Guided Inquiry Project: Coulometric Titration

Nathan Millward
Partner: Wei-Ming Tan
Experiment Date: 2023-11-22, 2023-11-29
Submission Date: 2023-12-06
Lab ID: L09
TA: Kelly Rees
Abstract
In this investigation, coulometric titration methods were designed and applied to determine the
concentration of analytes. An acid-base coulometric titration was performed to determine the
concentrations of hydrochloric acid and acetic acid samples. An iodometric back titration was performed
to determine the concentration of iodine samples. The results of the coulometric titrations were
statistically analyzed through comparison to the results of volumetric titration methods and a true analyte
concentration, respectively. The coulometric acid titration determined the concentration of the
hydrochloric acid sample to be 0.24 ± 0.01 M, and the concentration of the acetic acid sample to be 0.23
± 0.03 M. Statistical analysis of coulometric titration results for the hydrochloric acid sample indicated
that the coulometric titration results were statistically different from the volumetric titration results at the
95% confidence level. Statistical analysis of coulometric titration results for the acetic acid sample
indicated that the coulometric titration results were not statistically different from the volumetric titration
results at the 95% confidence level. The coulometric back titration determined the concentration of the
iodine sample to be 0.0027 ± 0.0008 M. Statistical analysis of coulometric back titration results indicated
no significant statistical difference from the true concentration of the iodine sample at the 95% confidence
level.
Introduction
Coulometry is an electrochemical method applied to quantify the process of redox conversion of
an analyte. Coulometric titration methods rely on the accurate measurement of charge consumed in a
desired redox reaction process to determine the amount of analyte substance reacted 1. Coulometric
methods are advantageous in comparison to other quantification methods due to the ease of design of
constant current systems, the absence of precisely determined standard solutions in experimental designs,
the inconsequence of titrant dilution effects, and high sensitivity and accuracy 2.
In this investigation, coulometric titration methods will first be applied to determine the
concentrations of hydrochloric acid and acetic acid samples. A current will be applied to pass through a
solution containing the analyte acid. The current application induces the oxidation of a silver anode,
2𝐴𝑔( ) → 2𝐴𝑔 + 2𝑒 .

This process induces the corresponding reduction of water at the graphite cathode,
𝐻 𝑂 + 2𝑒 → 𝐻 + 2𝑂𝐻 .
Generated hydroxide neutralizes the added sample of analyte acid,
𝐻𝐴 + 𝑂𝐻 → 𝐻 𝑂 + 𝐶𝑙 .
Notably, sodium chloride is added to the analyte-containing solution, resulting in the precipitation of
produced silver ions as solid silver chloride,
𝐴𝑔 + 𝐶𝑙 → AgCl( ) .

This process prevents the migration of silver ions to the graphite cathode, where the resulting reduction
would interfere with the reaction process.
A pH probe is implemented in the experimental design to detail the neutralization process. The
derivative curve of pH versus time data may be considered to determine the time of acid-base endpoint
achievement. Current data will be recorded with Labquest software. The charge applied to achieve the
endpoint may be determined through the application of the trapezoidal approximation, where,

∫ ∑ ( )(∆ )
𝐶ℎ𝑎𝑟𝑔𝑒 (𝐶) = ≈ .

The total charge applied to achieve the endpoint may be used to determine the concentration of
analyte acid using Faraday’s constant and stoichiometric relationships,
1 1 𝑚𝑜𝑙 𝐻𝑦𝑑𝑟𝑜𝑥𝑖𝑑𝑒 1 𝑚𝑜𝑙 𝐴𝑐𝑖𝑑 1
[𝐴𝑐𝑖𝑑](𝑀) = 𝐶ℎ𝑎𝑟𝑔𝑒 (𝐶) × × × × .
𝐶 1 𝑚𝑜𝑙 𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 1 𝑚𝑜𝑙 𝐻𝑦𝑑𝑟𝑜𝑥𝑖𝑑𝑒 𝑉𝑜𝑙𝑢𝑚𝑒 𝐴𝑐𝑖𝑑 (𝐿)
𝐹𝑎𝑟𝑎𝑑𝑎𝑦 𝑠 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ( )
𝑚𝑜𝑙 𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠

Concurrently, sodium hydroxide will be standardized against potassium hydrogen phthalate;

volumetric titration of the hydrochloric acid and acetic acids against the standardized sodium hydroxide
will be conducted. Statistical analysis will be conducted to compare the results of the volumetric and
coulometric methods.
A coulometric iodometric back titration will then be conducted to determine the concentration of
a provided sample of iodine. An excess of sodium thiosulfate will be added to a solution containing the
iodine sample to induce the reduction of iodine to iodide,
𝐼 + 2𝑆2 𝑂2− − 2−
3 → 2𝐼 + 𝑆4 𝑂6 .

A current will be applied to pass through the solution. The current application induces the oxidation of
iodide at a graphite anode,
2𝐼 → 𝐼2 + 2𝑒− .

Generated molecular iodine will react with remaining thiosulfate ions until exhaustion of the initial
excess. The remaining iodide will form a triiodide complex with molecular iodine,
𝐼 + 𝐼− → 𝐼−3 ,
which will complex with the starch indicator to convert the solution from a clear to a dark blue colour
upon endpoint achievement. The graphite cathode in this experimental design is sequestered from the
analyte solution in a capped Falcon tube with a semi-permeable membrane for separation, such that
reaction products do not interfere with the desired reduction reaction,
𝐻 𝑂 + 2𝑒 → 𝐻 + 2𝑂𝐻 .
Phenolphthalein is added to this Falcon tube to visually indicate successful reaction progression.
A photometer apparatus connected to lab software will be used to detail the reaction process and
provide corresponding voltage data. The derivative curve of pH versus time data may be considered to
determine the time of iodometric titration endpoint achievement. Current data will be recorded with
Labquest software. The charge applied to achieve the endpoint may be determined through the application
of the trapezoidal approximation.
The total charge applied to achieve the endpoint may be used to determine the amount of
thiosulfate reacted using Faraday’s constant and stoichiometric relationships,
 ( )
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑆 𝑂 𝑖𝑛 𝑒𝑥𝑐𝑒𝑠𝑠 = ,
( )

And,

𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑆 𝑂 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 = 𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑆 𝑂 𝑎𝑑𝑑𝑒𝑑 − 𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑆 𝑂 𝑖𝑛 𝑒𝑥𝑐𝑒𝑠𝑠.

Stoichiometry thus may be manipulated to determine the concentration of the iodine sample,

[𝐼𝑜𝑑𝑖𝑛𝑒](𝑀) = 𝑀𝑜𝑙𝑒𝑠 𝑇ℎ𝑖𝑜𝑠𝑢𝑙𝑓𝑎𝑡𝑒 𝑅𝑒𝑎𝑐𝑡𝑒𝑑 × × .

( )

The true concentration of the iodine sample is provided to be 0.003 M. Statistical analysis will be
applied to the results of the coulometric iodometric back titration in comparison to this true value.
Statistical analysis will indicate the accuracy and precision of applied coulometric titration
procedures, allowing for the assessment of the effectiveness of the experimental design to be determined.

