DETERMINATION OF CHLORIDES

A Laboratory Report Presented to the

Faculty of the Department of Chemical Engineering
School of Engineering and Architecture
Saint Louis University

In Partial Fulfillment of the Requirements for the Course:

CHE 424AL: Environmental Engineering for CHE (Lab)

by:
Cudia, Genery Mae P.
De Guzman, Marriane Camille J.
Del Rosario, Jehra Luz J.
Dial, Katherine Joyce A.

December 2020
Department of Chemical Engineering
School of Engineering and Architecture
Saint Louis University
 LABORATORY REPORT EVALUATION SHEET

Laboratory Course: CHE3131L Schedule: 1:30-6:00 WTh

Experiment Number: 3
Experiment Title: Determination of Chlorides
Group Number: 7 Date Performed: December 1, 2020
Group Members: Cudia, Genery Mae P. Date Submitted: December 5, 2020
De Guzman, Marriane Camille J.
Del Rosario, Jehra Luz J.
Dial, Katherine Joyce A.

CONTENTS TOTAL REMARKS SCORE

POINTS
I. Abstract 15

II. Introduction 10

III. Design and Methodology 10

IV. Results and Discussions 15

V. Conclusion and 10
Recommendations
VI. Appendices: 15
a. List and Uses of
Apparatus
b. Definition of Terms
c. Documentation
d. Computations
e. Answers to
Questions/Problems

VII. Table of Contents/ List of 10

Tables/ List of Figures
VIII. Bibliography/References 5
(APA format)
IX. Format and Neatness 10

TOTAL POINTS: 100 SCORE: ________

Evaluated by: Engr. Benedict Marzan
Date: December 5, 2020
 ABSTRACT

One of the major inorganic anions present in water and wastewater is chloride anions (Cl-
). It's one of the essential ions required to be present in an optimum quantity, especially
in potable water. The objective of this experiment focused on the determination of
chlorides present in the water sample by the Argentometric method. This method was
based on the fact that silver reacts with all the chlorides and gives white precipitate. In
this experiment, the water sample was titrated using standardized silver nitrate using
potassium chromate as an indicator. As the titrant is added, a white precipitate of silver
chloride formed. It was found out that the water sample contains a small concentration of
chloride ion and sodium chloride compound, which results in a small amount of salinity of
the water sample. This result also indicates that the sample water used containing small
amounts of chlorides is suitable for the aquatic organisms' cell functions. The students
recommend that the titration be done at a constant temperature because the solubilities
of silver chloride and silver chromate depend on the temperature.
Keywords: Chloride ions, Argentometric method, Silver nitrate, Potassium
chromate
 INTRODUCTION
Chlorine is an abundant and essential mineral on earth. Chlorine is the most
commonly manufactured chemical for it is use as a bleach in the manufacture of paper
and cloth, but it is also used to make pesticides, rubber, and solvents. It does kill bacteria,
and protozoans that lives in water supply reservoirs. Chlorine disinfects water but does
not purify it. When chlorine is added to water, it destroys the membrane of many
microorganisms and kills them. However, it is ineffective against some cysts, such as
cryptosporidium, which are resistant to chlorine disinfection due in part to their thick outer
wall. The process only works, however, if the chlorine comes into direct contact with the
organisms (Reed R., Godfrey,S.& et.al, 2014).
Freshwater organisms are generally hyperosmotic and thereby have to
continuously excrete water (with some solute loss) to maintain equilibrium. Freshwater
organisms therefore must take up ions to replace the ones lost, which can result in
elevated energy expenditures until a threshold of intolerance is reached (Holland et al
2010). Chlorine takes time to kill organisms. At temperatures of 18OC and above, the
chlorine should be in contact with the water for at least 30 minutes. If the water is colder
then, the contact time must be increased.
The test for chloride ions described here is based on precipitation of an insoluble
chloride salt. When a few drops of a silver nitrate solution are added to a slightly acidic
aqueous solution that contains chloride ions, a white precipitate of silver chloride will form.
If standard solutions with known chloride ion concentration are available for comparison,
the amount of precipitate can be used to estimate the concentration of chloride ions
(Government of Canada, 2018).
Titration is a process by which the concentration of an unknown substance in
solution is determined by adding measured amounts of a standard solution that reacts
with the unknown. Then the concentration of the unknown can be calculated using the
stoichiometry of the reaction and the number of moles of standard solution needed to
reach called end point.
Precipitation titrations are based upon reactions that yield ionic compounds of
limited solubility. The most important precipitating reagent is silver nitrate. Titrimetric
methods based upon silver nitrate are sometimes termed argentometric methods.
Potassium chromate can serve as an endpoint indicator for the argentometric
determination of chloride, bromide and cyanide ions by reacting with silver ions to form a
brick-red silver chromate precipitate in the equivalence point region.
 DESIGN AND METHODOLOGY

