ANALYTICAL CHEMISTRY

FOR CHEMICAL TECHNOLOGY PROGRAM

EXERCISES AND PROBLEMS

(Semester 3/2024-2025)
 Chapter 12: EDTA Titrations
53. What fraction 𝑎𝑌 4− of free EDTA is in the form Y4- at pH 9.00?
54. A 10.00 mL solution of 0.0500 M Mn+ buffered to pH 9.00 was titrated with 0.0500 M EDTA.
a. What is the equivalence volume, Ve, in milliliters?
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b. Calculate the concentration of Mn+ at 𝑉 = 2 𝑉𝑒 .
c. The formation constant (Kf) is 1012.00. Calculate the value of the conditional formation
constant 𝐾𝑓′ (=𝑎𝑌 4− 𝐾𝑓 ).
d. Calculate the concentration of Mn+ at V=Ve.
e. What is the concentration of Mn+ at V = 0.99Ve and V = 1.10 Ve?
55. Calculate pCu2+ at each of the following points in the titration of 50.00 mL of 0.001 00 M Cu2+
with 0.00100 M EDTA at pH 8.00 in a solution with [NH3] fixed at 1.00 M:
a) 0 mL ; b) 1.00 mL ; c) 45.00 mL ; d) 50.00 mL ; e) 55.00 mL
56. Give an example of the use of a masking agent.
57. What is meant by water hardness? Explain the difference between temporary and permanent
hardness.
58. A 10.00 mL sample of Mg2+ 0.025 M buffered to pH 10 was treated with 0.0500 M EDTA
a. The formation constant (Kf) is 108.7. Calculate the value of the conditional formation constant.
b. Calculate pMg at each of the following points: 0.99Ve; Ve and 1.10 Ve.
c. Which indicator could use in this titration?
59. A 50.0-mL sample containing Ni2+ was treated with 25.0 mL of 0.0500 M EDTA to complex all
the Ni2+ and leave excess EDTA in solution. The excess EDTA was then back-titrated, requiring
5.00 mL of 0.0500 M Zn2+. What was the concentration of Ni2+ in the original solution?

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 Chapter 14: Fundamentals of electrochemistry
60. Find the voltage of the cell drawn here if the right half-cell contains 0.50 M AgNO3(aq) and the
left half-cell contains 0.010 M Cd(NO3)2(aq). Write the net cell reaction and state in which
direction electrons flow.

61. Calculate E° and K for each of the following reactions.

a. 𝐼2 (𝑠) + 5𝐵𝑟2 (𝑎𝑞) + 6𝐻2 𝑂 ⇄ 2𝐼𝑂3 − + 10𝐵𝑟 − + 12𝐻 +
b. 𝐶𝑟 2+ + 𝐹𝑒(𝑠) ⇄ 𝐹𝑒 2+ 𝐶𝑟(𝑠)
c. 5𝑀𝑛𝑂2 (𝑠) + 4𝐻 + ⇄ 3𝑀𝑛2+ + 2𝑀𝑛𝑂4− + 2𝐻2 𝑂
d. 𝐴𝑔+ + 2𝑆2 𝑂32− ⇄ 𝐴𝑔(𝑆2 𝑂3 )3− 2
62. Calculate the voltage of each of the following cells. State the direction of electron flow.
a. Fe(s) ‫ ׀‬FeBr2(0.010 M) ‖ NaBr(0.050 M) ‫ ׀‬Br2(l) ‫ ׀‬Pt(s)
b. Cu(s) ‫ ׀‬Cu(NO3)2(0.020 M) ‖ Fe(NO3)2(0.050 M) ‫ ׀‬Fe(s)
63. Calculate the potential of a zinc electrode immersed in:
a. 0.0500 M Zn(NO3)2
b. 0.0200 M in NaOH and saturated with Zn(OH)2
c. 0.0150 M in 𝑍𝑛(𝑁𝐻3 )2+
4 Zn(NH3)4 and 0.350 M in NH3. Formation constant for
2+

