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org/jchemeduc Laboratory Experiment

A Comprehensive Teaching Laboratory Program on Titration

Analysis: Transition from Classic to Modern Approaches
Yan Wang, Jinling Geng, and Zhiwei Zhu*
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ABSTRACT: This paper outlines a comprehensive teaching laboratory

course program that centers on titration analysis, a timeless and essential
technique in analytical chemistry spanning various disciplines, such as
Downloaded via UNIV FED DO PARANA on March 14, 2024 at 12:48:33 (UTC).

environmental science, medicine, and industry. In these fields, titration

analysis is paramount for determining the concentrations of substances and
evaluating their purity. The uniqueness of this course program resides in its
methodical exhibition of the titration process in its entirety. This
encompasses everything from manual stopcocks in glass burets to modern,
precise metering pumps in automated titrators and from human-reliant
indicator color changes to advanced potential indicating systems.
Furthermore, the program spans conventional chemical reagents as titrants
to electrogenerated titrants, providing an all-encompassing educational
experience. The course design follows a structured, step-by-step pedagogy,
progressing from fundamental monoprotic acid−base titration to complex
polyprotic acid−base titration and from acidity-modulated redox titration to titrations involving both redox and precipitation
reactions. This scaffolded approach ensures a gradual yet comprehensive understanding of titration analysis. By investing in this 8 h
course program, students can anticipate achieving a profound comprehension and proficiency in the foundational principles and
operational techniques of titration analysis. Moreover, they will cultivate a deep appreciation for the connotations of “titrating” and
“determining” in the realm of analytical chemistry.
KEYWORDS: First-Year Undergraduate, Analytical Chemistry, Laboratory Program, Titration, Volumetric Analysis,
Automatic Potentiometric Titration, Coulometric Titration

■ INTRODUCTION
Titration has found widespread practical applications due to its
simplicity, reliability, and adaptability. In the pharmaceutical
industry, for instance, titration is used to ascertain the active
ingredient concentration in drugs, ensuring consistency across
batches. In the food industry, it is employed to analyze the
composition of food products, thereby guaranteeing their
safety and quality. While titration is a familiar concept to high
school students and chemistry enthusiasts alike, university
students in lower-level analytical chemistry laboratory courses
must not only master its basic operation but also demonstrate
their understanding of advanced chemistry principles through
experiments.1,2 Consequently, when devising analytical chem-
istry laboratory courses, it is imperative to consider the varying
levels of students and craft suitable experimental programs for
them. Beyond traditional buret experiments,3 a plethora of
intriguing experiments can be devised by coupling burets with
other gadgets. For instance, titration experiments can be
amalgamated with mobile phones,4,5 virtual experimental
software for simulation exercises,6−10 or even practical
applications for scientific research projects.11−15 These experi-
ments are certainly innovative and captivating, yet students
© 2024 American Chemical Society and
Division of Chemical Education, Inc.
612
yearn for an experimental program that comprehensively
illustrates the entire spectrum of titration. In other words, they
desire an experiment that unveils the titration process in its
entirety, showcasing its various dimensions, practical applica-
tions, and multiple layers. This will enable them to develop a
more profound understanding of the underlying scientific
principles and the real-world relevance of titration.
Titration is an important technique in chemical analysis,
encompassing two primary steps: “titrating” and “determining”.
During the “titrating” phase, standard solutions are gradually
added to the analyte solution until the chemical reaction
attains the equivalence point. This can be executed using
conventional glass burets, modern precise metering pumps, or
even electrolyte in situ electrolysis (coulometric titration).16,17
The equivalence point can be approximated by observing
Received: October 22, 2023
Revised: December 26, 2023
Accepted: December 29, 2023
Published: January 25, 2024
https://doi.org/10.1021/acs.jchemed.3c01091
J. Chem. Educ. 2024, 101, 612−620
Journal of Chemical Education
Figure 1. Flow diagram illustrating the transition of titration analysis from classic to modern approaches in this teaching laboratory program.
