Quantitative Analytical Chemistry

Redox Titration Applications

Prepared by

Farah Moustafa Mohammed

ID: 1200180 – Group C2

Supervised by

Prof. Hesham Salem

2020/2021
Quantitative Analytical Chemistry
Quantitative analysis depends on portraying and deciphering objects measurably
and with numbers. Quantitative examination means to decipher the information
gathered for the wonder through numeric factors and insights. Quantitative
investigation incorporates computational and factual strategies for examination.
Quantitative analysis begins with a distinct factual examination stage (which can
likewise be the objective of the cycle of investigation). You follow this stage
with either a closer examination, for instance, of causality and connection or the
creation of arrangements dependent on the unmistakable factual investigation.
You need to design the whole cycle of quantitative examination prior to
completing the exploration on the grounds that the exploration points,
information assortment strategies and information investigation impact one
another.
Qualitative and quantitative examination structure a methodological pair.
Qualitative examination intends to expand the general comprehension of the
quality, attributes and implications of the investigated item or point. There is an
unmistakably characterized contrast among subjective and quantitative
examination. You can utilize the two procedures in a single exploration extend
and examine a solitary examination pointwith the two techniques, yet in an
unexpected way. While either subjective or quantitative techniques
straightforwardly structure the premise of most strategies for examination, a mid-
path pointbetween subjective or quantitative techniques applies to a few
techniques for investigation. Regardless of whether you choose to join subjective
and quantitative strategies in a single report relies upon the points of your
examination and your philosophical position.

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Discussion
Redox Titration
Scientific titrations utilizing redox responses were presented soon after the
advancement of acid–base titrimetry. The most punctual Redox titration
exploited the oxidizing intensity of chlorine. In 1787, Claude Berthollet
presented a technique for the quantitative examination of chlorine water (a
combination of Cl2, HCl, and HOCl) based on its capacity to oxidize indigo, a
color that is vapid in its oxidized state. In 1814, Joseph Gay-Lussac built up a
comparable technique for determining chlorine in blanching powder. In the two
techniques the end pointis an adjustment in shading. Before the equivalence
pointthe arrangement is vapid because of the oxidation of indigo. After the
equivalence point, be that as it may, unreacted indigo confers a perpetual shading
to the arrangement.
The number of redox titrimetric methods increased in the mid-1800s with the
introduction of MnO4–, Cr2O72–, and I2 as oxidizing titrants, and of Fe2+ and
S2O32– as reducing titrants. Even with the availability of these new titrants, redox
titrimetry was slow to develop due to the lack of suitable indicators. A titrant can
serve as its own indicator if its oxidized and reduced forms differ significantly
in color. For example, the intensely purple MnO4– ion serves as its own indicator
since its reduced form, Mn2+, is almost colorless. Other titrants require a separate
indicator. The first such indicator, diphenylamine, was introduced in the 1920s.
Other redox indicators soon followed, increasing the applicability of redox
titrimetry.
• Oxidation: It can be defined as loss of electrons or increase in oxygen content.
• Reduction: It can be defined as gain of electrons or increase of hydrogen
content.
• Oxidizing agent: substance which get reduced.
• Reducing agent: substance which get oxidized.
• Both processes are combined and occur together so we combine them in one
word as REDOX reaction.

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Where is the Equivalence Point?
For an acid–base titration or a complexometric titration the equivalence pointis
practically indistinguishable from the intonation pointon the soaking rising piece
of the titration bend. On the off chance that you glance back at Figure 9.7 and
Figure 9.28, you will see that the intonation pointis in this lofty ascent in the
titration bend, which makes it generally simple to discover the equivalence
pointwhen you sketch these titration bends. We consider this a symmetric
equivalence point. In the event that the stoichiometry of a redox titration is
symmetric—one mole of titrant responds with every mole of titrand—at that
point the equivalence pointis symmetric. On the off chance that the titration
response's stoichiometry isn't 1:1, at that point the equivalence pointis closer to
the top or to lower part of the titration bend's sharp ascent. For this situation we
have a deviated equivalence point.
Finding the End pointwith an Indicator
Three kinds of indicators are utilized to flag a redox titration's end point. The
oxidized and decreased types of some titrants, for example, MnO4–, have various
shadings. An answer of MnO4–is strongly purple. In an acidic arrangement,
notwithstanding, permanganate's decreased structure, Mn2+, is almost vapid.
When utilizing MnO4–as a titrant, the titrand's answer stays dreary until the
equivalence point. The principal drop of overabundance MnO4–produces a
perpetual hint of purple, flagging the end point.
Some indicators structure a hued compound with a particular oxidized or
diminished type of the titrant or the titrand. Starch, for instance, frames a dull
blue complex with I3–. We can utilize this unmistakable shading to flag the
presence of overabundance I3–as a titrant—an adjustment in shading from drab
to blue—or the finishing of a response burning-through I3–as the titrand—an
adjustment in shading from blue to dull. Another illustration of a particular
indicator is thiocyanate, SCN–, which frames a dissolvable red-shaded complex
of Fe(SCN)2+ with Fe3+.
The main class of indicators are substances that don't take an interest in the redox
titration, yet whose oxidized and diminished structures vary in shading. At the
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point when we add a redox indicator to the titrand, the indicator grants a shading
that depends on the arrangement's latent capacity. As the arrangement's likely
changes with the expansion of titrant, the indicator changes oxidation state and
changes tone, flagging the end point.
To understand the relationship between potential and an indicator’s color,
consider its reduction half-reaction