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𝑍𝑛(𝑁𝐻3 )2+
4 is 7.76 * 10
64. Given the formation constant:
𝐹𝑒 3+ + 𝑌 4− ⇌ 𝐹𝑒𝑌 − 𝐾𝑓 = 1025.1
𝐹𝑒 2+ + 𝑌 4− ⇌ 𝐹𝑒𝑌 2− 𝐾𝑓 = 1014.3
calculate E0 for the process: 𝐹𝑒𝑌 − + 𝑒 − ⇌ 𝐹𝑒𝑌 2−
65. A solution contains 0.100 M Ce3+, 10-4 M Ce3+, 110-4 M Mn2+, 0.100 M MnO4- , and 1.00 M
HClO4.
a. Write a balanced net reaction that can occur between species in this solution.

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 b. Calculate K and Δ𝐺 𝑜 for the reaction.
c. Calculate E for the condition given
d. Calculate ΔG for the condition give
66. Mix equal volumes of two solutions A (𝐶𝑢2+ , 0.1 M) and B (KI, 0.4 M)
a. Write the reaction equation and calculate the equilibrium constant for this reaction.
b. When the reaction reaches equilibrium, calculate the potential of the solution (with
reference electrode 𝐴𝑔𝐶𝑙/𝐴𝑔, 𝐶𝑙 − (3𝑀))
𝑜 𝑜 −12 𝑜 −9.75
𝐸𝐶𝑢 2+ /𝐶𝑢 + = 0.153 𝑉, 𝐸𝐼 /𝐼− = 0.545 𝑉, 𝑇𝐶𝑢𝐼 = 10
2
, 𝐸𝐴𝑔 + /𝐴𝑔𝑜 = 0.8 𝑉, 𝑇𝐴𝑔𝐶𝑙 = 10

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 Chapter 15: Electrodes and potentiometry

67. A 100.0-mL solution containing 0.1000 M NaCl was titrated with 0.1000 M AgNO3, and the
voltage of the cell shown in drawn Figure was monitored.
The equivalence volume is Ve = 100.0mL. Calculate the voltage after the addition of
a. 65.0 mL of AgNO3.
b. 135.0 mL of AgNO3.

68. A fluoride ion-selective electrode has a selectivity coefficient 𝐾𝐹𝑃𝑜𝑡

− , 𝑂𝐻 − = 0.1 0.1. What will be

the change in electrode potential when 1.0 × 10-3 M F− at pH 5 is raised to pH 10?

69. Write the half-reactions for the silver-silver chloride and calomel reference electrodes.
70. Predict the voltage for the following cell.

71. A cell was prepared by dipping a Cu wire and a saturated calomel electrode into 0.10 M CuSO4
solution. The Cu wire was attached to the positive terminal of a potentiometer and the calomel
electrode was attached to the negative terminal.
a. Write a half-reaction for the Cu electrode.
b. Write the Nernst equation for the Cu electrode.
c. Calculate the cell voltage.

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 Chapter 16 Redox titrations

72. Suppose that we titrate 100.0 mL of 0.0500 M Fe2+ with 0.100 M Ce4+, using the cell shown in
drawn Figure. The equivalence point occurs when 𝑉𝐶𝑒 4+ = 50.0 mL. Calculate the cell voltage
at 49.5; 50.0, and 50.5 mL.

73. Would indigo tetra sulfonate be a suitable redox indicator for the titration of Fe(CN)64+ with Tl3+
in 1 M HCl?
74. Consider the titration of 100.0 mL of 0.0100 M Ce4+ in 1 M HClO4 by 0.0400 M Cu+ to give
Ce3+ and Cu2+, using Pt and saturated Ag‫׀‬AgCl electrodes to find the end point.
a. Write a balanced titration reaction.
b. Write two different half-reactions for the indicator electrode.
c. Write two different Nernst equations for the cell voltage.
d. Calculate E at the following volumes of Cu+: 1.00, 12.5, 24.5, 25.0, 25.5, 30.0, and 50.0mL.
Sketch the titration curve.
75. Write balanced half-reactions in which MnO42- acts as anoxidant at pH 0, pH 10, and pH 15.

