Determination of Calcium in Limestone

Armas, Ma. Juryst Chelsea A.

School of Chemistry and Chemical Engineering,
MAPUA Institute of Technology

Abstract A redox titration is based on oxidation-reduction reaction between analyte

(Na2C2O4) and titrant (KMnO4). It determines the concentration of an analyte containing either
an oxidizing or a reducing agent by measuring it against a standardized titrant. Potassium
permanganate is a powerful oxidizing agent and serves as a self-indicator in the titration with
reducing agent. The analyte in a redox titration must be in a single oxidation state at the outset.
The steps that precede the titration the sample preparation and elimination of interferences which
usually involve converting the analyte to a mixture of oxidation states. Prereduction is done to
ensure that the analyte is present in a single oxidation state. Limestone usually contains a mixture
of calcium carbonate and magnesium carbonate, which is called dolomitic limestone. Calcium is
conveniently determined by precipitation with oxalate ion and it was found out that its average
percent weight is 38.14% while its percent error is 16.48%. Errors in coprecipitation and loss of
precipitate are just some of the few errors that account for this experiment discuss in the
conclusion part.

Keywords: redox titration, calcium, limestone, oxidation states

INTRODUCTION can donate an electron. Consider, for

An oxidation/reduction (redox)
reaction is one in which electrons are
transferred from one reactant to another. It
can be analogous to the Brönsted-Lowry
concept of acid/base reactions. Both involve
the transfer of one or more charged particles
from a donor to an acceptor – the particles
being electrons in a redox reaction and
protons in an acid-base reaction.
A substance that has a strong affinity
to electrons is called oxidizing agent, or an
oxidant. A reducing agent, or reductant, is a
specie that easily donates electrons to
another specie. When a reducing agent
donates an electron, it becomes an oxidizing
agent that can accept an electron.
Conversely, when an oxidizing agent gains
an electron, it becomes a reducing agent that
example, a titration in which a titrant in a
reduced state, Ared, reacts with a titrant in an
oxidized state, Box.
Ared+Box⇌Bred+Aox
Limestone is usually described as
rock made from calcium carbonate, CaCO3 ,
but in fact most limestone rock contains
significant amounts of magnesium, silicates,
manganese, iron, titanium, aluminum,
sodium, potassium, sulphur (as sulphides or
sulphates) and phosphorus. In this
experiment, a sample of limestone is be to
analyzed to determine how much calcium it
contains.
In common with a number of other
cations, calcium is conveniently determined
by precipitation with oxalate ion. The solid
calcium oxalate is filtered, washed free of