Figure 2. Schematic diagram integrating experimental equipment configurations and titration curve profiles.
specific physical changes that accompany chemical equiv-
alence. “Determining”, on the other hand, pertains to
establishing the end point of a titration reaction, either by
adding an appropriate indicator or by harnessing other
instrumental analysis techniques. The indicator method,
renowned for its simplicity and reliability, pinpoints the
titration end point by discerning color changes due to an
indicator. Conversely, instrumental analysis methods ascertain
the end point more precisely and sensitively by detecting and
quantifying alterations in a specific physical signal,18−21 with
the potentiometric method being the most prevalent and
pragmatic. Potentiometric titration provides a comprehensive
record of the entire titration process, manifested in a clear-cut
titration curve. By pinpointing the inflection point on this
curve, the titration end point can be unequivocally and
accurately determined, thereby greatly simplifying the titration
process and enhancing the accuracy of the obtained results.
pubs.acs.org/jchemeduc Laboratory Experiment
Our teaching team prides itself on decades of expertise in
imparting the intricacies of quantitative analytical chemistry
laboratory experiments. We offer a comprehensive suite of
classical chemical titration analysis experiments alongside
several instrumental analysis experiments. By enrolling in this
course, students will acquire a solid grasp of fundamental
knowledge, essential manipulations, and basic skills pertinent
to quantitative analytical chemical experiments. They will also
become well-versed in typical analytical methods and
experimental data processing techniques. In our previous
experiment, we conducted potentiometric titration, where
students performed manual titration aided by glass burets.
They used a pH meter to manually record pH value changes in
the solution and ultimately determined the titration end point
by plotting a titration curve. While such experiments can be
time-consuming and procedurally intricate, the evolving times
necessitate the introduction of a comprehensive and efficient
titration experiment that not only encapsulates the knowledge
613 https://doi.org/10.1021/acs.jchemed.3c01091
J. Chem. Educ. 2024, 101, 612−620
Journal of Chemical Education pubs.acs.org/jchemeduc
Table 1. Key Information for Lab Sessions
Lab Reference Calibration Reaction or Electrode
Session Analyte Reagent Titrator
1 Butyric Acid Oxalic Acid NaOH H2C2O4·2H2O + 2NaOH = Na2C2O4 +
4H2O
2 Industrial Sodium HCl Na2CO3 + 2HCl = 2NaCl + CO2(g) +
Alkali Carbonate 2H2O
3 Vitamin C Electron I2 3I− → I3− + 2e
4 Zinc Ion Electron [Fe(CN)6]4− [Fe(CN)6]3− + e → [Fe(CN)6]4−
system of titrimetric methods but also exemplifies the fusion of
classic methodologies with modern instrumentation. The
design of this experimental program encompasses multiple
analytical experiments on titration, while seamlessly integrating
diverse titration procedures and end point determination
methods into the analysis of real substances.
This 8 h laboratory program is composed of four integrated
sessions, which involve automatic titration of organic acids
(industrial alkalis) and coulometric titration of vitamin C (zinc
ions). To provide students with a more focused learning
experience, we have meticulously developed three specific
learning objectives: (1) to grasp the theory and measurement
techniques of potentiometric titration, (2) to comprehend the
fundamental principles and implement the requirements of
coulometric titration, and (3) to appreciate the distinctions
among classic, potentiometric, and coulometric titration
methods.
These laboratory sessions not only showcased the wide-
spread application of titration technology but also assisted our
students in gaining a deeper understanding and mastery of the
principles and methodologies of titration experiments.
Through these hands-on experiences, our students have fully
grasped the concepts of “titrating” and “determining” in
analytical chemistry.
■ DESIGN OF THE LABORATORY PROGRAM
KNOWLEDGE SYSTEM
In this laboratory program, we aim to seamlessly integrate all
components of the titration experiment, as shown in Figure 1.
This is not just a linear series of steps but an interconnected
system forming a comprehensive knowledge base. Prior lab
assignments familiarized students with classical titration
experiments, such as acid−base, complex, and redox titrations,
equipping them with relevant theoretical knowledge. However,
their grasp of concepts, such as the titration curve,
potentiometric titration, and coulometric titration, remained
at a superficial level. Through this holistic laboratory program,
students will gain practical experience, deepening their
understanding of this important chemical analysis technique
and refining their analytical skills.
“Titrating” in Titration Analysis: Titration Process
We begin with simple acid−base titration reactions using an
automatic potentiometric titrator, progressing from neutraliza-
tions between a weak acid and a strong base to stepwise
titrations of a polyprotic weak base with a strong acid. This
allowed students to observe titration curve shifts (Figure 2).