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 Chapter 18: Fundamentals of Spectrophotometry
76. Why does a compound whose visible absorption maximum is at 480 nm (blue-green) appear to
be red?
77. The absorbance of a 2.31 × 10−5 M solution of a compound is 0.822 at a wavelength of 266 nm
in a 1.00-cm cell. Calculate the molar absorptivity at 266 nm.
78. A compound with molecular mass 292.16 g. mol−1 was dissolved in a 5-mL volumetric flask. A
1.00-mL aliquot was withdrawn, placed in a 10-mL volumetric flask, and diluted to the mark.
The absorbance at 340 nm was 0.427 in a 1.00-cm cuvet. The molar absorptivity at 340 nm is
ε340 = 6130 M −1 . cm−1 .
a. Calculate the concentration of compound in the cuvet.
b. What was the concentration of compound in the 5-mL flask?
c. How many milligrams of compound were used to make the 5-mL solution?
79. You have been sent to India to investigate the occurrence of goiter disease attributed to iodine
deficiency. As part of your investigation, you must make field measurements of traces of iodide
(I − ) in groundwater. The procedure is to oxidize I− to I2 and convert the I2 into an intensely
colored complex with the dye brilliant green in the organic solvent toluene.
a. A 3.15 × 10−6 M solution of the colored complex exhibited an absorbance of 0.267 at
635nm in a 1.00-cm cuvet. A blank solution made from distilled water in place of
groundwater had an absorbance of 0.019. Find the molar absorptivity of the colored
complex.
b. The absorbance of an unknown solution prepared from groundwater was 0.175. Find the
concentration of the unknown.
80. How much ferrous ethylene diammonium sulfate
(Fe(H3 NCH2 CH2 NH3 )(SO4 )2 . 4H2 O, FM 382.15) should be dissolved in a 500-mL volumetric
flask with 1 M H2SO4 to obtain a stock solution with ~500 μgFe. mL−1?
a. When making stock solution (a), you weighed out 1.627 g of reagent. What is the Fe
concentration in μgFe. mL−1?
b. How would you prepare 500 mL of standard containing ~1, 2, 3, 4, and 5 μgFe. mL−1 in
0.1 M H2 SO4 from stock solution (b) using any Class A pipets from Table 2-4 with only
500-mL volumetric flasks?

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 Chapter 20: Spectrophotometers
81. Describe the role of each component of the spectrophotometer in Figure 20-1

82. Which variables increase the resolution of a grating? Which variables increase the dispersion of
the grating? How is the blaze angle chosen to optimize a grating for a particular wavelength?
83. The true absorbance of a sample is 1.000, but the monochromator passes 1.0% stray light. Add
the light coming through the sample to the stray light to find the apparent transmittance of the
sample. Convert this answer back into absorbance and find the relative error in the calculated
concentration of the sample.

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 Chapter 21: Atomic Spectroscopy
84. Describe the role of each component of the spectrophotometer in following Figure

85. Describe the basic differences among atomic emission, atomic absorption.
86. Describe the processes occurring when the mist enters the flame.
87. Explain what a “rich” or “lean” flame is.

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 Chapeter 23 Introduction to Analytical Separations

88. Consider a chromatography experiment in which two components with retention factors k1 =
4.00 and k2 = 5.00 are injected into a column with N = 1.00 x 103 theoretical plates. The retention
time for the less-retained component is tr1 = 10.0 min.
(a) Calculate tm and tr2. Find w1/2 (width at half-height) and w (width at the base) for each peak.
(b) Using graph paper, sketch the chromatogram analogous to following Figure, supposing that
the two peaks have the same amplitude (height). Draw the half-widths accurately

(c) Calculate the resolution of the two peaks and compare this value with those drawn in following
Figure.

89. (a) Find the retention factors for octane and nonane in following Figure. When you measure
distances, estimate them to the nearest 0.1 mm.