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excess precipitating agent, and dissolved in
dilute acid. The oxalic acid liberated in this
step is then titrated with standard
permanganate or some other oxidizing
reagent. This method is applicable to
samples that contain magnesium and alkali
metals. Most other cations must be absent
since they either precipitator coprecipitate
and cause positive errors in the analysis.
Consider the reaction below:
These are the equations for the redox
analysis of Ca in the unknown limestone
sample that are used in calculating the
%weight of CaO in the unknown
EXPERIMENTAL
This experiment is divided into two
parts. First is the preaparation of the sample
and second is the precipitation of the oxale
to determine the calciumcontent in the
limestone.
The unknown sample is dried for 2
hours and cooled after in the desiccator and
duplicate samples of the unknown are
weighed from 0.25-0.30g. This is done for
two trials. To each sample placed in a 500-
mL Erlenmeyer flask, 10mL water is added
and 10mL HCl is added.
Second, is the preparation or th
precipitation of the oxalate ion. A 5 drop of
Bromine solution added in the solution and
heat after for 5 minutes inside the fume
hood; note: Bromine is highly toxic. Dilute
each sample to 50 mL water and add 100
mL of hot 6% (w/v)(𝑁𝐻2 )4 𝐶2 𝑂2 , 3-4 drops
of methyl red. PRecipitae calcium oxalate
by adding 6M Ammonia.
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Continue adding ammonia until the
solution becomes an intermediate to yellow-
orange indicator. Let the solution stand for
awhile to allow the precipitate to settle down
and filter. Wash the precipitate to
remove(𝑁𝐻2 )4 𝐶2 𝑂2 , by several portions of
10mL cold water.
After separating the precipitate, a 50-
mL of 3M sulfuric acid is added to each
flask and was titrated using
0.1687mmoles/mL of potassium
permanganate solution while maintaining its
temperature to about 55-90℃ using
thermometer and placed a magnetic stirrer to
each flask for continuous swirling of the
sample to avoid over titration. results are
reported in % CaO in the sample.
RESULTS/ DISCUSSIONS
In common with a number of other
cations, calcium is conveniently determined
by precipitation with oxalate ion. The solid
calcium oxalate is filtered, washed free of
excess precipitating reagent, and dissolved
in dilute acid. The oxalic acid liberated in
this step is then titrated with standard
permanganate or some other oxidizing
reagent. This method is applicable to
pthealkali metals. Most other cations must
be absent since they either precipitate or
coprecipitate as oxalates and cause positive
errors in the analysis.
For example, the calcium oxalate
formed in a neutral or an ammoniacal
solution is likely to be contaminated with
calcium hydroxide or a basic calcium
oxalate, either of which will cause low
results. The formation of these compounds
is prevented by adding the oxalate to an
acidic solution of the sample and slowly
forming the desired precipitate by the
dropwise addition of ammonia. The coarsely
crystalline calcium oxalate that is produced
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under these conditions is readily filtered. interference through the formation of
Losses resulting from the solubility of soluble oxalate complexes of magnesium.
calcium oxalate are negligible above pH 4, Prompt filtration of the can also help
provided that washing is limited to freeing prevent interference because of the
the precipitate of excess oxalate. pronounced tendency of magnesium oxalate
to form supersaturated solutions from which
Table-1 precipitate formation occurs only after an
TRIAL e.1 TRIAL 1 hour or more. These measures do not suffice
Wt of 0.2161 02638 for samples that contain more magnesium
sample,g than calcium. Here, reprecipitation of the
Volume of 9.9 9.3 calcium oxalate becomes necessary.
𝑲𝑴𝒏𝑶𝟒
used,mL Limestones are composed principally
Volume of 0.1
of calcium carbonate; dolomitic limestones
𝑲𝑴𝒏𝑶𝟒 in
blank det’n
contain large amounts of magnesium
used,mL carbonate as well. Calcium and magnesium
Net volume 9.8 9.2 silicates are also present in smaller amounts,
of 𝑲𝑴𝒏𝑶𝟒 along with the carbonates and silicates of
,mL iron, aluminum, manganese, titanium,
% CaO in 42.92 33.36 sodium, and other metals. Hydrochloric acid
the sample is an effective solvent for most limestones.
Wt of CaO in 0.2116 0.2008 Only silica, which does not interfere with
the the analysis, remains undissolved. Some
sample,mg limestones are more readily decomposed
Average % 38.14 after they have been ignited; a few yield
weight of only to a carbonate fusion.
CaO
The method that follows is
The data above shows the tabulated remarkably effective for determining
results gathered from this experiment which calcium inmost limestones. Iron and
shows that the weight percent of CaO is aluminum, in amounts equivalent to that of
38.14% while its true value is 45.67%.It is calcium, do not interfere. Small amounts of
essential that the mole ratio between calcium manganese and titanium can also be
and oxalate be exactly unity in the tolerated
precipitate and thus in solution at the time of
titration. A number of precautions needed to CONCLUSION/RECOMMENDATION
ensure this condition.
Redox titration is important in
Coprecipitation of sodium oxalate determination of the mass of calcium in a
becomes a source of positive error in the sample and then determination of the
determination of calcium whenever the percent of mass in limestone is by titrating it
concentration of sodium in the sample with KMnO4. The result is 38.14% and it
exceeds that of calcium. The error from this shows that there are many sources of errors
source can be eliminated by reprecipitation. in this experiment as it has obtained a
Magnesium, if present in high concentration, 16.48% experimental error.
may also be a source of contamination. An
excess of oxalate ion helps prevent this

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 Co-precipitate of the other cations
with the calcium oxalate and incomplete
precipitation of CaC2O4 when adding NH3,
standardization process of KMnO4,
impurities of the chemical, wrong
determination of the end point, errors in
reading the burette, errors in the analytical
balance and the glassware used, incomplete
heating at a specific temperature and doing
the titration when the media is cool, loss of
precipitate during filtration and loss of
precipitate during transferring are errors that
are encountered durng this experiment.

REFERENCES

[1]http://www.cengage.com/resource_uploa
ds/downloads/0030355230_17073.pdf

[2] "Redox Titration”,Sulatanat of Oman

Sultan Qaboos university Collage of science
Department ofChemistryCHEM4441

[3]Raquel Marquez, and others, “Laboratory

Manual for Analytical Chemistry 1”:
Gravimetric Determination of Calcium, 20-
23.

APPENDIX

“See attachment”

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