Drawing these curves not only aids in visualizing the titration
reaction but also constitutes an essential aspect of acid−base
titration knowledge. Students then engage in a comparative
analysis of classical and coulometric titrations, gaining a
comprehensive understanding of the fundamental procedures
614
Laboratory Experiment
Reaction Titration Reaction
(CH2COOH)2 + 2NaOH = (CH2COONa)2 +
2H2O
Na2CO3 + 2HCl = 2NaCl + CO2(g) + 2H2O
C6H8O6 + I2 = C6H6O6 + 2HI
3Zn2+ + 2K+ + 2[Fe(CN)6]4− =
K2Zn3[Fe(CN)6]2(s)
and discerning the distinct differences between the two
methods. Through this rigorous comparison, students are
able to deeply appreciate and experience the remarkable
advantages offered by electric titrants, fostering a deeper
appreciation for the precision and accuracy of modern
analytical chemistry techniques. Next, we will probe the
impact of experimental conditions on redox titration reaction
systems. These conditions have a profound effect on the
reaction rate, extent, and titration accuracy, underscoring the
crucial nature of choosing suitable experimental conditions to
ensure dependable outcomes. Finally, students investigate the
amalgamation of redox and precipitation titrations, increasing
complexity while fostering deeper comprehension and
explanation of titration principles and applications. This
carefully designed series of experiments aims to impart a
profound realization to students that “titrating”, though often
perceived as a straightforward technique, is in fact replete with
intricate and profound scientific principles that extend far
beyond its facade of simplicity.
“Determining” in Titration Analysis: End Point
Determination
It is crucial to understanding how the titration curve impacts
the end point determination. By analysis of the reaction curves,
students probe the reaction mechanism, rate, and stoichiom-
etry. Establishing a unified understanding of diverse titration
reaction curves is paramount for proficiency in titrating and
determining. We initiate with chemical indicators and pH
titration curves for end point determination, progressing to
electrical signals for titration end point judgment. This
introduction to physical and chemical measurements solidifies
fundamental principles. By examining titration curve examples,
students unify their understanding in a binary coordinate
system, with measured signals (color, pH, and electrical
signals) as ordinates and measured physical quantities
(solution volume, time) as abscissas. This clarity helps students
grasp the essence of “determining” in titration analysis.
In summary, this knowledge system that combines “titrating”
and “determining” forms a robust foundation for students to
confidently apply their skills in diverse analytical chemistry
contexts.
■ LABORATORY PROGRAM AND LEARNING
OBJECTIVES
The following laboratory sessions will be conducted with key
information summarized in Table 1:
1. Automatic Potentiometric Titration of Organic Acids
2. Automatic Potentiometric Titration of Industrial Alkalis
3. Coulometric Titration of Vitamin C
4. Coulometric Titration for Zinc Ions Determination
Our learning objectives for students are 3-fold:
https://doi.org/10.1021/acs.jchemed.3c01091
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Journal of Chemical Education pubs.acs.org/jchemeduc
1. Develop a thorough understanding of the theory and
practical aspects of potentiometric titration, enabling
students to confidently perform and interpret results
from related experiments.
2. Foster a deep comprehension of the fundamental
principles and operational requirements of coulometric
titration, empowering students to apply this technique in
various analytical scenarios.
3. Facilitate a comparative analysis of classic titration,
potentiometric titration, and coulometric titration,
allowing students to appreciate the merits and
limitations of each method in diverse practical contexts.
To achieve our learning objectives, we devised an
experimental protocol with strategic inquiries to stimulate
students’ thinking and encourage them to seek solutions
through experimentation. For Lab Sessions 1 and 2, which
involve automatic potentiometric titration, we encouraged
students to explore several questions. These include examining
the influence of the titration speed on both the experimental
process and the results obtained. Additionally, we ask students
to consider whether an automatic potentiometric titrator can
accurately titrate to bicarbonate. Furthermore, we discuss the
advantages and limitations of using automatic potentiometric
titration in chemical analysis. Moving on to Lab Sessions 3 and
4, which focus on coulometric titration, our inquiries center on
the construction of titration systems. Specifically, we delve into
the impact of pH on titration when conducting coulometric
titration of vitamin C. We also explore the role and appropriate
dosage of potassium iodide in the coulometric titration of
vitamin C. Lastly, we discuss potential sources of error that
may arise during coulometric titration experiments, fostering a
critical understanding of experimental methodology and its
pitfalls. Briefly speaking, our aim is to cultivate their innate
curiosity and enhance their capacity for active exploration.
