Jesse Buffington

Taylar Crist

Using Calibration Curves While Standardizing Unknown

Concentrations of NaOH and Sodium Thiosulfate Via Titration to

Improve Accuracy and Precision

Date: 9/25/2019
 Abstract

During week 1 the purpose of the lab was to determine the correction factors for

sequential 10 mL aliquots of water delivered via buret into a 250 mL flask in order to generate a

volume correction factor calibration curve to be used for two titrations in the second week. Each

10 mL aliquot of deionized water delivered to the flask was massed out and the mass of the water

delivered was compared to the recorded volume on the buret to determine the correction factor.

The purpose of part two was to perform a standardization titration on KHP to determine the

molarity of the unknown NaOH solution. Further another standardization titration was performed

using a triiodide anion in solution and an unknown concentration of sodium thiosulfate to

determine its molarity. Both titrations were performed using the buret to deliver the titrant NaOH

or sodium thiosulfate to a 250 mL beaker holding a known amount of KHP or triiodide anion

respectively. The average concentration of NaOH was 0.0814 ± 0.0001 M with an relative

standard deviation of 0.2%. The average concentration of sodium thiosulfate was 0.0453 ±

0.0001 with a relative standard deviation of 0.3%. The relative standard deviations for both

titrations were less than 0.8% indicating that both titration methods were successful for

determining the concentration of the standard solutions of NaOH and sodium thiosulfate.

Introduction

Determining the correction factor for the recorded buret volume reading and generating a

correction factor plot was the objective for week 1. For week 2, performing a successful titration

of KHP and triiodide anion to determine the molarity of the unknown concentration of NaOH

and sodium thiosulfate respectively, further ensuring the titration molarities were within 0.8%
relative standard deviation were the desired outcomes. The procedure from week 1 and week 2 is

important because it outlines the proper technique for creating standard solutions. Creating

standard solutions is important due to their high purity and accurately determined concentration.

This makes them useful in analytical chemistry for various techniques such as titrations and

dilutions.

Calibration is an important technique that is used to minimize method error and random

error in a procedure. In addition, calibration improves the accuracy and precision of each

measurement. In terms of the experiment, calibrating the buret improves accuracy and precision

of the actual amount of titrant added to the analyte. Calibrating a buret is important because the

ability of the buret to deliver an accurate volume degrades over time. The glass of the buret can

warp overtime due to the temperature fluctuations the tip of the buret can build up with

particulates, and the solution put in the buret can succumb to thermal expansion. More

specifically to the experiment, calibrating the burets improves the accuracy of the actual amount

of sodium thiosulfate or NaOH delivered during the titration, which makes the objective of

achieving a relative standard deviation of less than 0.8% more attainable. The calibration

experiment from the first week provided a correction factor for any volume of substance

delivered via the buret. Once the correction factors were graphed, it was used in the second part

of the experiment to determine the more accurate volume of NaOH and sodium thiosulfate

delivered which in turn increases the accuracy of the calculated molarity of the unknown titrants.

The correction factor calculation is displayed below in the results section labeled sample

calculation 3.

In the second week of experimentation two standardization titrations were performed. A

standardization titration was used to determine the concentration of NaOH with high accuracy
using a KHP as the primary standard. KHP was titrated with NaOH of an unknown concentration

and a triiodide anion was titrated with an unknown concentration of sodium thiosulfate. A

primary standard is a reference chemical of a known concentration that is used to determine the

concentration of an unknown solution. In this experiment the NaOH and sodium thiosulfate

solution concentrations were unknown. The titration of KHP was performed to the endpoint

which was measured by the color change in the solution caused by the indicator phenolphthalein.

NaOH reacts with KHP in a 1:1 molar fashion that results in the formation of water molecule and

a base salt, as shown in the reaction labeled KHP reaction with NaOH. This is important to take

into consideration when calculating the molarity of NaOH.

KHP reaction with NaOH

O O
- + -
OK O Na+
+ Na+OH- - +
+ H2O
OH O K

O O

The titration for the triiodide anion with sodium thiosulfate is not as straight forward. In

the first reaction of this titration, the triiodide anion is formed by reacting KIO3 and KI with

sulfuric acid.

