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JOURNAL OF

Laboratory Experiment

Redox Titration
Krizzi Eve Garcia, Arnold John Granda

1 CHEM 1, BS Chemistry, Chemistry Department, College of Science

University of Santo Tomas

España Blvd, Sampaloc, Manila, 1008 Metro Manila

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ABSTRACT: Analyzing certain substances for composition is an essential technique in chemistry


that the modern world needs. Qualitative analysis is a method of chemical analysis that determined the
chemical composition in a given sample. The principle of precipitation with the addition of a precipitating
agent to separate group of ions was employed. Chemical reactions enable the detection of the presence of
a particular ion by adding a reagent that will cause the appearance of a visible reaction to the sample. In
this laboratory experiment, the identity of the cations present in the unknown sample was determined by
qualitative analysis. The Group III and the Group IV ions were precipitated according to their group
precipitant which were NH4OH in NH4Cl and (NH4)2CO3 in neutral or alkaline medium respectively.
The detected ions in the sample were Mn2+ and Ca2+. The appearance of a pink color upon adding
NaBiO3 signaled the presence of Mn2+ ion while a dull yellow red flame from the flame test conducted
indicated the presence of Ca2+ ion. Correct laboratory techniques and procedures should always be
followed to properly separate and detect ions.

KEYWORDS: qualitative analysis, chemical analysis, cations, precipitation, flame test

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INTRODUCTION
Chemical analysis can be divided into two---qualitative and quantitative. Qualitative analysis is the method
of identification of the chemical composition of a substance. However, it does not measure the amount of
substance but instead its factors such as colour, smell, atomic structure, texture and the ability of the
substance to conduct electricity or reflect light. [5][8] The process of determination of ions in a certain sample
is based on chemical reactions given off by measured and known chemicals. The addition of a reagent that
will react with the ion being considered is the main principle of the analysis. The consequent reaction will
then produce a visible result that indicates the presence of a particular ion. These visible results could be a
precipitate, gas or a colored solution. However, there could be other ions that will react with the same
reagent added that will cause an error in the analysis. The interference is omitted through separation
techniques that will eliminate other ions until interference is no longer present. In the unknown sample
provided, it includes particular ions from Group III through Group V which is divided into five groups
accordingly for convenience. The separation of the five groups is done by adding a precipitating agent that
selectively precipitates the ions of a particular group. The solubility-product constants of certain elements

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Laboratory Experiment

and compounds can be compared to know the extent of solubility of the components in the solution, an
essential information in selective precipitation. [2]

Characteristic of ions in a particular group differ from another group which makes the separation of ions
possible. The ions from Group III do not react either with dilute hydrochloric acid, or with hydrogen
sulphide in a medium of dilute mineral acid. But reacts with ammonium sulphide in neutral or ammoniacal
medium to form precipitates. Cations of this group are iron(II), iron(III), cobalt(II), nickel(II),
manganese(II), chromium(III), aluminium(III), and zinc(II). Group IV ions do not react with the reagents
for Group III. These ions form precipitate with ammonium carbonate (NH4)CO3 in ammonium chloride in
neutral medium. While the Group V ions react differently from the previous groups, these ions can be
detected through flame tests. [1]

In the process of the analysis, correct laboratory techniques must be observed. Keen observation and strict
compliance of the execution of the procedures in the experiment is also required to successfully detect the
ions in the sample.

The main objective of the laboratory experiment is to determine the ions present in the unknown sample
by qualitative analysis using proper laboratory techniques and the principle of precipitation and solubility
constants of the component ions.

STUDENT LEARNING GOALS


This laboratory experiment aims the students to 1) observe the chemical properties of the ions involved 2)
conduct series of tests for the separation of ions 3) determine the ions present in the unknown sample

EXPERIMENTAL SECTION
Separation of the Group III Cations

For the separation of the Group III cations, from the given unknown sample, 20 drops were isolated and
placed into a medium-sized test tube. The solution was added and mixed well with 2 drops of 2M NH4Cl.
Dropwise concentrated NH4OH was then added afterwards until the solution is slightly alkaline (4-5 drops).

Figure 1. Resulting solution after separation of Group III cations

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Then additional 2-3 drops (NH4)2S was put into solution. The precipitates formed was treated accordingly
by centrifuging for 1 minute then was separated from the solution using a dropper. The remaining
precipitates were washed with a 1:1 solution of H2O:6M NH4CH3COO and was marked as GRP III. The
test tube containing the precipitates were added with 20 drops of a 1:1 mixture of concentrated
HCl:concentrated HNO3 then was transferred into a casserole. Using a hot plate, the mixture was gently
heated until the precipitates dissolved. Any sulfur that formed was discarded. The mixture was evaporated
to incipient dryness then was added with 20 drops of H2O and was finally transferred into a test tube. The
test tube was then warmed in a water bath to expel Cl2 that formed and was cooled afterwards.