In the preceding class, students gained an understanding of
titration operations and completed pertinent laboratory
exercises. In this laboratory program, they will acquire
knowledge on utilizing an automatic potentiometric titrator
to continuously monitor alterations in solution potential using
a composite electrode and automatically document the
titration curve. Additionally, they will compute experimental
results based on the volume of titrant consumed at the end
point corresponding to the titration jump. The samples
selected for this experiment are butyric acid and industrial
alkali (the main ingredient is sodium carbonate).
“Determination of organic acids” has been established as one
of the foundational practical experiments for learning acid−
base titration. In this laboratory, students will transition from
classical burets to exploring automated titration techniques.
Regarding the “determination of industrial alkali”, it has been
addressed in previous experimental programs where students
employed glass burets to add titrant dropwise and utilized a
chemical indicator color change to determine the end point.
However, because carbonic acid is a polyprotic acid, there are
intermediate reactions generating monoprotic acid during
acid−base interactions. The usage of the indicator method for
end point determination is limited, and the intermediary
process cannot be clearly observed. The introduction of
automatic potentiometric titrators into the laboratory not only
enhances the efficiency of titration operations but also
facilitates a deeper understanding of chemical reaction kinetics
and the establishment of chemical equilibrium among students.
615
Laboratory Experiment
By observing fluctuations in titration curves, students can gain
a comprehensive grasp of the principles and techniques of the
titration process, thereby improving the precision and
reliability of experiments.
In the two aforementioned laboratory sessions, precise
metering pumps and potential detection systems in automatic
potentiometric titrators have replaced the buret equipped with
a glass stopcock for a valve and chemical indicators.
Nevertheless, students still need to prepare and calibrate the
titrant. Subsequently, we devised two advanced laboratory
sessions with the primary objective of comparing coulometric
titration to classical titrations. The setup process and operation
exhibit marked differences, providing students with a unique
opportunity to discern the disparities between the two
techniques. In coulometric titration, the “titrant” is a constant
direct electrical current of a known magnitude that consumes
the analyte. The quantity of analyte can be precisely
determined by measuring the duration required to complete
the electrolysis reaction based on Faraday’s law of electrolysis
and the stoichiometry of the titration reaction. The
coulometric titration method is a highly effective analytical
technique suitable for determining numerous types of
compounds. The simplicity and ease of operation of the
coulometric titrator allow students to concentrate primarily on
the analyte determination, eliminating the need for additional
reference reagents. Integrating this technique into the
laboratory curriculum not only enhances students’ compre-
hension of electrolytic processes but also acquaints them with
alternative titration methods applicable in diverse fields.
Lab Session 3 focuses on determining the vitamin C content
using coulometric titration. This experiment encompasses
critical knowledge points on oxidation reactions and
emphasizes the comparison and exploration of analytical
methodologies. Through this laboratory, students can acquire
and master the technique of determining substance content
using coulometric titration and conduct in-depth research on
the application of oxidation−reduction reactions in titration.
Lab Session 4 presents a more challenging task: determining
zinc ions by coulometric titration in conjunction with
precipitation reactions. In this session, students are required
to devise an experimental plan independently under the
guidance of a teacher.
Through this program, students will not only enhance their
analytical chemistry proficiency but also cultivate critical
thinking and problem-solving skills, laying a solid foundation
for future academic and professional pursuits in the field.
■ COURSE ORGANIZATION
This laboratory program is designed to cultivate students’
analytical chemistry skills through systematic experimental
teaching, enabling them to master the knowledge of
experimental principles, standard operating procedures, and
data interpretation. Specifically, the program is organized as
follows:
• A 1 h lecture is provided to introduce practical aspects of
experiments, including experimental principles, proce-
dural steps, and necessary precautions.
• Students engage in a total of 7 h of experiments, divided
equally between automatic potentiometric titration and
coulometric titration. Due to time constraints, students
select one experiment from two options each: “Organic
acids” or “Industrial alkalis” and “Vitamin C” or “Zinc
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Table 2. Experimental Data for Automatic Potentiometric Titration of Organic Acids
Mass of Primary- Volume of Mean of
Standard Oxalic Acid NaOH Concentration Concentration of
No. (g) (mL) of NaOH (M) NaOH (M)
1 0.1516 22.38 0.1075
2 0.1691 25.03 0.1072 0.1074
3 0.1636 24.13 0.1076
ions” based on academic interest and practical
application. This selection mechanism allows students
to focus on their chosen experiments and develop a
deeper understanding of the techniques and method-
ologies involved.
• Students work in pairs during experiments, promoting
teamwork and collaboration and enhancing their under-
standing of experimental principles and techniques
through discussion.