Precautions
The following precautions should be observed while performing the experiment:
1. A uniform sample size must be used, preferably 100 mL (or 50 mL), so that ionic
concentrations needed to indicate the end point will be constant.
2. The pH must be in the range of 7 to 8 because Ag+ is precipitated as AgOH at high
pH levels and the CrO42- is converted to Cr2O72- at low pH levels,
3. A definite amount of indicator must be used to provide a certain concentration of
CrO4; otherwise Ag2CrO4 may form too soon or not soon enough.
4. The chromate solution needs to be prepared and used with care as chromate is a
known carcinogen.
5. Silver nitrate solution causes staining of skin and fabric (chemical burns). Any spills
should be rinsed with water immediately.

Procedure
A 250 mL Erlenmeyer flask is washed with distilled water and was rinsed with the pure
sample. Next, a 100 mL of water sample was measured and placed on the Erlenmeyer
flask. If the sample pH is not in range, it must be adjusted to 7 to 10 with H2SO4 or NaOH.
After that, 1 mL of K2CrO4 indicator was added. Then, the solution was titrated with
standard AgNO3 titrant until the pinkish yellow end point. Consistency is needed at the
end point recognition.

Note: If more than 7 or 8 mL of silver nitrate solution are required, the entire procedure
should be repeated using a smaller sample diluted to 50 ml with distilled water. In here a
blank (distilled water) is needed to determine its Cl - concentration.
 RESULTS AND DISCUSSION
Standard Silver Nitrate Concentration: 0.01357 M
TRIAL Volume Volume A, ml B, ml Cl- mg/L NaCl mg/L
of of blank titration titration for
sample used for blank
used, mL sample
1 100 0 3.5 0 16.8370 27.7811
2 100 0 3.2 0 15.3938 25.4000
Table 1.1 Obtained Data in the Titration
In this experiment, the determination of chlorides ion concentration of a solution is
done by titration with silver nitrate in the presence of potassium chromate as an indicator.
The sample contains unknown quantity of chloride ions and is determined by titration with
a silver nitrate solution of a known concentration. The known silver nitrate solution is
added to the unknown chloride solution until the same number of moles of AgNO3 to the
mixture as there are moles of chloride ion present is obtained. To indicate the endpoint
of a titration of chloride ions with a standard AgNO3 solution, it is assumed that the visual
endpoint of this titration is also the equivalence point and used this assumption to
calculate the quantity of chloride present in the unknown sample. In other words, the
analysis depends on two quantities: the concentration of standard AgNO3 solution and
the endpoint volume. The AgNO3 solution is standardized against a primary standard of
NaCl. It is a general property of ionic precipitates like AgCl to adsorb their own ions from
solution. Thus, a silver chloride precipitate standing in a solution containing excess
chloride ions causes a layer of chloride ions to adhere to its surface. Likewise, AgCl in
the presence of a solution containing excess Ag+ ions form an adsorbed layer of Ag+. An
amount of 3.5 mL titrant was used for the first trial before the sample reached the endpoint
while an amount of 3.2 mL was used for the second trial.
The titration was carried out at a pH between 7 and 10 because chromate ion is
the conjugate base of the weak chromic acid (2, 3). Therefore, when the pH is lower than
7, chromate ion is protonated, and the chromic acid form predominates in the solution.
Consequently, in more acidic solutions the chromate ion concentration is too low to
produce the precipitate at the equivalence point. If the pH is above 10, brownish silver
hydroxide forms and masks the end point. The sample volume for both trials are 100 mL
and the sample did not need the usage of blank volume since it did not require more than
7 or 8 mL of silver nitrate solution.
 CONCLUSION AND RECOMMENDATIONS
The purpose of this experiment was to determine chlorides ion concentration of a
sample solution using titration with silver nitrate of Mohr’s method in the presence of
potassium chromate as an indicator.
From the data obtained, a value of 16.8370 mg/L Cl- was calculated for the first
trial and a value of 15.3938 mg/L Cl- was calculated for the second trial using the formula
𝑚𝑔 𝐶𝑙− 𝐴 𝑥 𝑁 𝑥 35,450
= 𝑠𝑎𝑚𝑝𝑙𝑒 𝑣𝑜𝑙𝑢𝑚𝑒,𝑚𝐿, while a value 27.7811 mg/L NaCl was calculated for the first trial
𝐿
and a value of 25.4000 mg/L NaCL was calculated for the second trial using the formula
𝑚𝑔 𝑁𝑎𝐶𝑙 𝑚𝑔 𝐶𝑙−
= 𝐿 𝑥 1.65.
𝐿