(b) Find the ratio:

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 Time octane spends in stationary phase
Total time octane spends on column
(c) Find the relative retention for octane and nonane.
(d) Find the partition coefficient for octane by assuming that the volume of the stationary phase
equals half the volume of the mobile phase.
90. If you are extracting a substance from water into ether, is it more effective to do one extraction
with 300 mL of ether or three extractions with 100 mL?
91. When performing liquid-liquid extraction, it is common practice to shake the separatory funnel
to disperse one phase into the other.
(a) Does shaking the separatory funnel change the partition coefficient?
(b) Explain the purpose of shaking the funnel.
92. The partition coefficient for a solute in chromatography is K = cs/cm, where cs is the concentration
in the stationary phase and cm is the concentration in the mobile phase. The larger the partition
coefficient, the longer it takes a solute to be eluted. Explain why.
93. The retention volume of a solute is 76.2 mL for a column with Vm = 16.6 mL and Vs = 12.7 mL.
Calculate the retention factor and the partition coefficient for this solute.
94. Which of the following columns will provide:
(a) highest number of plates?
(b) greatest retention?
(c) highest relative retention?
(d) best separation?
Column 1: N = 1000; k2 = 1.2; α = 1.16; resolution = 0.6
Column 2: N = 5000; k2 = 3.9; α = 1.06; resolution = 0.8
Column 3: N = 500; k2 = 4.7; α = 1.31; resolution = 1.1
Column 4: N = 2000; k2 = 2.4; α = 1.24; resolution = 1.5
95. Chromatograms of compounds A and B were obtained at the same flow rate with two columns
of equal length. The value of tm is 1.3 min in both cases.
(a) Which column has more theoretical plates?
(b) Which column has a larger plate height?
(c) Which column gives higher resolution?
(d) Which column gives a greater relative retention?
(e) Which compound has a higher retention factor?
(f) Which compound has a greater partition coefficient?
96. Calculate the number of theoretical plates needed to achieve a resolution of 2.0 if:
(a) α = 1.05 and k2 = 5.00.
(b) α = 1.10 and k2 = 5.00.
(c) α = 1.05 and k2 = 10.00.
(d) How can you increase N, α, and k2 in a chromatography method? In this problem, which has a
larger effect on resolution, α or k2?

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97. Two compounds with partition coefficients of 15 and 18 are to be separated on a column with
Vm/Vs = 3.0 and tm = 1.0 min. Calculate the number of theoretical plates needed to produce a
resolution of 1.5.
98. Fill in the blanks in the diagram below regarding the influence of the factors k’, N, and α
on the separation of two chromatographic peaks and provide an explanation.

99. (a) A mixture consisting of benzene, toluene, ethylbenzene, and methane is separated using gas
chromatography. Methane, which is not retained by the column, gives a signal at 42 s, benzene
elutes at 251 s, and toluene elutes at 333 s. Calculate the adjusted retention time and the
selectivity factor between toluene and benzene.
(b) Ethylbenzene elutes at 353 s. Calculate the retention factor and the selectivity factor between
ethylbenzene and toluene.
100. In chromatography, resolution is affected by three factors:
(a) the number of theoretical plates,
(b) the selectivity, and
(c) the retention factor.
Provide the equation that expresses this dependency and draw a graph showing the influence of
each factor. Make observations about the nature of the influence of each factor on resolution.
101. An open tubular column has an internal diameter of 207 µm and a stationary phase film thickness
of 0.50 µm. An unretained compound travels from the start to the end of the column in 63 s. An
analyte retained on the column takes 433 s to travel from the start to the end. Calculate the
distribution coefficient of the analyte and the time the analyte spends in the stationary phase.
102. (a) A chromatographic column has a length of 10.3 cm and an internal diameter of 4.61 mm,
packed with stationary phase particles, which occupy 61.0% of the column volume. If the flow
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 rate used is 1.13 mL/min, determine the linear velocity in cm/min.
(b) How long does it take for a compound that does not interact with the column (or the solvent)
to travel from the beginning to the end of the column?
(c) Calculate the retention time of an analyte with a retention factor of 10.0.
103. The chromatograms of two compounds A and B are obtained using two different columns under
the same flow rate. The value of tm is 1.3 min in both cases.

(a) Which column provides better resolution, and why?

(b) Which column provides better selectivity, and why?
(c) Which compound has a greater retention factor?
(f) Which compound has a greater distribution coefficient?
(g) Calculate the retention factor of peak A.
(h) Calculate the retention factor of peak B.
(i) Calculate the selectivity factor in both cases.