• Students are required to individually draft lab reports,
which helps reinforce their knowledge and skills and
deepens their analysis and interpretation of experimental
data.
• This program falls under electrochemical experiments
and is alternated with other spectroscopic experimental
programs. This rotation provides students with a
broader perspective on the various branches of analytical
chemistry and enables them to grasp the similarities and
differences between diverse experimental techniques. By
rotating through various experiments, students are
exposed to a range of analytical techniques and
methodologies, allowing them to gain hands-on
experience and understand the applications of different
techniques in different contexts. This versatility fosters a
well-rounded understanding of analytical chemistry and
its diverse applications in various fields.
• The class size is limited to 14−16 students, divided into
7−8 groups, with 4 days per week for 7 weeks, totaling
422 students.
This course structure facilitates students’ mastery of
analytical chemistry experimental techniques and method-
ologies, enhances their independent thinking and problem-
solving capabilities, fosters collaboration, enhances laboratory
proficiency, and provides a strong foundation for further
studies in analytical chemistry. It also offers students a taste of
scientific research and the scientific inquiry ethos.
■ HAZARDS AND SAFETY
Safety precautions are paramount when handling any
chemicals. When working with acidic and basic solutions,
such as 0.5 M H2SO4, 0.2 M HCl, and 0.1 M NaOH, as
outlined in this experiment, protective eye gear, nitrile gloves,
and a lab coat resistant to chemicals are mandatory. Notably,
concentrated solutions of HCl (6 M) and HAc (36%, 6 M) are
highly corrosive and irritating, and their handling should be
confined to a fume hood. Oxalic acid, which is also corrosive
and irritating, must be promptly sealed after usage and kept
away from direct sunlight. Special care is required when
handling potassium iodide due to its potential irritation to the
skin and respiratory tract and the risk of causing serious and
enduring harm to the digestive tract. Avoid inhalation or
ingestion during its handling. The other chemicals used in this
lab pose minimal or no significant hazards, and there are no
major safety concerns related to instrumentation.
616
Laboratory Experiment
Volume of Content of
Mass of Organic NaOH Butyric Acid Mean of Content of
Acid Sample (g) (mL) (%) Organic Acid (%)
0.1436 22.62 99.89
0.1678 26.38 99.69 99.79
0.1602 25.21 99.79
■ RESULTS AND DISCUSSION
Lab Sessions 1 and 2: “Organic Acids” and “Industrial
Alkalis”
Through the utilization of an automatic potentiometric titrator,
students quickly familiarized themselves with the intricacies of
potentiometric titration, thereby gaining proficiency in the
operational steps essential to chemical analysis experiments. By
comparing the manual operation of a buret with the automatic
dispensing process of a precise metering pump, students gained
insights into the principles and applications of instrumental
analysis. The introduction of an indicator within the
potentiometric indicating system further enhanced students’
understanding of the relationship between acid−base indicator
color changes and acidity through careful observation of
potentiometric curve variations.
The majority of students adeptly completed these experi-
ments, initially adapting and subsequently mastering the use of
the automated titrator. Emphasis was placed on observing
titration curve formation and comparing it with chemical
indicator end-point changes. In the “Organic Acids” experi-
ment, using phenolphthalein as an indicator, the end point was
discernible by a barely perceptible pink coloration. Students
observed that this color change aligned precisely with the end
point denoted by the potentiometric curve, enabling them to
witness the indicator’s transformation process firsthand. The
automated titrator’s precision mitigated human error, instilling
confidence in students’ ability to generate high-quality
analytical data. Experimental data obtained also served as an
indicator of whether initial weighing and solution preparation
met the experimental requirements. Only a few students
encountered minor challenges, primarily related to interpreting
data to ascertain the content of unknown organic acids and
accounting for experimental errors. However, these issues were
swiftly resolved through collaborative discussions because
students worked in pairs.
For the “Industrial Alkalis” experiment, students encoun-
tered it in previous experiments but faced limitations imposed
by the chemical indicator (methyl red-bromocresol green
mixed indicator), which could only discern the second end
point. This hindered observations of intermediate product
formation and reaction processes, such as bicarbonate,
necessitating cumbersome boiling to eliminate carbon dioxide.