Experimental
First, analytes for the acid-base coulometric titration were collected. A 250 mL solution of ~ 0.2
M analyte hydrochloric acid was first prepared by diluting 100 mL of ~ 0.5 M hydrochloric acid with 150
mL of distilled water. Provided acetic acid was already concentrated to ~ 0.2 M; no dilution was
necessary.
Provided ~ 0.1 M sodium hydroxide was standardized through volumetric titration. Samples of
potassium hydrogen phthalate were collected from a desiccator. Samples of ~ 0.3 g of potassium
hydrogen phthalate were accurately weighed and dissolved in ~ 50 mL of distilled water. The sample of
potassium hydrogen phthalate was titrated against the provided sodium hydroxide using 2 drops of
phenolphthalein as the indicator. Aliquots of 6 mL of the ~ 0.2 M hydrochloric acid and the ~ 0.2 M acetic
acid were then similarly titrated against the ~ 0.1 M sodium hydroxide. A total of 6 volumetric titrations
of potassium hydrogen phthalate, hydrochloric acid, and acetic acid were conducted.
Solutions of potassium nitrate and sodium chloride were prepared. A sample of 25.15 g of solid
potassium nitrate was measured and dissolved in 625 mL of distilled water to produce a ~ 0.4 M solution
of potassium nitrate. A sample of 3.6493 g of solid sodium chloride was measured and dissolved in 625
mL of distilled water to produce a ~ 0.1 M solution of sodium chloride.
The coulometric acid-base titrations were then conducted. The LabQuest program and pH meter
were first calibrated using the provided procedures. In a 100 mL beaker, ~ 12.5 mL of the ~ 0.4 M
potassium nitrate solution, ~ 12.5 mL of the ~ 0.1 M sodium chloride solution, ~ 25 mL of distilled water,
2 drops of phenolphthalein, an accurately measured aliquot of 0.1 mL of ~ 0.2 M hydrochloric acid, and a
stir bar were combined. A piece of silver foil was sanded to remove any deposit, then clamped to the red
lead to serve as the anode. A piece of graphite was clamped to the black lead to serve as the cathode. The
apparatus was placed on a stirring plate, and the calibrated pH meter was added to the solution. The
current and pH detector data recording programs were started simultaneously, and the anode was added to
the solution immediately afterward. Upon the establishment of a dark pink endpoint, the recording
programs were stopped. The coulometric acid-base titration was conducted to a total of 6 successful trials:
3 using the ~ 0.2 M acetic acid and 3 using the ~ 0.2 M hydrochloric acid.
 Solutions of potassium iodide, potassium nitrate, and sodium thiosulfate were prepared. A
standard solution of 25 mL of sodium thiosulfate was produced by accurately weighing 0.3013 g of solid
sodium thiosulfate pentahydrate and diluting the volumetric flask to the mark with distilled water
(producing a 0.04856 M solution). A sample of 12.17 g of solid potassium nitrate was measured and
dissolved in 300 mL of distilled water to produce a ~ 0.4 M solution of potassium nitrate. A sample of
24.61 g of solid potassium iodide was measured and dissolved in 750 mL of distilled water to produce a ~
0.2 M solution of potassium iodide.
The coulometric iodometric back titrations were then conducted. The LabQuest program and
photometer were first calibrated using the provided procedures. In a 100 mL beaker, ~ 25 mL of the ~ 0.2
M potassium iodide solution, ~ 25 mL of a provided ~ 0.2 M acetate buffer solution, an accurately
measured aliquot of 1 mL of a provided iodine solution, an excess of 1 mL of a 1% starch indicator
solution, and a stir bar were combined. The beaker was placed within the photometer apparatus, situated
on a stirring plate. The stirring plate and photometer were turned on. An accurately measured aliquot of
0.5 mL of the 0.04856 M sodium thiosulfate solution was added to the beaker. A piece of filter paper was
placed at the base of the Falcon tube, and the tube was capped. The Falcon tube was then partially
submerged in the solution. Enough volume of the ~ 0.4 M solution of potassium nitrate solution was
added to the tube to match the height of the solution in the beaker; 2 drops of phenolphthalein were also
added. The photometer was then adjusted to minimize interference with photometer detection. The black
and red leads were clamped to graphite electrodes. The cathode was then placed into the Falcon tube. The
current and voltage-detecting programs were started simultaneously, and the anode was added to the
solution immediately afterward. Upon the establishment of a dark blue endpoint, the programs were
stopped. The coulometric iodometric titration was conducted to a total of 3 successful trials.
Chemical hazards included hydrochloric acid, acetic acid, sodium hydroxide, potassium nitrate,
potassium iodide, iodine, sodium thiosulfate pentahydrate, and phenolphthalein solutions. Appropriate
Personal Protective Equipment, including safety glasses, shielding clothing, and a lab coat were worn
throughout the duration of the experiment.
Raw Data and Calculations
Figure 1: Standardizing Sodium Hydroxide (Q1)

Trial Number Mass KHP (g) Volume NaOH (mL) Concentration NaOH (M)
1 0.320 15.75 0.09964 M
2 0.2991 15.03 0.09744 M
3 0.2956 14.61 0.09907 M
4 0.3064 15.05 0.09969 M
5 0.2987 15.09 0.09963 M
6 0.3176 15.65 0.09937 M

Figure 1a: sample calculation for determining concentration from titration data (Q1)
𝑀𝑎𝑠𝑠 𝐾𝐻𝑃 (𝑔) 1
𝑔 × 𝑉𝑜𝑙𝑢𝑚𝑒 𝑁𝑎𝑂𝐻 (𝑚𝐿) = 𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑁𝑎𝑂𝐻 (𝑀)
𝑀𝑜𝑙𝑎𝑟 𝑀𝑎𝑠𝑠 𝐾𝐻𝑃 ( )
𝑚𝑜𝑙
0.3205 1
[𝑁𝑎𝑂𝐻] × = 0.09964 𝑀
204.22 15.75 × 10
Figure 2a: average concentration of sodium hydroxide (Q1)

Mean [NaOH] (M) Standard Deviation (M)

0.09869 0.001198

Figure 2b: sample calculations for determining average concentration and standard deviation (Q1)
∑ [𝑁𝑎𝑂𝐻]
𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑁𝑎𝑂𝐻 (𝑀) =
𝑛
0.09964 + 0.09744 + 0.09907 + 0.09969 + 0.09963 + 0.09937
= 0.09869 𝑀
6
𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝐷𝑒𝑣𝑖𝑎𝑡𝑖𝑜𝑛 = 0.001198 𝑀

∑ ([𝑁𝑎𝑂𝐻] − [𝑁𝑎𝑂𝐻] )
𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝐷𝑒𝑣𝑖𝑎𝑡𝑖𝑜𝑛 [𝑁𝑎𝑂𝐻] =
𝑛−1

(0.09964 − 0.09869) + (0.09744 − 0.09869) + (0.09907 − 0.09869) + (0.09969 − 0.09869) + (0.09963 − 0.09869) + (0.1469 − 0.09937)
𝑠𝑑[ ] = = 0.001198
6−1

Figure 3: plot of pH as a function of time; coulometric titration of hydrochloric acid (Q2)

Coulometric HCl Titration: Trial 2

12

10

6
pH

0
100 120 140 160 180 200 220 240 260 280
Time (s)
Figure 4: plot depicting first derivative of date represented in Figure 3 (Q2)

1st Derivative Plot of Coulometric HCl Titration: Trial 2

0.12

0.1

0.08
ΔpH/Δt (s-1)