Separation of the Iron and the Aluminum Subgroup

Twenty drops of the resulting solution from the subsequent steps were placed into a test tube. The solution
was added with 6M NaOH dropwise until the precipitates formed. Taking note of the completeness of the
precipitation by observing cloudiness that occurred when 2 drops of the precipitant was added. If cloudiness
appeared, solution must be stirred, centrifuged and tested again for cloudiness. Then an excess of 5 drops
of NaOH was added when precipitation was complete. H202 was added into the solution afterwards. For 5
minutes, the solution was heated in a water bath. The resulting solution was centrifuged then separated into
the precipitates and the solution components. The precipitates were labeled as the iron subgroup while the
solution was aluminum subgroup.

Dissolution of Fe3+, Co 2+, Ni2+, Mn2+

The precipitates labeled as iron subgroup were washed with distilled water and added with 20 drops(or
more) of distilled water then transferred into a casserole. Five drops of concentrated HNO3 was also added
into the mixture which was heated in a hot plate. The warm mixture was carefully added with 30% H2O2
dropwise and was stirred after each drop. When the solids have dissolved, the addition of H2O2 was
stopped. Then the solution was evaporated to approximately half its original volume. The solution was
transferred into a test tube while the casserole was rinsed with 10 drops of distilled water to insure the
complete transfer of the ions. The test tube was marked as Fe subgroup then was centrifuged and decanted.

Detection of Mn2+

Five drops of the solution from the test tube marked Fe subgroup was transferred into a test tube. A drop of
concentrated HNO3 was then added into the new test tube. Then a smaller than a pinch of NaBiO3 was
added. The resulting solution was then placed in a water bath for 5 minutes, allowing the reaction to occur
faster. The warmed solution was observed for any visible changes in color.

Separation of the Group IV Cations from the Group V Cations

The solution obtained from Part C was transferred into a casserole. A drop of concentrated HCl was then
added and was evaporated using a hot plate until residues appear. The resulting residue was treated by
dissolving with 20 drops of hot distilled water, stirred until the residues disappear. The solution formed was
transferred to a test tube. Then 4 drops of 6M NH4Cl, 4 drops of concentrated NH3, and 10 drops 3M
(NH4)2CO3 was added into the test tube and centrifuged afterwards. With the precipitates present, the
solution was separated from the solids using the dropper and was labeled accordingly with the precipitate
as GRP IV and the solution as GRP V.

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Separation and Detection of Ba2+

The test tube marked with Group IV was washed with a 1:1 solution of H2O:3M (NH4)2CO3 and was
dissolved with a smallest volume of 6M CH3COOH. Then transferred to a casserole and evaporated to
incipient dryness. The residue was dissolved with 30 drops of a 1:1 mixture of 1M CH3COOH:3M
NH4CH3COO and was transferred to a test tube. A drop of 1M k2CrO4 was added.

Separation and Detection of Sr2+

The solution was made alkaline by adding 6M NH3. The same number of drops added was also put into the
test tube with 95% ethanol. Then was allowed to stand for 5 minutes. Then centrifuged afterwards. The
solution was separated and marked with Ca.

Detection of Ca2+

The solution was added with 5 drops of 1M K2C2O4 and was centrifuged afterward when precipitate was
present. The precipitate was washed with distilled water then was dissolved with least volume of HCl. On
the small portion of the mixture, flame test was performed. A dull yellow flame indicates the presence of
Ca2+.

HAZARDS
Concentrated solutions of chemicals may pose risks on the body when in contact. Aqueous ammonia,
acetic acid, HNO3 and HCl are highly hazardous. These are corrosive to eyes, skin, and mucous
membranes. The fume emitted by the warming of highly concentrated acids can affect the lungs when
inhaled. Ammonium carbonate decomposes in air to release ammonia. Correct handling and wearing of
protective equipment must be observed at all times. Gloves and eye protection must be worn when
obtaining acid samples to ensure safety and avoid unwanted spills. Disposal of acids should be always in
the designated waste bins.[7]

RESULTS AND DISCUSSIONS


The purpose of this laboratory experiment was to determine the cations present in the unknown sample by
qualitative analysis. The addition of certain reagents with the ion being considered will cause a visible
chemical reaction that will signal the presence of the ion.

In the separation of the Group III cations, the ions were precipitated as hydroxides or sulfides from an
aqueous solution buffered with ammonia and ammonium chloride and saturated with hydrogen sulfide. The
addition of (NH4)2S turned the solution into yellowish with white precipitate which could be a strong
indicator of the presence of the Mn2+ ion however there are still possible other elements that could react
with the reagent added.