8𝐼 − (𝑎𝑞) + 𝐼𝑂3− (𝑎𝑞) + 6𝐻 + (𝑎𝑞) ↔ 3𝐼3− (𝑎𝑞) + 3𝐻2 𝑂(𝑙)

This reaction shown above is assumed to go to completion. This assumption is important

because it allows us to determine the moles of I3- in solution. Next sodium thiosulfate is oxidized

by the triiodide anion in the following reaction.

 𝐼3− (𝑎𝑞) + 2𝑆2 𝑂32− (𝑎𝑞) → 3𝐼 − (𝑎𝑞) + 𝑆4 𝑂62− (𝑎𝑞).

The common form of thiosulfate, 𝑁𝑎2 𝑆2 𝑂3 ∗ 5𝐻2 𝑂, is not pure enough. Solutions of

𝑁𝑎2 𝑆2 𝑂3 had to be freshly prepared by dissolving thiosulfate in boiling water to promote the

disproportionation of 𝑆2 𝑂32− ,

𝐻 + (𝑎𝑞) + 𝑆2 𝑂32− (𝑎𝑞) ↔ 𝐻𝑆𝑂3− (𝑎𝑞) + 𝑆(𝑠).

Methods

Buret Calibration

The 50 mL buret washed according to the washing instructions printed out at the

glassware washing station. The 50 mL buret was determined to be clean after distilled water had

been flushed through the buret and there were not any distilled water droplets sticking to the

walls of the buret. The 50 mL buret was filled with deionized water a few mL over the 0.00 mL

mark. The water was drained into a waste beaker until the air bubble below the stop-cock

disappeared. Once the stop-cock was retightened the tip of the buret was gently grazed with the

side of the beaker to remove that last drop of water. The initial volume was noted and after 5

minutes the volume of the buret did not change. A 250 mL flask and glass stopper was massed

out. 10 mL portions of deionized water from the buret were drained into the 250 ml flask at a rate

of about 0.5 mL/sec. After each 10 ml draining the 250 ml flask was massed out, in addition the

deionized water in the buret was allowed to settle for about a minute after each 10 mL draining

in order to get an accurate and precise reading. After 50 ml of deionized water was drained, the

remaining water was drained and the buret was rewashed. The procedure was repeated a second

time.
 After all of the data had been collected, a correction factor was computed for the volume

of deionized water dispensed by taking the volume per gram that the deionized water occupies at

24°C and multiplying it by the mass of water the was dispensed by the buret. A reproducibility

factor was calculated for between each trial for each aliquot of deionized water delivered. A

correction graph was made by plotting the recorded volume of deionized water from the buret

versus the average correction factor calculated for each aliquot of water delivered.

Standardization NaOH Titration

An NaOH solution was prepared by measuring out about 1000 mL of boiled deionized

water. 5.3 mL of NaOH was added to the flask once cooled. Following, about 0.5 grams of KHP

was added to each of the four 250 mL flasks, and each flask was filled with 30 mL of deionized

water in order to dissolve the KHP. A buret was washed according to the washing protocol

posted in the lab. The buret wash additionally flushed with 10 mL of the NaOH before filling the

buret just over the 0.00 mL mark. The excess NaOH was drained into a waste beaker to get the

initial recording. The first titration was performed quickly, while the following three titrations of

KHP were performed carefully and slowly.

Standardization of Sodium Thiosulfate

A 0.01 M KIO3 solution was made by dissolving 0.4 g of KIO3 in a 200 mL volumetric

flask. In addition, a 0.044 M Na2S2O3 solution was made by dissolving 2.77 g of Na2S2O3 ·5H2O

in 250 mL of boiled deionized water containing 0.025 g of Na2CO3. The 0.044 M Na2S2O3 was

made up in a tightly capped bottle. Next 20.00 mL of KIO3 was pipetted using a volumetric pipet
into and Erlenmeyer flask. 0.8 g of KI solid and 4 mL of 0.5 M H2SO4 was added to the

Erlenmeyer flask, and the sodium thiosulfate was immediately titrated following the addition of

H2SO4. The sodium thiosulfate solution eventually turned a pale yellow color and at that point 1

mL of starch indicator was added and the solution was titrated until the deep blue color of the

solution disappeared, the endpoint.