0.06

0.04

0.02

0
100 120 140 160 180 200 220 240 260 280
1 x Average Time (s)

Figure 5a: volumetric and coulometric results quantifying hydrochloric acid (Q3)
Trial Number Coulometric/Volumetric Charge (C) Concentration HCl (M)
1 Volumetric N/A 0.1846
2 Volumetric N/A 0.1831
3 Volumetric N/A 0.1824
4 Volumetric N/A 0.1834
5 Volumetric N/A 0.1892
6 Volumetric N/A 0.1878
7 Coulometric 2.207 0.2287
8 Coulometric 2.361 0.2438
9 Coulometric 2.396 0.2474

Figure 5b: sample calculation: volumetric hydrochloric acid titration (Q3):

𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝐻𝐶𝑙 (𝑀) = 𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑁𝑎𝑂𝐻 × 𝑉𝑜𝑙𝑢𝑚𝑒 𝑁𝑎𝑂𝐻 (𝐿) ×

( )

1
[𝐻𝐶𝑙] = 0.09869 𝑀 𝑁𝑎𝑂𝐻 × 11.22 × 10 𝐿 𝑁𝑎𝑂𝐻 × = 0.1846 𝑀
6.000 × 10 𝐿 𝐻𝐶𝑙
Figure 5c: sample calculation for application of trapezoidal rule (Q3):

1
𝑇𝑟𝑎𝑝𝑒𝑧𝑜𝑖𝑑𝑎𝑙 𝐴𝑟𝑒𝑎 = (𝑓 + 𝑓 )(∆𝑥 )
2
Approximating the trapezoidal area under the curve of the Current Versus Time curve for Coulometric
HCl Titration between 12 and 13 seconds,

1 1
𝑇𝑟𝑎𝑝𝑒𝑧𝑜𝑖𝑑𝑎𝑙 𝐴𝑟𝑒𝑎 = (𝑓 + 𝑓 )(∆𝑥 ) = (11.58 𝑚𝐴 + 12.28 𝑚𝐴)(1 𝑠) = 11.93 𝑚𝐶
2 2

Figure 5d: sample calculation of charge transfer with trapezoidal approximation: coulometric
hydrochloric acid titration (Q3):
1
∑ (𝑓 + 𝑓 )(∆𝑥 )
𝐶ℎ𝑎𝑟𝑔𝑒 (𝐶) = 2
1000
In trial 1, the endpoint was reached at 257 seconds.
𝑄 .
.

Figure 5e: sample calculation of concentration of hydrochloric acid: coulometric hydrochloric acid
titration (Q3):
1 1 𝑚𝑜𝑙 𝐻𝑦𝑑𝑟𝑜𝑥𝑖𝑑𝑒 1 𝑚𝑜𝑙 𝐻𝑦𝑑𝑟𝑜𝑐ℎ𝑙𝑜𝑟𝑖𝑐 𝐴𝑐𝑖𝑑 1
𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝐻𝐶𝑙 (𝑀) = 𝐶ℎ𝑎𝑟𝑔𝑒 (𝐶) × × × ×
𝐶 1 𝑚𝑜𝑙 𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 1 𝑚𝑜𝑙 𝐻𝑦𝑑𝑟𝑜𝑥𝑖𝑑𝑒 0.1 × 10 𝐿
𝐹𝑎𝑟𝑎𝑑𝑎𝑦𝑠 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ( )
𝑀𝑜𝑙
1 𝑚𝑜𝑙 𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 1 𝑚𝑜𝑙 𝐻𝑦𝑑𝑟𝑜𝑥𝑖𝑑𝑒 1 𝑚𝑜𝑙 𝐻𝑦𝑑𝑟𝑜𝑐ℎ𝑙𝑜𝑟𝑖𝑐 𝐴𝑐𝑖𝑑 1
[𝐻𝐶𝑙] = 2.207 𝐶 × × × × = 0.2287𝑀
96485 𝐶 1 𝑚𝑜𝑙 𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 1 𝑚𝑜𝑙 𝐻𝑦𝑑𝑟𝑜𝑥𝑖𝑑𝑒 0.1 × 10 𝐿

Figure 7a: summary statistics for titration of hydrochloric acid (Q4)

Titration Average Concentration (M) Standard Deviation (M) 95% Confidence Limits (M)
Volumetric 0.1851 0.003 ±0.003
Coulometric 0.2400 0.01 ±0.02

Figure 7b: sample calculation for average concentration of hydrochloric acid: coulometric hydrochloric
acid titration (Q4):
∑ [𝐻𝐶𝑙]
𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝐻𝑦𝑑𝑟𝑜𝑐ℎ𝑙𝑜𝑟𝑖𝑐 𝐴𝑐𝑖𝑑 (𝑀) =
𝑛
0.2287 + 0.2438 + 0.2474
[𝐻𝐶𝑙] = = 0.2400 𝑀
3
Figure 7c: sample calculation for standard deviation of concentration of hydrochloric acid: coulometric
hydrochloric acid titration (Q4):

∑ ([𝐻𝐶𝑙] − [𝐻𝐶𝑙] )
𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝐷𝑒𝑣𝑖𝑎𝑡𝑖𝑜𝑛 [𝐻𝐶𝑙] =
𝑛−1

(0.2287 − 0.2400) + (0.2438 − 0.2400) + (0.2474 − 0.2400)

𝑠𝑑[ ] = = 0.009919 𝑀
3−1
Figure 7d: sample calculation for 95% confidence limits of concentration of hydrochloric acid:
coulometric hydrochloric acid titration (Q4):
𝑡×𝑠
𝐶𝑜𝑛𝑓𝑖𝑑𝑒𝑛𝑐𝑒 𝐿𝑖𝑚𝑖𝑡𝑠 [𝐻𝐶𝑙] = ±
√𝑛
4.303 × 0.009919
𝐶𝑜𝑛𝑓𝑖𝑑𝑒𝑛𝑐𝑒 𝐿𝑖𝑚𝑖𝑡𝑠 [𝐻𝐶𝑙] = ± = ±0.02464 𝑀
√3

Figure 8: comparing volumetric and coulometric methods for titration of hydrochloric acid (Q5):
F-test:

𝑠
𝐹 =
𝑠

9.83804 × 10
𝐹 = = 12.78
7.699 × 10
𝐹 , , = 5.786

𝐹 >𝐹

It may be concluded that the two variances are statistically different.

Case 2 t-test given negative result F-test:
|𝑥 − 𝑥 |
𝑡 =
𝑠 𝑠
+
𝑁 𝑁

|0.1851 − 0.2400|
𝑡 = = 9.41
9.83804 × 10 7.699 × 10
+
3 6
𝑠 𝑠
( + )
𝑁 𝑁
𝐷𝑂𝐹 = −2
𝑠 𝑠
( ) ( )
𝑁 𝑁
+
𝑁 +1 𝑁 +1
9.83804 × 10 7.699 × 10
( + )
𝐷𝑂𝐹 = 3 6 − 2 = 2.32
9.83804 × 10 7.699 × 10
( ) ( )
3 + 6
3+1 6+1
𝑡 , = 4.303
 𝑡 >𝑡

Thus, the t-test indicates that the two results are statistically different. The null hypothesis is rejected.
Case 2 t-test given negative result F-test:
|𝑥 − 𝑥 |
𝑡 =
𝑠 𝑠
+
𝑁 𝑁

|0.1851 − 0.2400|
𝑡 = = 9.41
9.83804 × 10 7.699 × 10
+
3 6
𝑠 𝑠
( + )
𝑁 𝑁
𝐷𝑂𝐹 = −2
𝑠 𝑠
( ) ( )
𝑁 𝑁
+
𝑁 +1 𝑁 +1
9.83804 × 10 7.699 × 10
( + )
𝐷𝑂𝐹 = 3 6 − 2 = 2.32
9.83804 × 10 7.699 × 10
( ) ( )
3 + 6
3+1 6+1
𝑡 , = 4.303

𝑡 >𝑡

Thus, the t-test indicates that the two results are statistically different.