In the unknown sample provided, the warmed solution with the added HNO3 and NaBiO3 turned the
solution into a pink color. The chemical equation for the reaction is given by:

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5NaBiO3 + 2MnSO4 + 16HNO3 → 5Bi(NO3)3 + 2HMnO4 + 2Na2SO4 + NaNO3 + 7H2O

Figure 2. Pale pink color formed with the formation of permanganate

The reaction of manganese sulfate with nitric acid and sodium bismuthate is a redox reaction. [6] Sodium
bismuthate is a strong oxidizer that converts manganese into permanganate. The Mn2+ ion gets oxidized,
losing its electrons and the resulting ion is colored purple/pinkish. As the reaction goes into completion, the
resulting solution turns pink because of the increase in the concentration of permanganate. [3]

The other ion present in the unknown sample is Ca2+ which was not detected directly through experimental
means was a member of the Group IV ions. The presence of such ion can be detected through performing
of flame tests. Flame tests are analytical procedures used to detect the presence of elements especially metal
ions based on each of their unique characteristic emission spectrum. [5] The color of the flame indicates the
ion present, as with the Ca2+ ion; a dull yellow red flame should be emitted. Experimental errors could
have affected the detection of the ions. Failure to wash the precipitates properly can contaminate the sample
being analyzed. Also, the decantation procedure or the transfer of precipitates might have also caused errors
due to incomplete transfer of ions. Incomplete precipitation then proceeding with the next separation step
can also be a source of error. Other ion species could react with the reagent added if incomplete precipitation
was made. [7]

CONCLUSION
Qualitative analysis is a method of chemical analysis used in the determination of the chemical composition
of a particular sample. The determination uses the principle of separation through a precipitating agent
added. In the sample provided, the ions present are Mn2+ and Ca2+. The identification was made by
isolation of the Group III from the Group IV ions then adding a reagent that will eliminate other ions that
might react with the ion being considered. The presence of the Mn2+ ion was determined through the
appearance of a pink color with the addition of the NaBiO3 in a hot solution of HNO3. The oxidation of

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the Mn2+ ion released the pink color signaling its presence. In the analysis of ions, laboratory techniques
like centrifuging, decantation, evaporation and transferring of solutions or precipitates should always be
done correctly to avoid contamination and loss of ions which could cause errors in the analysis. Careful
observation should also be done with each reagent added into the sample being analyzed in order to
systemize facts and infer correctly.

REFERENCES:
[1] Adapted from an experiment by Rod O’Connor and Warren C. Woelfel, W. C., Freeman Library
of Laboratory Separates in Chemistry, W. H. Freeman Company, San Francisco, 1971, Vol. 11, No. 1121.

[2] Binag, C.A., Dilan, R.H., Bergantin, J.H. & Tan, J.T. (2019). Analytical Chemistry 1
(CHM414 Lab) Laboratory Manual (for Chemistry Majors). Manila, Metro Manila. Department of
Chemistry.

[3] Birk, P.J. (2018). Characteristic Reactions of Manganese Ions (Mn²⁺). Retrieved March 31, 2019
from
https://chem.libretexts.org/Bookshelves/Analytical_Chemistry/Supplemental_Modules_(Analytical_Chemistr
y)/Qualitative_Analysis/Characteristic_Reactions_of_Select_Metal_Ions/Characteristic_Reactions_of_Mang
anese_Ions_(Mn%C2%B2%E2%81%BA).
[4] Case Chemicals. (2016). Importance of Qualitative Chemical Analysis. Retrieved March 31, 2019
from https://www.casechemicals.co.uk/blog/importance-of-qualitative-chemical-analysis/.
[5] Helmenstine ,Anne Marie, Ph.D. (2010) Qualitative Analysis: Introduction to Qualitative
Analysis-Identifying Anions and Cations.(online). Retrieved March 31, 2019 from
http://chemistry.about.com/od/lectureclassnotes/a/Qualitative-Analysis.htm.
[6] No name. Sodium bismuthate react with manganese(II) sulfate and nitric acid . Retrieved March
31, 2019 from https://chemiday.com/en/reaction/3-1-0-7535.
[7] Salim, S. Classification of the Cations and AnionsTESTING FOR A SINGLE CATION IN SOLUTION
The identification of a single cation in solution is a fairly simple andResidue FiltrateGroup IIB. Retrieved
March 31, 2019 from
https://www.academia.edu/4060591/Classification_of_the_Cations_and_AnionsTESTING_FOR_A_SIN
GLE_CATION_IN_SOLUTION_The_identification_of_a_single_cation_in_solution_is_a_fairly_simple
_andResidue_FiltrateGroup_IIB.

[8] Skoog, D. A., West, D. M., & Holler, F. J. (1988). Fundamentals of analytical chemistry.
New York: Saunders College Pub.