Results

From the recorded masses of water delivered from the buret, the actual volume of water

was calculated by taking the mass of water delivered and multiplying it by the density of water at

24°C as shown in sample calculation 1.

Sample Calculation 1

𝒎𝑳
𝟗. 𝟗𝟕𝟖𝟖 𝒈 (𝟏. 𝟎𝟎𝟑𝟖 ) = 𝟏𝟎. 𝟎𝟏𝟕 𝒎𝑳 𝑯𝟐 𝑶
𝒈

The buret readings were determined by taking the final buret reading for that aliquot of

water and subtracting it from the initial reading displayed in sample calculation 2.

Sample Calculation 2

𝟏𝟗. 𝟖𝟎 𝒎𝑳 − 𝟎. 𝟎𝟎 𝒎𝑳 = 𝟏𝟗. 𝟖𝟎 𝒎𝑳

The correction factor was calculated by taking the actual amount of water delivered

determined from its mass and subtracting it from the observed amount delivered read from the

buret as shown in sample calculation 3. This was done for both titrations.
Sample Calculation 3

𝑨𝒄𝒕𝒖𝒂𝒍 𝑨𝒎𝒐𝒖𝒏𝒕 𝒐𝒇 𝑯𝟐 𝑶 𝒅𝒆𝒍𝒊𝒆𝒗𝒆𝒓𝒆𝒅 − 𝑽𝒐𝒍𝒖𝒎𝒆 𝒓𝒆𝒄𝒐𝒓𝒆𝒅 𝒃𝒚 𝒃𝒖𝒓𝒆𝒕

→ 𝟗. 𝟗𝟏𝟔𝟑𝒎𝑳 − 𝟗. 𝟗𝟏𝒎𝑳 = 𝟎. 𝟎𝟎𝟔𝟑 𝒎𝑳

Once the correction factors were calculated from the first and second trial, the

reproducibility of the correction factors were calculated by taking the difference between the

correction factors from each trial with respect to the aliquot of water delivered. Meaning the

correction factor produced for the 1 aliquot of water in trial 1 was subtracted by the correction

factor calculated for the first aliquot delivered in trial 2. The reproducibility factor calculation is

displayed in sample calculation 4.

Sample Calculation 4

𝑹𝒆𝒑𝒓𝒐𝒅𝒖𝒄𝒊𝒃𝒊𝒍𝒊𝒕𝒚 𝑭𝒂𝒄𝒕𝒐𝒓 → 𝟎. 𝟎𝟎𝟔𝟑 − 𝟎. 𝟎𝟒𝟓𝟗 = 𝟎. 𝟎𝟑𝟗 𝒎𝑳

The reproducibility factor was less than 0.04 mL for all trials, which means that the

correction factors were significantly reproducible. Once the correction factors were confirmed by

the reproducibility factor, the average of the correction factors was plotted on the y-axis, while

the observed volume delivered was plotted on the x-axis. For the NaOH titration, the graph in

figure 1 was used to correct for the volume of NaOH delivered while the graph in figure 2 was

used to correct for the sodium thiosulfate delivered. The correction factor graphs were applied to

the procedure in week 2 to record an accurate and precise volume of titrant delivered. Based on

the amount of NaOH or sodium thiosulfate delivered determines the correction factor that is

applied to that volume as seen in sample calculation 4. Once the three solution samples were

titrated, the concentration of the NaOH solution was determined by taking the moles of KHP in
solution and converting moles of KHP to moles of NaOH, and then dividing the moles of NaOH

by the corrected volume of NaOH to determine the molarity of the NaOH solution.