In general, a high chloride content may indicate pollution by sewage or industrial

wastes or by the intrusion of seawater or saline water into a freshwater body or aquifer.
And increasing chloride in surface waters results in increased salinity, thereby affecting
the ability of some organisms (stenohaline more so than euryhaline) to effectively
osmoregulate, which could in turn affect endocrine balance, oxygen consumption
following chronic exposures, and overall changes in physiological processes (Holland et
al 2010).
The solubilities of silver chloride and silver chromate depend on temperature,
therefore titration must be carried out at about the same temperature to avoid error in the
data. Good stirring during the addition of the silver nitrate is also required for a sharp and
reproducible end point; otherwise, silver chromate that forms locally before the endpoint
can become occluded in the silver chloride precipitate instead of re-dissolving.
Furthermore, for improved and more accurate results, it is recommended to make sure
that the materials to be used are properly cleaned before using them to avoid
contamination, follow the procedures given in a proper and orderly manner to avoid error
and any unnecessary breakages, and ensure to conduct and finish the experiment within
the same conditions (temperature and pressure) since it will affect the results.
 APPENDICES

Appendix A: List and Uses of apparatus

Apparatus Illustration Use/s

It is a volumetric instrument used to deliver an

1. Burette indeterminate amount of liquid accurately when
titrating.

2.
It is also known as titration flask used to hold sample
Erlenmeyer
liquids and performing mixing for titration process.
flask

3.
Graduated It is used to measure the volume of a liquid.
cylinder

Appendix B: Definition of Terms

Chloride Ion Content. Is the concentration or amount of chloride ions in a solution
Mohr’s Method. Method commonly used to determine the chloride ion concentration
of a solution by titration with silver nitrate. As the silver nitrate solution is slowly added,
a precipitate of silver chloride forms. The end point of the titration occurs when all the
chloride ions are precipitated.
Salinity. The saltiness or amount of salt dissolved in a body of water. Salinity can take
three forms, classified by their causes: primary salinity (also called natural salinity);
secondary salinity (also called dryland salinity), and tertiary salinity (also called
irrigation salinity)
 Titration. Process of chemical analysis in which the quantity of some constituent of a
sample is determined by adding to the measured sample an exactly known quantity
of another substance with which the desired constituent reacts in a definite, known
proportion.
Appendix C: Documentations
(There was no documentation for this experiment because it was not done in an
actual laboratory set-up)
Appendix D: Computations

M = 0.01357 M
N = 0.01357 N

Equation:
-
mg Cl (A)(N)(35,450)
=
L 100 mL

A = titration volume in mL
N = Normality of AgNO3

Trial 1:
𝑚𝑔 𝐶𝑙 − (3.5 𝑚𝐿)(0.01357 𝑁)(35,450)
=
𝐿 100 𝑚𝐿
𝒎𝒈 𝑪𝒍−
= 𝟏𝟔. 𝟖𝟑𝟕𝟎
𝑳

𝑚𝑔 𝑁𝑎𝐶𝑙 𝑚𝑔 𝐶𝑙 −
= (1.65) = 16.8370 (1.65)
𝐿 𝐿
𝒎𝒈 𝑵𝒂𝑪𝒍
= 𝟐𝟕. 𝟕𝟖𝟏𝟏
𝑳

Trial 2:
𝑚𝑔 𝐶𝑙 − (3.2 𝑚𝐿)(0.01357 𝑁)(35,450)
=
𝐿 100 𝑚𝐿
𝒎𝒈 𝑪𝒍−
= 𝟏𝟓. 𝟑𝟗𝟑𝟖
𝑳

𝑚𝑔 𝑁𝑎𝐶𝑙 𝑚𝑔 𝐶𝑙 −
= (1.65) = 15.3938 (1.65)
𝐿 𝐿
𝒎𝒈 𝑵𝒂𝑪𝒍
= 𝟐𝟓. 𝟒𝟎𝟎𝟎
𝑳
Appendix E: Answers to Questions/ Problems