Automatic potentiometric titration circumvented these chal-
lenges, allowing for the observation of two distinct titration
curve jumps, which piqued students’ interest. Additionally,
students could track the methyl orange indicator’s color
change throughout the titration process. The titration of
sodium carbonate presented two end points: one correspond-
ing to carbonate converting to bicarbonate (approximately pH
8.3) and another to the formation of carbonic acid and carbon
dioxide (approximately pH 3.8). Notably, when the solution
exhibited the indicator’s transition color, orange (approx-
imately pH 4.0), it coincided with the second titration curve
jump. This alignment guided students to contemplate changes
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Table 3. Experimental Data for Automatic Potentiometric Titration of Industrial Alkalis

Mass of Primary- Mean of Mass of Mass Fraction of Mean of Mass Fraction
Standard Sodium Volume of Concentration Concentration of Industrial Volume of Sodium Carbonate of Sodium Carbonate
No. Carbonate (g) HCl (mL) of HCl (M) HCl (M) Alkali (g) HCl (mL) (%) (%)
1 0.2264 20.94 0.2040 0.3744 26.72 76.29
2 0.2023 18.81 0.2029 0.2032 0.3537 25.26 76.34 76.30
3 0.2377 22.12 0.2028 0.3097 22.10 76.28

in chemical equilibrium during titration, encouraging them to
shift their focus beyond solely the chemical indicator at the
titration’s end point and embrace the broader chemical
reaction processes.
The incorporation of an automated titrator proved
instrumental in students successfully acquiring reliable data
results for these two acid−base equilibrium experiments,
reflecting the experiments’ smooth progression. Furthermore,
student feedback in reports underscored their grasp of the
significance of the titration curve significance. Tables 2 and 3
showcase experimental data obtained from students’ “Organic
Acids” and “Industrial Alkalis” experiments, respectively.
Lab Sessions 3 and 4: “Vitamin C” and “Zinc Ions”
Coulometric titration stands out as an effective method for
determining both vitamin C and zinc ions, with each process
having its own distinct characteristics. Mastering this technique
hinges on having a profound understanding of coulometric
analysis fundamentals and using reference substances to gauge
the current efficiency, which should ideally be close to 100%.
This efficiency serves as a pivot for assessing the suitability of
electrolyte acidity and the supporting electrolyte concen-
tration.
When delving into the coulometric titration determination
of vitamin C, students must grasp the underlying principle:
generating titrant I2 to oxidize vitamin C through constant-
current electrolysis of a KI solution. Vitamin C is highly
reducible and prone to oxidation by ambient oxygen,
necessitating the preparation of relevant standard solutions of
ascorbic acid and vitamin C supplement tablet solutions just
prior to use. Since the end point is denoted by a sharp increase
in the titration curve, a slight excess of titration is necessary.
Students must exercise caution in managing the titrant quantity
to prevent excessive iodine production, which can be
detrimental. Moreover, the titration reaction is significantly
influenced by acidity, making it imperative to comprehend the
impact of this factor on experimental outcomes. For instance,
I− can be oxidized by air, and as the acidity increases, the
reaction accelerates; conversely, if the acidity is too low, I2 will
decompose into HIO and IO3−, thereby affecting the current
efficiency of coulometric titration.
It is vital to guide students in comprehending that chemical
experiments center on experimenting with varied conditions
through meticulous experiment design. Unexpected results
during experiments often pique curiosity, a trait that
distinguishes experimental teaching from classroom instruc-
tion.
In addition, students often find determining vitamin C
content in commercially available supplement tablets fascinat-
ing, since they can analyze a real-world sample. However, it is
pivotal to emphasize the importance of meticulous sample
pretreatment, as it significantly impacts experimental results.
Commercially available vitamin C supplement tablets often
contain water-insoluble substances like dextrin, which can
disrupt current efficiency and, consequently, titration results.
Therefore, after dissolving the volumetric sample solution, it is
imperative to perform a filtration step prior to coulometric
titration, ensuring homogeneity in the titration reaction
system.
In determining zinc ions via coulometric titration, we
adopted a designed experiment approach, providing students
with experimental hints and encouraging them to independ-
ently devise experimental procedures and draw conclusions.
The experiment’s foundation lies in using constant-current
electrolysis to reduce [Fe(CN)6]3− and then using the reduced
[Fe(CN)6]4− as a titrant to quantitatively react with Zn2+ to
form a precipitate. Here, titration reactions involve precip-
itation reactions where varying precipitation forms emerge at
different acidities, leading to multiple precipitation−dissolution
equilibria. Moreover, this constitutes a heterogeneous solid−
liquid system, where precise control over acidity and related
experimental conditions is paramount for maintaining current
efficiency and avoiding significant deviations in experimental
results.