Figure 9a: volumetric and coulometric results quantifying acetic acid (Q3)
Concentration Acetic
Trial Number Coulometric/Volumetric Charge (C)
Acid (M)
1 Volumetric N/A 0.1966
2 Volumetric N/A 0.1974
3 Volumetric N/A 0.1949
4 Volumetric N/A 0.1933
5 Volumetric N/A 0.1974
6 Volumetric N/A 0.1908
7 Coulometric 2.432 0.2521
8 Coulometric 2.218 0.2299
9 Coulometric 1.948 0.2019

Figure 9b: sample calculation: volumetric acetic acid titration (Q3):

𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝐴𝑐𝑒𝑡𝑖𝑐 𝐴𝑐𝑖𝑑 (𝑀) = 𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑁𝑎𝑂𝐻 × 𝑉𝑜𝑙𝑢𝑚𝑒 𝑁𝑎𝑂𝐻 (𝐿) ×
( )
 1
[𝐻𝐶𝐻 𝐶𝑂𝑂𝐻] = 0.09869 𝑀 𝑁𝑎𝑂𝐻 × 11.95 × 10 𝐿 𝑁𝑎𝑂𝐻 × = 0.1966 𝑀
6.000 × 10 𝐿 𝐻𝐶𝐻 𝐶𝑂𝑂𝐻

Figure 9c: sample calculation of charge transfer with trapezoidal approximation: coulometric acetic acid
titration (Q3):
1
∑ (𝑓 + 𝑓 )(∆𝑥 )
𝐶ℎ𝑎𝑟𝑔𝑒 (𝐶) = 2
1000
𝑄 .
.

Figure 5d: sample calculation of concentration of acetic acid: coulometric acetic acid titration (Q3):
1 1 𝑚𝑜𝑙 𝐻𝑦𝑑𝑟𝑜𝑥𝑖𝑑𝑒 1 𝑚𝑜𝑙 𝐴𝑐𝑒𝑡𝑖𝑐 𝐴𝑐𝑖𝑑 1
𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝐴𝑐𝑒𝑡𝑖𝑐 𝐴𝑐𝑖𝑑 (𝑀) = 𝐶ℎ𝑎𝑟𝑔𝑒 (𝐶) × × × ×
𝐶 2 𝑚𝑜𝑙 𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 1 𝑚𝑜𝑙 𝐻𝑦𝑑𝑟𝑜𝑥𝑖𝑑𝑒 0.1 × 10 𝐿
𝐹𝑎𝑟𝑎𝑑𝑎𝑦𝑠 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ( )
𝑀𝑜𝑙
1 𝑚𝑜𝑙 𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 1 𝑚𝑜𝑙 𝐻𝑦𝑑𝑟𝑜𝑥𝑖𝑑𝑒 1 𝑚𝑜𝑙 𝐴𝑐𝑒𝑡𝑖𝑐 𝐴𝑐𝑖𝑑 1
[𝐻𝐶𝐻3 𝐶𝑂𝑂𝐻] = 2.423 𝐶 × × × × = 0.2521 𝑀
96485 𝐶 1 𝑚𝑜𝑙 𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 1 𝑚𝑜𝑙 𝐻𝑦𝑑𝑟𝑜𝑥𝑖𝑑𝑒 0.1 × 10 𝐿

Figure 10a: summary statistics for titration of acetic acid (Q4)

Titration Average Concentration (M) Standard Deviation (M) 95% Confidence Limits (M)
Volumetric 0.1951 0.003 ±0.003
Coulometric 0.2279 0.03 ±0.06

Figure 10b: sample calculation for average concentration of acetic acid: coulometric acetic acid titration
(Q4):
∑ [𝐻𝐶𝐻3 𝐶𝑂𝑂𝐻]
𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝐴𝑐𝑒𝑡𝑖𝑐 𝐴𝑐𝑖𝑑 (𝑀) =
𝑛
(0.2521) + (0.2299) + (0.2019)
[𝐻𝐶𝐻3 𝐶𝑂𝑂𝐻] = = 0.2279 𝑀
3
Figure 10c: sample calculation for standard deviation of concentration of acetic acid: coulometric acetic
acid titration (Q4):

∑ ([𝐻𝐶𝐻3 𝐶𝑂𝑂𝐻] − [𝐻𝐶𝐻3 𝐶𝑂𝑂𝐻] )

𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝐷𝑒𝑣𝑖𝑎𝑡𝑖𝑜𝑛 [𝐻𝐶𝐻3 𝐶𝑂𝑂𝐻] =
𝑛−1

(0.2521 − 0.2279 ) + (0.2299 − 0.2279 ) + (0.2019 − 0.2279 )

𝑠𝑑[𝐻𝐶𝐻3 𝐶𝑂𝑂𝐻] = = 0.02515 𝑀
3−1

Figure 10d: sample calculation for 95% confidence limits of concentration of acetic acid: coulometric
acetic acid titration (Q4):
𝑡×𝑠
𝐶𝑜𝑛𝑓𝑖𝑑𝑒𝑛𝑐𝑒 𝐿𝑖𝑚𝑖𝑡𝑠 [𝐻𝐶𝐻3 𝐶𝑂𝑂𝐻] = ±
√𝑛
 4.303 × 0.02515
𝐶𝑜𝑛𝑓𝑖𝑑𝑒𝑛𝑐𝑒 𝐿𝑖𝑚𝑖𝑡𝑠 [𝐻𝐶𝐻3 𝐶𝑂𝑂𝐻] = ± = ±0.06249 𝑀
√3

Figure 11: comparing volumetric and coulometric methods for titration of acetic acid (Q6):
F-test:

𝑠
𝐹 =
𝑠

6.326 × 10
𝐹 = = 92.00
6.877 × 10
𝐹 , , = 5.786

𝐹 >𝐹

It may be concluded that the two variances are statistically different.