Determining Molarity of Unknown Solution (NaOH)

Moles of KHP to Moles of NaOH

1𝑚𝑜𝑙 1 𝑚𝑜𝑙 𝑁𝑎𝑂𝐻

0.5188 𝑔 𝐾𝐻𝑃 ( )( )
204.22𝑔 1 𝑚𝑜𝑙 𝐾𝐻𝑃

= 0.0025404 𝑚𝑜𝑙𝑒𝑠 𝑁𝑎𝑂𝐻

Molarity of NaOH

0.0025404𝑚𝑜𝑙 𝑁𝑎𝑂𝐻
= 0.081214757 𝑀
0.03128 𝐿 𝑁𝑎𝑂𝐻

This was done for the three solution samples for NaOH and sodium thiosulfate. Next the

average molarity was taken shown in sample calculation 6.

Sample Calculation 6 (Average)

𝟎. 𝟎𝟖𝟏𝟐𝟏𝟒𝟕𝟓𝟕 𝑴 + 𝟎. 𝟎𝟖𝟏𝟑𝟖𝟎𝟓𝟑𝟔 + 𝟎. 𝟎𝟖𝟏𝟒𝟕𝟔𝟎𝟖𝟐

= 𝟎. 𝟎𝟖𝟏𝟒
𝟑

The standard deviation of the average of the three solutions for NaOH and sodium

thiosulfate was calculated shown in sample calculation 7.

Sample Calculation 7

𝑺𝒕𝒂𝒏𝒅𝒂𝒓𝒅 𝑫𝒆𝒗𝒊𝒂𝒕𝒊𝒐𝒏 (Excel)

 𝑺𝑻𝑫𝑬𝑽. 𝑺(𝑱𝟑: 𝑱𝟓) = 𝟎. 𝟎𝟎𝟎𝟏

The relative standard deviation was calculated by dividing the standard deviation by the

average molarity as shown in sample calculation 8.

Sample Calculation 8

Relative Standard Deviation

𝟎𝟎𝟎𝟏
𝟏𝟎𝟎 ( ) = 𝟎. 𝟏%
𝟎. 𝟎𝟖𝟏𝟒

The standard deviation of the mean was calculated by taking the standard deviation and

dividing it by the square root of the sample size as shown in calculation 9.

Sample Calculation 9 (Standard Deviation of the Mean)

𝟎. 𝟎𝟎𝟎𝟏
= 𝟎. 𝟎𝟎𝟎𝟎𝟔
𝟑𝟎.𝟓

Lastly the 95 percent confidence interval was calculated using the CONFIDENCE.T

formula from Microsoft excel shown in sample calculation 10.

Sample Calculation 10

𝟗𝟓%𝒄𝒐𝒏𝒇𝒊𝒅𝒆𝒏𝒄𝒆 𝑰𝒏𝒕𝒆𝒓𝒗𝒂𝒍 = 𝑪𝑶𝑵𝑭𝑰𝑫𝑬𝑵𝑪𝑬. 𝑻(𝟎. 𝟎𝟓, 𝑺𝒕𝒅. 𝑫𝒆𝒗. , 𝒏)

 Correction Factor of Buret Reading
0.04
0.03

Average Correction Factor (mL) 0.02

0.01
0
0.0000 10.0000 20.0000 30.0000 40.0000 50.0000 60.0000
-0.01
-0.02
-0.03
-0.04
-0.05
Average Buret Reading (mL)

Figure 1. NaOH Titration Correction Volume for Observed Buret Reading.

NaOH Titration Table

Mean (Molarity) 0.0814

Std Dev (Molarity) 0.0001

RSD 0.2

Std Dev of Mean (Molarity)

0.00004
95% Confidence Interval
0.0002
 Buret Calibration Plot
0.22
0.2
0.18
0.16
Correction Value

0.14
0.12
0.1
0.08
0.06
0.04
0.02
0
0 10 20 30 40 50
Volume Delivered (mL)

Figure 2. Sodium Thiosulfate Titration Correction Volume for Observed Buret Reading.