Through literature review and analysis of their own
experimental data, students identified pH = 2−3 as the ideal
range for quantitative precipitation of K2Zn3[Fe(CN)6]2.
Elevated pH levels can lead to the conversion of some
precipitate forms into Zn2[Fe(CN)6], altering the stoichio-
metric ratio for Zn2+ determination. Based on independently
devised experimental schemes, students conducted exploratory
experiments by introducing interfering ions such as Fe3+, Cu2+,
and Ni3+. They observed that these ions exert some influence
on titration results. Notably, two students demonstrated
exceptional interest in investigating the influence of Ni3+ on
the determination of Zn 2+ . They devised their own
experimental plan and conducted extensive research outside
of class hours to explore the impact of Ni3+ on Zn2+
determination when the Ni−Zn ratio ranged from 0 to 0.4.
Their initial speculation on potential mechanisms is a
commendable accomplishment for first-year undergraduates.
Furthermore, this serves as indirect affirmation of the
effectiveness of this laboratory program, highlighting its success
in fostering critical thinking and hands-on learning experiences.
Tables 4, 5, and 6 present experimental data obtained by
students for both “Vitamin C” and “Zinc Ions” experiments.
Table 4. Effect of the Acidity of the Electrolyte Solution on
the Accuracy of the Experimental Results for Coulometric
Titration of Vitamin C
pH of Electrolyte Potential of End Time of End Relative
Solutiona Point (mV) Point (s) Deviation (%)
1 320.4 246 −1.6
3 315.4 248 −0.8
5 303.6 245 −2.0
a
Other experimental conditions: the mass of KI added into electrolyte
solution, 1 g; electrolysis current, 10 mA.

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Table 5. Effect of the Amount of KI on the Accuracy of the “Organic Acids” and “Industrial Alkalis”, 60 students (39.7%)
Experimental Results for Coulometric Titration of Vitamin and 51 students (33.8%) selected these sessions, respectively.
C These findings align closely with our teaching objectives, and it
is worth noting that those who opted for “Organic Acids” and
Mass of KI Potential of End Point Time of End Relative
(g)a (mV) Point (s) Deviation (%) “Industrial Alkalis” may have engaged in deeper contemplation
due to the necessity of observing titration curves and
0.03 316.7 228 +0.4
comprehending the underlying chemical principles, which
0.15 219.4 224 −1.3
further solidified their grasp on analytical methods and
1.00 195.7 222 −2.2
a
scientific inquiry.
Other experimental conditions: pH ≈ 3 acetate buffer solution; 122 students (80.8%) expressed a desire for more
electrolysis current, 10 mA.
comprehensive experimental guides, including precise reagent
quantities and detailed, step-by-step procedures provided by
Table 6. Effect of the K3[Fe(CN)6] Concentration on the instructors. Only 29 students (19.2%) believed that instructors
Accuracy of the Experimental Results for Coulometric should confine their role to offering general experimental
Titration for Zinc Ion Determination directions, allowing students to develop the experimental
Concentration of Time of End Concentration of Relative protocol independently. This highlights that undergraduate
K3[Fe(CN)6] (M)a Point (s) Zn2+ (M) Deviation (%) students, particularly those in the earlier stages of their
0.02 548 0.4260 +159.7 education, tend to prefer a more structured, “menu-style”
0.05 292 0.2270 +38.4 approach to experimental guidance and require gradual
0.1 207 0.1609 −1.9 acclimation to a research-oriented experimental training
0.2 203 0.1578 −3.8 paradigm.
a
Other experimental conditions: 0.01 M H2SO4 solution; electrolysis The laboratory session deemed most popular, or engaging,
current, 10 mA. was “Vitamin C”, chosen by 67 students (44.4%). This
preference may stem from students’ inclination toward
■ QUESTIONNAIRE RESULTS AND ANALYSIS
At the conclusion of the course, we administered an
experimental programs with practical applications, such as
the analysis of real-world samples.