Case 2 t-test given negative result F-test:
|𝑥 − 𝑥 |
𝑡 =
𝑠 𝑠
+
𝑁 𝑁

|0.2279 − 0.1951|
𝑡 = = 2.259
6.326 × 10 6.877 × 10
+
3 6
𝑠 𝑠
( + )
𝑁 𝑁
𝐷𝑂𝐹 = −2
𝑠 𝑠
( ) ( )
𝑁 𝑁
+
𝑁 +1 𝑁 +1

6.326 × 10 6.877 × 10
( + )
𝐷𝑂𝐹 = 3 6 − 2 = 2.04
6.326 × 10 6.877 × 10
( ) ( )
3 + 6
3+1 6+1
𝑡 , = 4.303

𝑡 <𝑡

The t-test indicates that there is no significant statistical difference between the results at the 95%
confidence interval.
Figure 12: plot of voltage against time; coulometric iodometric back titration (Q7)

Iodometric Back Titration: Trial 4

1.4

1.2

1
Voltage (V)

0.8

0.6

0.4

0.2

0
0 50 100 150 200 250
Time (s)

Figure 13: plot depicting the first derivative of date represented in Figure 12 (Q7)

1st Derivative Plot of Iodometric Back Titration: Trial 4

0.15

0.1

0.05

0
ΔV/Δt (s-1)

0 50 100 150 200 250

-0.05

-0.1

-0.15

-0.2

-0.25
1 x Average Time (s)

Figure 14a: iodometric back titration results quantifying iodine (Q8)

Trial Number Charge (C) Moles Excess S2O32- [I2] (M)
3 1.884 1.952x10-5 0.002378
4 1.647 1.707x10-5 0.003606
5 1.947 2.018 x10-5 0.002051
Figure 14b: sample calculation for charge transfer using trapezoidal approximation (Q8):
For trial 4, the endpoint was reached at 182 seconds.
1
∑ (𝑓 + 𝑓 )(∆𝑥 )
𝐶ℎ𝑎𝑟𝑔𝑒 (𝐶) = 2
1000
𝑄 .
.

Figure 14c: sample calculation for excess moles of thiosulfate (Q8):

𝐶ℎ𝑎𝑟𝑔𝑒 (𝐶)
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑆 𝑂 =
𝐶
𝐹𝑎𝑟𝑎𝑑𝑎𝑦 𝑠 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ( )
𝑚𝑜𝑙

1.647 𝐶
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑆 𝑂 = = 1.707𝑥10 𝑚𝑜𝑙𝑠
𝐶
96, 485 ( )
𝑚𝑜𝑙
Figure 14d: sample calculation for concentration of sodium thiosulfate: coulometric iodometric back
titration (Q8):
1 1
𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑇ℎ𝑖𝑜𝑠𝑢𝑙𝑓𝑎𝑡𝑒 (𝑀) = 𝑚𝑎𝑠𝑠 𝑆𝑜𝑑𝑖𝑢𝑚 𝑇ℎ𝑖𝑜𝑠𝑢𝑙𝑓𝑎𝑡𝑒 𝑃𝑒𝑛𝑡𝑎ℎ𝑦𝑑𝑟𝑎𝑡𝑒 (𝑔) × 𝑔 × 25 × 10 𝐿
𝑀𝑜𝑙𝑎𝑟 𝑀𝑎𝑠𝑠 𝑆𝑜𝑑𝑖𝑢𝑚 𝑇ℎ𝑖𝑜𝑠𝑢𝑙𝑓𝑎𝑡𝑒 𝑃𝑒𝑛𝑡𝑎ℎ𝑦𝑑𝑟𝑎𝑡𝑒 (
𝑚𝑜𝑙)

1 1
[𝑁𝑎 𝑆 𝑂 ] = 0.3013 𝑔 × 𝑔 × 25 × 10 𝐿 = 0.04856 𝑀
248.18 (
𝑚𝑜𝑙)

Figure 14e: sample calculation for concentration of iodine: coulometric iodometric back titration (Q8):

𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑁𝑎 𝑆 𝑂 𝑎𝑑𝑑𝑒𝑑 − 𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑆 𝑂 𝑖𝑛 𝑒𝑥𝑐𝑒𝑠𝑠 1

𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐼𝑜𝑑𝑖𝑛𝑒 (𝑀) = ×
2 1 × 10 𝐿
0.04856 𝑚𝑜𝑙𝑠
× 0.5 × 10−3 𝐿 − 1.707𝑥10 𝑚𝑜𝑙𝑠 1
[𝐼 ] = 1 𝐿 × = 0.003606 𝑀
2 1 × 10−3 𝐿

Figure 15a: summary statistics for coulometric iodometric back titration (Q9)
Titration Average Concentration (M) Standard Deviation (M) 95% Confidence Limits (M)
Back Titration 0.002679 0.0008 ±0.002

Figure 15b: sample calculation for average concentration of iodine: coulometric iodometric back titration
(Q9):
∑ [𝐼 ]
𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝐼𝑜𝑑𝑖𝑛𝑒 (𝑀) =
𝑛
 (0.002378) + (0.003606) + (0.002051)
𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝐼𝑜𝑑𝑖𝑛𝑒 (𝑀) = = 0.002679 𝑀
3
Figure 15c: sample calculation for standard deviation of concentration of iodine: coulometric iodometric
back titration (Q9):

∑ ([𝐼 ] − [𝐼 ] )
𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝐷𝑒𝑣𝑖𝑎𝑡𝑖𝑜𝑛 [𝐼 ] =
𝑛−1

(0.002378 − 0.002679) + (0.003606 − 0.002679) + (0.002051 − 0.002679)

𝑠𝑑[ ] = = 0.0008 𝑀
3−1

Figure 15d: sample calculation for 95% confidence limits of concentration of iodine: coulometric
iodometric back titration (Q9):
𝑡×𝑠
𝐶𝑜𝑛𝑓𝑖𝑑𝑒𝑛𝑐𝑒 𝐿𝑖𝑚𝑖𝑡𝑠 [𝐼2 ] = ±
√𝑛
4.303 × 0.0008
𝐶𝑜𝑛𝑓𝑖𝑑𝑒𝑛𝑐𝑒 𝐿𝑖𝑚𝑖𝑡𝑠 [𝐼2 ] = ± = ± 0.02037 𝑀
√3

Figure 16: comparing iodometric back titration result to true value (Q10)
Case-1 t-test:

|𝑥̅ − 𝜇|√𝑁
𝑡 =
𝑠
|0.002679 − 0.003|√3
𝑡 = = 0.6950
0.0008
𝑡 , = 4.303

𝑡 <𝑡

The results are not statistically different at the 95% confidence level.
Results
Table 1: Calculated Concentrations of Sodium Hydroxide

Trial [NaOH] (M)

1 0. 09964

2 0. 09744

3 0. 09907

4 0. 09969

5 0. 09963

6 0.09937

Table 2: Average Concentration of Sodium Hydroxide

Mean [NaOH] (M) Standard Deviation (M)

0.099 0.001

Table 3: Determinations from Volumetric and Coulometric Titrations of Hydrochloric Acid

Hydrochloric Acid (HCl)

Trial Titration Type Charge (C) [HCl] (M)

1 Volumetric - 0. 1846

2 Volumetric - 0. 1831

3 Volumetric - 0. 1824

4 Volumetric - 0. 1834

5 Volumetric - 0. 1892

6 Volumetric - 0.1878

6 Coulometric 2.21 0. 229

 7 Coulometric 2.36 0. 244

8 Coulometric 2.40 0. 247

Table 4: Summary Statistics for Titrations of Hydrochloric Acid

Hydrochloric Acid (HCl)

Titration Type Volumetric Coulometric

Mean [HCl] (M) 0.185 0.24

Standard Deviation (M) 0. 003 0.01

95% CL (M) ±0.003 ±0.02

Table 5: Determinations from Volumetric and Coulometric Titrations of Acetic Acid

Acetic Acid (CH COOH)