1. How does chlorides being introduced in natural water?

Chlorides are present in both fresh and salt water and are essential
elements of life. Salts such as table salt are composed of ions that are bonded
together. When table salt is mixed with water, its sodium and chloride ions
separate as they dissolve. Chloride ions in the environment can come from sodium
chloride or from other chloride salts such as potassium chloride, calcium chloride
and magnesium chloride.

2. Why do we need to have the indicator “blank” or “error” be subtracted from the
amount of silver nitrate used in titration?
A blank titration is carried out by titrating a fixed and known concentration
of titrant into a solvent with zero analyte. The only difference from the regular
titration is the absence of analyte. This allows the amount of reactive substance
within the plain solvent to be determined and hence allows a determination of the
error in future titration experiments using this solvent.

3. What are other methods of determining chlorides in water sample?

Other method for determining chlorides in water is the Volhar’s Method. This
method uses a back titration with potassium thiocyanate to determine the
concentration of chloride ions in a solution. Before the titration an excess volume
of a silver nitrate solution is added to the solution containing chloride ions, forming
a precipitate of silver chloride. The term “excess” is used as the moles of silver
nitrate added are known to exceed the moles of sodium chloride present in the
sample so that all the chloride ions present will react.

4. Why is it important to adjust the pH for the analysis of chlorides?

The Mohr titration should be carried out under conditions of pH 6.5 – 9. At
higher pH silver ions may be removed by precipitation with hydroxide ions, and at
low pH chromate ions may be removed by an acid-base reaction to form hydrogen
chromate ions or dichromate ions, affecting the accuracy of the end point.
 REFERENCES

Government of Canada. (2018, June 6). How to Test for Chloride Ions in Iron Treatment
Solutions Using Silver Nitrate – Canadian Conservation Institute (CCI) Notes 4/5.
https://www.canada.ca/en/conservation-institute/services/conservation-preservation-
publications/canadian-conservation-institute-notes/test-chloride-ions-iron-treatment-
silver-nitrate.html
Korkmaz, D. D. (n.d.). Precipitation Titration: Determination of Chloride by the Mohr
Method. Retrieved 4 December 2020, from
http://academic.brooklyn.cuny.edu/esl/gonsalves/tutorials/Writing_a_Lab_Report/xPr
ecipitation%20Titration%20edited%203.pdf
F. E. Clarke.)Analytical Chemistry 1950 22 (4), 553-555DOI: 10.1021/ac60040a011
Reed, Robert; Godfrey, Sam; Kayaga, Sam; Reed, Brian; Rouse, Jonathan; Fisher,
Julie; et al. (2013): Technical notes on drinking-water, sanitation and hygiene in
emergencies. Loughborough University. Book. https://hdl.handle.net/2134/14782
Uses, Benefits, and
Safety of Chlorine: Chemical Safety Facts. (2020, May 07). Retrieved December 4, 2020,
from https://www.chemicalsafetyfacts.org/chlorine/
Shukla, M., & Arya, S. (2018). DETERMINATION OF CHLORIDE ION(Cl-)
CONCENTRATION IN GANGA RIVER WATER BY MOHR METHOD AT KANPUR,
INDIA. Green Chemistry & Technology Letters, 4(1), 06-08.
https://doi.org/10.18510/gctl.2018.412
DISTRIBUTION OF WORK

DE GUZMAN, MARRIANE CAMILLE J. Abstract

Compilation
DEL ROSARIO, JEHRA LUZ J. Introduction
References
DIAL. KATHERINE JOYCE A. Results and Discussion
Conclusion and Recommendations
CUDIA, GENERY MAE P. Design and Methodology
Appendices