1023 M H2O2 ?

3.76 × 10 − 3 m ol H 2 O 2 34.02 g H 2 O 2 1000 m g

2-16. What is the mass in grams of solute in

0.264 mol H2 O 2 L 34.02 g H2 O 2

(b) 37.0 mL of 5.75 × 10−4 M benzoic acid (122 g/mol)?

5.75 ×10−4 mol benzoicacid L 122 g benzoicacid

pNa = − log (0.0635 + 0.0403) = −log(0.1038) = 0.9838

K+, OH−, and Fe ( CN )6

pK = − log(4 × 1.62 × 10−7 + 5.12 × 10−7 ) = − log(1.16 × 10−6 ) = 5.94

pOH = − log(5.12 × 10−7 ) = 6.291

2-19. Calculate the p-functions for each ion in a solution that is

(c) 4.5 × 1023 M in Ba ( OH) .

pBa = −log(4.5 × 10−3) = 2.35; pOH = −log(2 × 4.5 × 10−3) = 2.05

(e) 7.2 × 1023 M in CaCl and 8.2 × 1023 M in BaCl .

pCa = −log(7.2 × 10−3) = 2.14; pBa = −log(8.2 × 10−3) = 2.09

2-20. Convert the following p-functions to molar concentrations:

pH = 1.102; log[H3O+] = −1.102; [H3O+] = 0.0791 M

(c) pBr = 7.77.

pBr = 7.77; log[Br−] = −7.77; [Br−] = 1.70 × 10−8 M

(e) pLi = 12.35.

pLi = 12.35; log[Li+] = −12.35; [Li+] = 4.5 × 10−13 M

(g) pMn = 0 .135.

pMn = 0.135; log[Mn2+] = −0.135; [Mn2+] = 0.733 M

1.02 g 1000 mL mol SO 4

(b) the pNa and pSO4 for seawater.

pNa = − log(4.79 × 10−2 ) = 1.320

pSO4 = − log(2.87 × 10−3 ) = 2.543

5.76 g KCl ⋅ MgCl2 ⋅ 6H2 O mol KCl ⋅ MgCl2 ⋅ 6H2 O

(b) the molar concentration of Mg21.

(c) the molar concentration of Cl2 .

(d) the weight/volume percentage of KCl ⋅ MgCl2 ⋅ 6H2O.

(e) the number of millimoles of Cl2 in 25.0 mL of this solution.

3.12 × 10 −2 mol Cl− L 1000 mmol

(f) ppm K1.

1 mol K + 39.10 g K + 1000 mg

(g) pMg for the solution.

(h) pCl for the solution.

5.85 g Fe(NO 3 ) 3 1 1.059 g 1000 mL mol Fe(NO 3 ) 3

Between juices __ 8.45

Within juices 0.913