3

Trial Titration Type Charge (C) [CH COOH] (M)

3

1 Volumetric - 0. 1966

2 Volumetric - 0. 1974

3 Volumetric - 0. 1949

4 Volumetric - 0. 1933

5 Volumetric - 0. 1974

6 Volumetric - 0.1908

6 Coulometric 2.43 0.252

7 Coulometric 2.22 0.230

8 Coulometric 1.95 0.202

Table 6: Summary Statistics for Titrations of Acetic Acid

Acetic Acid (CH3COOH)

Titration Type Volumetric Coulometric

Mean [CH3COOH] (M) 0. 195 0. 23

Standard Deviation (M) 0.003 0.03

95% CL (M) ±0.003 ±0.06

Table 8: Result of Statistical Comparison of Titrations Results for Hydrochloric Acid

Hydrochloric Acid (HCl)

F-Test t-Test

Calculated Table Value Calculated Table Value

12.78 5.786 9.41 4.303

F > F = Statistically Different

cal table t > t = Statistically Different
cal table

Table 9: Result of Statistical Comparison of Titrations Results for Acetic Acid

Acetic Acid (CH3COOH)

F-Test t-Test

Calculated Table Value Calculated Table Value

92.00 5.786 2.259 4.303

F > F = Statistically Different

cal table t < t = Not Statistically Different
cal table
Table 10: Determinations from Coulometric Iodometric Back Titration

Coulometric Iodine Back Titration

Trial Charge (C) Moles Excess S O 2 3

2-
[I ] (M)
2

1 1.88 1.95x10-5 0.00238

2 1.65 1.71x10-5 0.00361

3 1.95 2.02 x10-5 0.00215

Table 11: Summary Statistics for Coulometric Iodometric Back Titration

Coulometric Iodine Back Titration

Mean [I ] (M)
2 0.0027

Standard Dev. 0.0008

95% CL ±0.002

Table 12: Result of Statistical Comparison of Titration Result to Provided Value

Coulometric Iodine Back Titration

t-Test

Calculated Table Value

0.6790 4.303

t < t = Not Statistically Different

cal table

Discussion
In this investigation, two different coulometric titration methods were used to determine the
concentration of different analyte species; the results of these methods were analyzed for accuracy and
precision to indicate the applicability of the respective methods.
Acid coulometric titration methods were first explored. This coulometric titration method
involved applying a current to a solution to induce the reduction of water to hydroxide; this process
induced the neutralization of an analyte acid. Lab software was used in conjunction with a pH probe and a
constant current system to allow the determination of charge applied to achieve an acid-base endpoint,
allowing for the quantification of analyte acid. Within the experimental design, the electrodes are inserted
into the same solution. The silver anode is selected to undergo oxidation; however, produced silver
cations may migrate to the graphite cathode to undergo reduction and interfere with the necessary titration
measurements. To prevent this, a halide salt is added to the solution. The halides chlorine, bromine, and
iodine form insoluble precipitates with silver cations; as the silver cations plate onto the silver anode, the
ions are not permitted to migrate to the cathode. To select between the common halide salts sodium
chloride, sodium iodide, and sodium bromide, the standard reduction potentials of the produced silver
halide are considered:
𝐸𝐴𝑔𝐶𝑙 = 0.2223 𝑉, 4

𝐸𝐴𝑔𝐵𝑟 = 0.071 𝑉, 4

𝐸𝐴𝑔𝐼 = −0.152 𝑉. 4

As silver chloride has the highest reduction potential of the listed silver halides, it also
corresponds to the lowest oxidation potential. This characteristic is desirable because the silver halides
plate onto the silver anode and are available to conduct charge through the system. If the alkyl halide
were to be oxidized instead of the silver anode, the known stoichiometric relationship of the coulometric
acid titration would be disrupted; a minimized standard oxidation potential is sought. Thus, sodium
chloride is applied to the solution despite the high solubility of silver chloride (Q7). Better accuracy is
possible as a result of this design.
While the charge detection software should be stringently calibrated, the applied experimental
design of the acid coulometric titrations is particularly useful in reducing the concern for mis-calibrated
pH detection equipment. For example, it is not particularly concerning if two pH probes measuring the
same sample display slightly different results. In either case, the pH data recorded throughout the trial is
used only to determine the time of endpoint achievement, which is indicated by a peak on the first
derivative curve of a curve of pH against time. A pH probe that displays a positively biased pH value will
indicate equivalence point occurrence at a higher pH value; however, as charge transfer is determined
with time of endpoint achievement, using pH data only as an indicative measure, the accuracy of endpoint
determination is not impacted (Q3). It is also important to note that an initial spike in pH occurs at the
beginning of the coulometric acid titration trials. This process occurs because the buffering capacity of the
acid solution is initially minimal when the acid is present in a large excess7. As the titration continues, the
addition of base results in the establishment of a buffer region causing the pH to increase at a slower rate.
Similarly, near the end of the titration, very little acid is present in the solution so the buffering capacity of
the acid decreases7. A sudden increase in pH is again to be expected (Q2).
Volumetric acid titration methods were used in contrast to acid coulometric titration methods.
potassium hydrogen phthalate was titrated against sodium hydroxide to standardize the base; volumetric
titrations were then conducted to quantify the analyte acids. The manual nature of volumetric titration
introduces several potential sources of complication and error. As titrant species must be standardized,
and added manually, the experimental process can become complicated. Additionally, reliance on an acid-
base indicator for determination of endpoint achievement introduces error. Acid-base indicators change
pH throughout a range of pH values; certain indicators are prone to systematic over-estimation or under-
estimation of acid-base endpoints (depending on the identities of titrant and titrand). Interpretation of an
indicator acid-base endpoint is also ambiguous due to the interpretive nature of the measurements.
Coulometric acid titrations, in contrast, rely on precise recording of current and pH data, allowing for
mathematical determination of an acid-base endpoint achievement and analyte concentration. As titrant is
generated to a high level of control, acid coulometric titration methods permit a great degree of precision
and are thus preferable to volumetric titration methods despite requiring sensitive equipment and a time-
consuming experimental design3 (Q6).
Within this investigation, the concentrations of hydrochloric acid and acetic acid were determined
from volumetric titration to be 0.185 ± 0.003 M and 0.195 ± 0.003 M respectively, and from coulometric
titration to be 0.24 ± 0.01 M and 0. 23 ± 0.03 M, respectively.
These results indicate reduced precision for coulometric acid titration methods in comparison to
volumetric acid titration methods. This result is indicated through the application of an F-test, through
which the variance of the results of the coulometric acid titrations were determined to be statistically
different from the variance of the results of the volumetric titrations. Further, the concentrations of
hydrochloric acid determined from coulometric acid titration methods were determined to be statistically
different from the concentrations of hydrochloric acid determined from volumetric acid titration methods,
while the concentrations of acetic acid determined from coulometric acid titration methods were
determined not to be statistically different from the concentrations of acetic acid determined from
volumetric acid titration methods. These results are indicated through the application of case 2 t-tests
(accounting for statistically dissimilar variances). It may be concluded that the accuracy of results
between methods in the determination of the concentration of Hydrochloric Acid was dissimilar, while the
accuracy of results between methods in the determination of the concentration of Acetic Acid was similar.
These results contradict the accepted characteristics of coulometric titration methods3 and
indicate the necessity of improvement to experimental design and implementation to improve accuracy
and precision. Error may have contributed to this result. It is possible that there was incomplete
precipitation of silver cations, resulting in migration to the cathode and reaction disruption. If this
interference occurred, an increased charge input would have been necessary to neutralize the analyte acid,
and the results of the coulometric acid titration would have been positively biased. The experimental
design could be adjusted to physically separate the anodic and cathodic compartments while
implementing a selectively permeable membrane in a future investigation test for the effect of this error.
Coulometric iodometric back titration methods were then explored. This titration method
involved reducing a provided sample of iodine to iodide with a known quantity of thiosulfate ions, then
applying a charge to the solution to induce the oxidation of iodide to form iodine. Generated iodine
reacted preferentially to exhaust the excess of thiosulfate ions, then to complex with the provided starch
indicator. Lab software was used in conjunction with a photometer and a constant current system to allow
the determination of charge applied to achieve an acid-base endpoint, which allowed for the
quantification of analyte Iodine. To permit accurate results, it is important to buffer the analyte solution at
an acidic pH by applying an acetate buffer to the solution. At the inert graphite cathode, the preferential
reduction half-reaction is the reduction of water to produce Hydroxide,
𝐻 𝑂 + 2𝑒 → 𝐻 + 2𝑂𝐻 .
However, unlike in the coulometric acid titration method, wherein the produced hydroxide was
immediately neutralized by the analyte acid, there is no source of hydronium in the coulometric
iodometric back titration experimental design to neutralize the produced hydroxide. Consequently, water
cannot be regenerated through the neutralization process,
𝑂𝐻 + 𝐻 𝑂 → 2𝐻 𝑂.
 As water becomes less abundant throughout the titration, the reduction of water at the cathode
would be impacted. An acetate buffer solution can cross the semi-permeable membrane separating the
Falcon tube from the analyte solution6 and is thus able to react with the produced hydroxide to produce
water,
𝐶𝐻 𝐶𝑂𝑂𝐻 + 𝑂𝐻 → 𝐶𝐻 𝐶𝑂𝑂 + 𝐻 𝑂.
This ensures the constant reduction of water occurs during the titration process 6 (Q4).
While the coulometric acid titration design allowed for the induced reduction of water to produce
the titrant Hydroxide, thus allowing for a direct coulometric titration to be performed, a similar design is
not possible in a process using iodine as the analyte. The inert electrodes provided by the experimental
design are graphite; the application of current induces the preferential reduction of water to hydroxide and
hydrogen gas, and the oxidation of iodide to iodine. The required titrant in an iodometric titration is
thiosulfate. However, no combination of the provided chemical substances would produce quantifiably
produce thiosulfate to act as the titrant in a direct coulometric titration design. Even if an excess of
tetrathionate ion was provided, a direct titration analogous to the design of the applied acid coulometric
titration would not function. The tetrathionate ion, produced through the oxidation of thiosulfate in a
reaction with iodine is not reduced preferentially at the cathode. Iodine, no longer separated from the
cathode by a semi-permeable membrane, would be reduced at the cathode 4,
𝐸𝑆 2− 2− = 0.080 𝑉,
4 𝑂6 /𝑆2 𝑂3