Sodium Thiosulfate Titration Table

Mean (Molarity) 0.0453

Std Dev (Molarity) 0.0001

RSD 0.3

Std Dev of Mean (Molarity) 0.0003

95% Confidence Interval 8E-05

 Discussion

The objective during the first experiment was to calibrate the buret, by finding the

correction factor for each aliquot of water delivered. The next step was to take the correction

factors and plot them according versus the volume of water delivered according to the buret. The

object during the second experiment was to perform a standardization titration with known

amounts of KHP and triiodide anion to determine the concentration of NaOH and sodium

thiosulfate respectively. In combination with the experiment from week 1, another objective for

the second experiment was to apply the correction factor curve to the volumes of NaOH and

sodium thiosulfate delivered to accurately and precisely calculate their concentrations. The

relative standard deviation for the NaOH titration was 0.2% and the relative standard deviation

for the sodium thiosulfate titration was 0.3%. Both of the relative standard deviations were less

than 0.8% indicating that our titrations were successful in determining the concentration for the

standardized solutions. The concentration of the NaOH solution was 0.0814 ± 0.0001 M while

the concentration of the sodium thiosulfate solution was 0.0453 ± 0.0001 M. The concentrations

of the solutions of NaOH and sodium thiosulfate can both be accepted as standard solutions

because both relative standard deviations are less than 0.8%. These solutions have been

determined to be reliable to standardize other solutions and make dilutions of these standard

solutions. These results match the expectations for the standardization protocol because the

concentration of the analytes, or primary standards were known and both of the primary

standards were stable, they did not decompose, and both of the reactions between the titrants and

the analytes went to completion. In addition, the expectation that calibrating the buret from the

first week in lab proved to significantly impact the accuracy and precision of the calculating
concentrations of sodium thiosulfate and NaOH because the relative standard deviation was less

than 0.8%.

One limitation in the experiment when titrating the KHP was being able to decipher when

the solution turned pink. There was no certain point where the solution was about to turn pink

gradually, a single drop of NaOH could turn the whole solutions vivid pink. Once the endpoint

was nearly reached all the analyte needed was an incredibly small amount of NaOH, which was

hard to control using the buret. In addition, when performing both titrations it was challenging to

get the last drop of the titrant into the flask. The last drop would run down the side of the flask

and would entirely work its way into solutions leaving traces of it on the side. Further it was

slightly challenging to operate the buret and swirl the flask at the same time, especially when the

titrations were nearing their endpoint. One area that needs to be improved upon is the use of the

95 percent confidence interval and the standard deviation of the mean. Neither of those two

calculated values could be used to support or antagonize the results because there is not another

known or true value to compare our mean to.

Conclusion

The purpose of the first week of the experiment was to perform a calibration protocol of a

50 mL buret and generate a calibration curve to improve the accuracy and precision of the

volume delivered by the buret. During the second week of the two-part lab, the purpose was to

apply the calibration curve to determine a more accurate measurement of the aliquot of sodium

thiosulfate and NaOH delivered to the analyte during the titration in order to standardize the

solutions of NaOH and sodium thiosulfate. During week 1 the burets were calibrated by

delivering sequential aliquots of distilled water and massing out each of the aliquots. The volume

recorded by the buret was compared to the actual amount of water delivered into the flask as
determined by calculating the volume of the water mass and density at 24°C. During the second

week of lab two titrations were performed. One of the titrations was a direct titration of a known

concentration of KHP with an unknown concentration of NaOH. The end point of the titration

was determined by the phenolphthalein indicator. The concentration of the standardized NaOH

solution was 0.0814 ± 0.0001 M with a relative standard deviation of 0.2%. The second titration

performed was sort of a back titration of a known concentration triiodide anion with an unknown

sodium thiosulfate. The reason this was not a direct titration was because there was an initial

reation between 𝐾𝐼𝑂3 and 𝐾𝐼 that formed the triiodide anion. The concentration of the sodium

thiosulfate was 0.0453 ± 0.0001. The relative standard deviation of the sodium thiosulfate

solution was 0.3%. Lastly we found that the concentrations of the standardized solutions are

accurate and precise because of the small standard deviations and the relative standard deviations

being less than 0.8%. There is a high confidence that the titrations were successful and the

calculated concentrations are accurate compared to the true value.

 References

1. Harris, D.C. Quantitative Chemical Analysis, 8th edition, W. H. Freeman and Co., New
York; 2006.