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 Chapter 24: Gas Chromatography
104. (a) What are the characteristics of an ideal carrier gas?
(b) Why do H2 and He allow more rapid linear velocities in gas chromatography than N2 does,
without loss of column efficiency (Figure 24-11)?

105.
(a)When would you use split, splitless, or on-column injection in gas chromatography?
(b) Explain how solvent trapping and cold trapping work in splitless injection
106. The graph shows van Deemter curves for n-nonane at 70oC in the 3.0-m-long microfabricated
column in Box 24-2 with a 1- to 2-µm-thick stationary phase.

(a) Why would air be chosen as the carrier gas? What is the danger of using air as carrier gas?
(b) Measure the optimum velocity and plate height for air and for H2 carrier gases.
(c) How many plates are there in the 3-m-long column for each carrier gas at an optimum flow
rate?
(d) How long does unretained gas take to travel through the column at optimum velocity for each
carrier gas?
(e) If stationary phase is sufficiently thin with respect to column diameter, which of the two mass
transfer terms (23-40 or 23-41) becomes negligible? Why?
(f) Why is the loss of column efficiency at high flow rates less severe for H2 than for air carrier
gas?
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107. Compare the thermal stability of the following stationary phases in gas chromatography, and
based on that, explain the difficulties in analyzing compounds that are both polar and have high
boiling points using gas chromatography.

108. The diagram illustrates the structure of a sample injection

port. Identify the names of the components corresponding
to the numbered parts in the figure. What injection
technique does this diagram represent? Explain.

109. Given the following compounds:

a) Which of these compounds can be analyzed
directly by gas chromatography? Provide a brief
explanation.
b) If a chromatographic column with a 5% phenyl –
95% methylpolysiloxane stationary phase is used,
which compounds can be analyzed? Provide a brief
explanation.

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110. A chromatogram on an HP-5 MS column of a mixture containing 5 compounds — Toluene,
Ethylbenzene, o-Xylene, m-Xylene, and p-Xylene — using GC-FID.
Given the information about the
compounds:
2
Nhiệt độ
3 4 Tên chất LogKow
sôi (oC)
1 Toluene 110.6 2.73
Ethylbenzene 136 3.15
o-Xylene 144 3.15
m-Xylene 139 3.15
p-Xylene 138.4 3.15

(a) Why are there only 4 peaks on the chromatogram even though 5 compounds were analyzed?
(b) In your opinion, which compounds correspond to peaks 1, 2, 3, and 4 on the chromatogram?
111. Trace Analysis of Benzene in a Water Sample Using Gas Chromatography with Flame
Ionization Detection (GC-FID)
Toluene is used as the internal standard. The concentration of toluene in all calibration
solutions is 20 ppb. The results are summarized in the table below.
(a) Why is toluene used as the internal standard for benzene?
(b) What conditions must be met to use toluene as an internal standard?
(c) Determine the concentration of benzene in the water sample.
Diện tích peak của Diện tích peak của
Ppb Benzene
Benzene Toluene
10.0 252 376
15.0 373 370
25.0 636 371
Mẫu 533 368

112. Design of an optimal gradient program to separate all peak

m
113. Two-compound analysis by gas chromatography was performed under isothermal conditions
using an open tubular capillary column of 15 m length (chromatogram shown on the left). If the

16
 same chromatographic conditions are used (including column oven temperature, carrier gas flow
rate, and column type — same stationary phase, internal diameter, and film thickness), but the
column length is changed to 30 m, do the following:
• Sketch the two chromatographic peaks on the right chromatogram to illustrate how they would
appear with the longer column. Precise drawing is not necessary, but the changes should be
clear.
• Calculate the new resolution (Rs) under the new conditions.

114. Given the Van Deemter plot of a 30-meter gas chromatography column operated with different
carrier gases:

(a) If nitrogen (N₂) is used as the carrier gas, calculate the number of theoretical plates when the flow
velocity is 25 cm/sec.
(b) Compare the column efficiency at a flow velocity of 28 cm/sec using helium (He) and hydrogen
(H₂) as carrier gases.
(c) Among the three carrier gases (N₂, He, H₂), which one is the most efficient in terms of column
performance?

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