𝐸𝐼2/𝐼− = 0.5355 𝑉,

𝐸𝐻2 𝑂/𝑂𝐻− = −0.828 𝑉,

which would interfere with the titration process. Aside, a coulometric iodometric back titration is
necessary in this case (Q9).
Though the quantification of iodine is strict in the necessary application of a coulometric
iodometric back titration; the quantification of an acid analyte is more flexible. For example, a
coulometric acid back titration may be conducted in place of the coulometric acid titration conducted in
this investigation. For example, a basic salt such as calcium phosphate may be dissolved in an excess of
strong acid, such as hydrochloric acid. A current can then be applied to the solution containing the excess
of hydrochloric acid; the preferential reduction of water to produce hydroxide again supplements the
titrant for excess determination (Q8). Such methods could be used to quantify many basic analytes.
Notably, unlike in the coulometric iodometric back titration, the use of the standard indicator, in
conjunction with a photometer, is not effective in detailing the reaction progress. While the starch and
triiodide complex produces a dark and opaque solution upon endpoint achievement, the reaction between
the generated hydroxide and phenolphthalein produces a translucent pink solution upon endpoint
achievement. The transmittance of light is reduced to a lesser extent upon the achievement of a
phenolphthalein and hydroxide endpoint in comparison to the achievement of a starch and Triiodide
endpoint5. As the visible endpoint will not be as sharp5, the determination of the acid-base endpoint
through this method is likely less accurate (Q5). Instead, a pH probe system in a similar design to that
used in the direct coulometric acid titration should be implemented.
It is important to note that the maximum possible current for the coulometric acid titration was
higher than that for the iodine titration when using the same LabQuest device. This is caused in part by
the higher ionic strength of the analyzed solution. A higher concentration of ions in solution contributes to
the higher ionic strength, which results in high solution conductivity 8. The high current observed in the
coulometric acid titration is advantageous in that the reaction occurs at a faster rate, as the rate of electron
transfer is increased. However, a higher current can induce more noise to be recorded in measurements of
current, as was observed during several conducted trials of the coulometric acid titration; resultingly,
calculations to determine charge transfer based on the applied Trapezoidal Approximation are less
accurate (Q1).

Within this investigation, the concentration of iodine was determined to be 0.0027 ± 0.0008 M
through coulometric iodometric back titration. This experimental value was contrasted with the provided
true concentration of the iodine sample of 0.003 M.
The concentration of iodine determined from the coulometric iodometric back titration method
was determined to be not statistically different from the provided true concentration of the iodine sample
at the 95% confidence level. This result is indicated through the application of a case 1 t-test.
The result contradicts the accepted characteristics of coulometric titration methods 3 and indicates
the necessity of improvement to experimental design and implementation to improve both accuracy and
precision. The production of triiodide (which complexes briefly with the starch indicator) throughout the
titration produced intermittent interferences of the photodetection measurement. This effect is visible as
the significant noise present on the curves derived from experimental data. As a result, determined
endpoints are imprecise and accuracy is impeded. A larger beaker (though not compatible with the
photodetector used), should be used to increase the distance between the cathodic reaction and the
photodetector. Recorded noise would be reduced as increased diffusion would more rapidly eliminate
visible complex.
Conclusion
Coulometric acid titration to determine the concentrations of samples of hydrochloric acid and
acetic acid yielded concentrations of 0.24 ± 0.01 M and 0. 23 ± 0.03 M, respectively. Additionally,
coulometric iodometric back titration to determine the concentration of a sample of iodine solution
yielded a concentration of 0.0027 ± 0.0008 M. Statistical analysis indicated that the determined
concentration of hydrochloric acid was statistically different from the volumetric titration result at the
95% confidence level, the determined concentration of acetic acid was not statistically different from the
volumetric titration result at the 95% confidence level, and the determined concentration of iodine
solution was not statistically different from the true value at the 95% confidence level. The results of the
investigation indicate that poor precision and varying levels of accuracy for the applied coulometric
methods imply the need for improved experimental design and implementation to justify the application
of coulometric methods. The results of the investigation may be applied to future investigations and
critical analyses of other titration methods.
References

1) Hauser, P.C. Encyclopedia of Analytical Science (Second Edition). Edited by Paul Worsfold et

al., Second ed., Elsevier, 2005, pp. 234–240.