It is noteworthy that only 31 students (20.5%) expressed a
anonymous and voluntary questionnaire to the 422 students willingness to continue delving into related experiments
who enrolled in the laboratory program (Figure 3). Ultimately, outside of class. This reluctance could be attributed to a
we received 151 completed questionnaires. range of factors, including a lack of opportunities to pursue
The questionnaire results suggest that, through this teaching related content, conflicting schedules, or other influential
laboratory program, students have developed a strong elements. This underscores the importance of condensing this
understanding and proficiency in pertinent theoretical comprehensive titration experiment program into a more
concepts, particularly in titration and electrochemical analysis manageable time frame to enhance student learning efficiency.
techniques. Across the four laboratory sessions, students In future curriculum development, we will prioritize the
progressively grasped the significance of analytical methods integration and condensation of essential knowledge points.
and scientific research, moving from basic measurement
experiments to those requiring the independent formulation
of experimental procedures. When presented with multiple
choices, 86 students (57.0%) felt that the laboratory session on
■ CONCLUSION
This laboratory program introduces students to the funda-
“Zinc Ions” provided them with the deepest experience in mentals of acid−base titration through a hands-on exercise, all
terms of analytical methods and scientific exploration. This was while familiarizing them with modern automatic titration
followed by “Vitamin C”, chosen by 82 students (54.3%). For instruments. This approach not only saves time typically

Figure 3. Questionnaire for students who took this laboratory program.

618 https://doi.org/10.1021/acs.jchemed.3c01091
J. Chem. Educ. 2024, 101, 612−620
Journal of Chemical Education
required for “titrating” but also reduces the complexity often
associated with traditional titration methods. By doing so, it
allows students to delve deeper into the experiment’s content
and gain practical experience with contemporary instrumenta-
tion. Throughout the titration process, students select the
potential jumps in the potential−volume correspondence curve
as the end point determination for “determining”. They also
employ indicators to observe color changes at the end point for
comparative analysis. This enables them to gain a compre-
hensive understanding of the chemical kinetics and chemical
equilibrium through observed potential changes. Specifically,
by utilizing automatic potentiometric titration, they can
precisely track concentration changes in bicarbonate ions in
sodium carbonate, enhancing their understanding of inter-
mediate chemical reactions.
In the advanced coulometric titrimetric experiment, the
principle of end point determination remains consistent with
the potential jump change. However, instead of relying on
titrant calibration with reference reagents, the method involves
generating titrant in situ through electrolysis of the electrolyte.
This innovative approach eliminates challenges related to the
preparation, standardization, and storage of standard solutions,
providing students with a more efficient and streamlined
experimental process. By doing so, students are given ample
time and energy to thoroughly delve into the intricacies of the
titration system, enabling them to gain a profound under-
standing of the pivotal factors that impact the precision of
titration analysis.
Looking ahead, we envision expanding the titration end
point detection methods such as amperometry in future
experimental classes. To further enhance students’ engagement
and motivation, we plan to continue diversifying the range of
substances used for testing. Our goal is to create a dynamic and
stimulating learning environment that encourages curiosity and
a deeper exploration of titration analysis.
In summary, this laboratory program has been instrumental
in helping students develop a profound understanding and
mastery of the fundamental principles and operational aspects
of titration analysis. Through a combination of practical hands-
on experiments and exposure to modern instrumentation, they
not only grasp the connotations of “titrating” and “determin-
ing” but also build a strong foundation in analytical chemistry.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available at https://pubs.ac-
s.org/doi/10.1021/acs.jchemed.3c01091.
Equipment and chemical information; student labora-
tory handout; pictures of the experimental teaching site;
excerpts from several student lab reports (PDF; DOCX)
Video guide for pH meter and automatic potentiometric
titrator (MP4)
Video guide for coulometric titrator operation (MP4)
■ AUTHOR INFORMATION
Corresponding Author
Zhiwei Zhu − National Demonstration Center for
Experimental Chemistry Education, College of Chemistry and
Molecular Engineering, Peking University, Beijing 100871, P.
R. China; orcid.org/0000-0001-8119-4166;
Email: zwzhu@pku.edu.cn
pubs.acs.org/jchemeduc Laboratory Experiment
Authors
Yan Wang − National Demonstration Center for Experimental
Chemistry Education, College of Chemistry and Molecular
Engineering, Peking University, Beijing 100871, P. R. China
Jinling Geng − National Demonstration Center for
Experimental Chemistry Education, College of Chemistry
and Molecular Engineering, Peking University, Beijing
100871, P. R. China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jchemed.3c01091
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This material is derived from work funded by the National
Natural Science Foundation of China (Grant No. 21775007).
We extend our gratitude to the 422 students enrolled in the
Spring 2023 Quantitative Analysis Laboratory Experiments
class for their active participation in the experiment. We also
express special appreciation to Ph.D. candidate Boyi Zhu from
the Faculty of Education at Monash University for her
insightful contributions and valuable discussions toward this
program.
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