2) De Agostini, A. Coulometric Titration. Usercom 7, May 2002 (Retrieved from

[Link]

[Link]/file/global/pdf/sinews/technical_explanation/[Link])

[Link]

000248d2000262f2000a96c1_files/UserCom7_coulometer.pdf ). Accessed 6 Dec. 2023.

3) Harvey, David. “11.3: Coulometric Methods.” Chemistry LibreTexts, 24 Dec. 2016,

[Link]/Courses/Northeastern_University/11%3A_Electrochemical_Methods/
11.3%3A_Coulometric_Methods. Accessed 6 Dec. 2023.
4) “P1: Standard Reduction Potentials by Element.” Chemistry LibreTexts, 2 Dec. 2013,

[Link]/Ancillary_Materials/Reference/Reference_Tables/Electrochemistry_

Tables/P1%3A_Standard_Reduction_Potentials_by_Element. Accessed Dec. 2023.

5) Harvey, David. “9.4: Redox Titrations.” Chemistry LibreTexts, 15 July 2019,

[Link]/Bookshelves/Analytical_Chemistry/Analytical_Chemistry_2.1_(Harv

ey)/09%3A_Titrimetric_Methods/9.04%3A_Redox_Titrations. Accessed 6 Dec. 2023.

6) Noria Corporation. “Karl Fischer Coulometric Titration Explained and Illustrated.”

[Link], [Link]/Read/594/karl-fischer-

coulometric-titration. Accessed 6 Dec. 2023.

7) Alviar-Agnew, Marisa , and Henry Agnew. “14.10: Buffers: Solutions That Resist PH

Change.” Libretexts, 11 Aug. 2017,

[Link]/Courses/Woodland_Community_College/WCC%3A_Chem_10_-

_Concepts_of_Chemistry/Chapters/14%3A_Acids_and_Bases/14.10%3A_Buffers%3A_

Solutions_That_Resist_pH_Change. Accessed 6 Dec. 2023.

Appendix

Hydrochloric Acid Titration: Trial One

Coulometric HCl Titration: Trial 1

15

10
pH

0
100 150 200 250
Time (s)

1st Derivative Plot of the Coulometric HCl

titration Trial 1
0.1
0.08
ΔpH/Δt (s-1)

0.06
0.04
0.02
0
100 150 200 250
1 x Average Time (s)

Coulometric Hydrochloric Acid

Titration: Trial 1
15
Current (mA)

10

0
0 100 200 300 400
-5
Time (s)
Hydrochloric Acid Titration: Trial Two

Coulometric HCl Titration: Trial 2

12

10

6
pH

0
100 150 200 250
Time (s)

1st Derivative Plot of Coulometric HCl Titration: Trial 2

0.12
0.1
0.08
ΔpH/Δt (s-1)

0.06
0.04
0.02
0
100 150 200 250
1 x Average Time (s)

Coulometric Hydrochloric Acid Titration:

Trial 2
15

10
Current (mA)

0
0 50 100 150 200 250 300
-5
Time (s)
Hydrochloric Acid Titration: Trial Three

Coulometric HCl Titration: Trial 3

12
10
8
6
pH

4
2
0
50 100 150 200 250 300
Time (s)

1st Derivative Plot of Coulometric HCl Titration: Trial 3

0.12

0.1

0.08
ΔpH/Δt (s-1)

0.06

0.04

0.02

0
100 150 200 250
1 x Average Time (s)

Coulometric Hydrochloric Acid Titration: Trial

3
14
12
Current (mA)

10
8
6
4
2
0
0 50 100 150 200 250 300 350
Time (s)
Acetic Acid Titration: Trial One

Coulometric Acetic Acid Titration: Trial 1

12

10

6
pH

0
50 100 150 200 250 300
Time (s)

1st Derivative Plot of Coulometric Acetic Acid Titration: Trial 1

0.1
0.09
0.08
0.07
ΔpH/Δt (s-1)

0.06
0.05
0.04
0.03
0.02
0.01
0
100 150 200 250
1 x Average Time (s)

Coulometric Acetic Acid Titration: Trial 1

14
12
10
Current (mA)

8
6
4
2
0
-2 0 50 100 150 200 250 300 350
-4
Time (s)
Acetic Acid Titration: Trial Two

Coulometric Acetic Acid Titration: Trial 2

12

10

6
pH

0
50 100 150 200 250
Time (s)

1st Derivative Plot of Coulometric Acetic Acid Titration: Trial 2

0.1
0.09
0.08
0.07
ΔpH/Δt (s-1)

0.06
0.05
0.04
0.03
0.02
0.01
0
100 150 200 250
1 x Average Time (s)

Coulometric Acetic Acid Titration: Trial 2

14
12
10
8
Current (mA)

6
4
2
0
-2 0 50 100 150 200 250 300
-4
Time (s)
Acetic Acid Titration: Trial Three

Coulometric Acetic Acid Titration: Trial 3

12

10

6
pH

0
50 100 150 200 250
Time (s)

1st Derivative Plot of Coulometric Acetic Acid Titration:

0.12 Trial 3

0.1

0.08
ΔpH/Δt (s-1)

0.06

0.04

0.02

0
100 150 200 250
1 x Average Time (s)

Coulometric Acetic Acid Titration: Trial 3

14
12
Current (mA)

10
8
6
4
2
0
0 50 100 150 200 250 300 350
Time (s)
Iodometric Titration: Trial Three

Iodometric Back Titration: Trial 3

1.4
1.2
1
Voltage (V)

0.8
0.6
0.4
0.2
0
0 50 100 150 200 250
Time (s)

1st Derivative Plot of Iodometric Back Titration:

Trial 3
0.1
ΔV/Δt (s-1)

0
0 50 100 150 200 250
-0.1

-0.2
1 x Average Time

Iodometric Back Titration: Trial 3

18
16
14
Current (mA)

12
10
8
6
4
2
0
0 50 100 150 200 250
Time (s)
Iodometric Titration: Trial Four

Iodometric Back Titration: Trial 4

1.4
1.2
1
Voltage (V)

0.8
0.6
0.4
0.2
0
0 50 100 150 200 250
Time (s)

1st Derivative Plot of Iodometric Back Titration:

Trial 4
0.15
0.1
0.05
ΔV/Δt (s-1)

0
-0.05 0 50 100 150 200 250

-0.1
-0.15
-0.2
-0.25
1 x Average Time (s)

Iodometric Back Titration: Trial 4

14
12
10
Current (mA)

8
6
4
2
0
0 50 100 150 200 250
Time (s)
Iodometric Titration: Trial Five

Iodometric Back Titration: Trial 5

1.4
1.2
1
Voltage (V)

0.8
0.6
0.4
0.2
0
0 50 100 150 200 250 300
Time (s)

1st Derivative Plot of Iodometric Back Titration: Trial 5

0.1

0.05

0
0 50 100 150 200 250 300
ΔV/Δt (s-1

-0.05

-0.1

-0.15

-0.2

-0.25
1 x Average Time (s)

Iodometric Back Titration: Trial 5

14
12
10
Current (mA)

8
6
4
2
0
0 50 100 150 200 250 300
-2
Time (s)