where Inox and Inred are, respectively, the indicator’s oxidized and reduced forms.
Quantitative Applications
Albeit numerous quantitative uses of redox titrimetry have been supplanted by
other insightful strategies, a couple of significant applications keep on being
important. In this segment we survey the overall utilization of redox titrimetry
with an accentuation on ecological, drug, and mechanical applications. We start,
in any case, with a short conversation of choosing and portraying redox titrants,
and techniques for controlling the titrand's oxidation state.
Adjusting the Titrand’s Oxidation State
If a redox titration is to be used in a quantitative analysis, the titrand must initially
be present in a single oxidation state. For example, iron can be determined by a
redox titration in which Ce4+ oxidizes Fe2+ to Fe3+. Depending on the sample and
the method of sample preparation, iron may initially be present in both the +2
and +3 oxidation states. Before titrating, we must reduce any Fe3+ to Fe2+. This
type of pretreatment can be accomplished using an auxiliary reducing agent or
oxidizing agent.
A metal that is easy to oxidize—such as Zn, Al, and Ag—can serve as
an auxiliary reducing agent. The metal, as a coiled wire or powder, is added to
the sample where it reduces the titrand. Because any unreacted auxiliary reducing
agent will react with the titrant, it must be removed before beginning the titration.
This can be accomplished by simply removing the coiled wire, or by filtering.
An alternative method for using an auxiliary reducing agent is to immobilize it
in a column. To prepare a reduction column an aqueous slurry of the finally

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divided metal is packed in a glass tube equipped with a porous plug at the bottom.
The sample is placed at the top of the column and moves through the column
under the influence of gravity or vacuum suction. The length of the reduction
column and the flow rate are selected to ensure the analyte’s complete reduction.
Two common reduction columns are used. In the Jones reductor the column is
filled with amalgamated zinc, Zn(Hg), prepared by briefly placing Zn granules
in a solution of HgCl2. Oxidation of zinc

provides the electrons for reducing the titrand. In the Walden reductor the
column is filled with granular Ag metal. The solution containing the titrand is
acidified with HCl and passed through the column where the oxidation of silver

Selecting and Standardizing a Titrant

If it is to be used quantitatively, the titrant’s concentration must remain stable
during the analysis. Because a titrant in a reduced state is susceptible to air
oxidation, most redox titrations use an oxidizing agent as the titrant. There are
several common oxidizing titrants, including MnO4–, Ce4+, Cr2O72–, and I3–.
Which titrant is used often depends on how easy it is to oxidize the titrand. A
titrand that is a weak reducing agent needs a strong oxidizing titrant if the
titration reaction is to have a suitable end point.
The two strongest oxidizing titrants are MnO4– and Ce4+, for which the reduction
half-reactions are

Solutions of Ce4+ usually are prepared from the primary standard cerium
ammonium nitrate, Ce(NO3)4•2NH4NO3, in 1 M H2SO4. When prepared using
a reagent grade material, such as Ce(OH)4, the solution is standardized against a

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primary standard reducing agent such as Na2C2O4 or Fe2+ (prepared using iron
wire) using ferroin as an indicator. Despite its availability as a primary standard
and its ease of preparation, Ce4+ is not as frequently used as MnO4– because it
is more expensive.
Inorganic Analysis
One of the most important applications of redox titrimetry is evaluating the
chlorination of public water supplies. , for example, describes an approach for
determining the total chlorine residual by using the oxidizing power of chlorine
to oxidize I– to I3–. The amount of I3– is determined by back titrating with S2O32–
.
The proficiency of chlorination depends on the type of the chlorinating species.
There are two commitments to the complete chlorine leftover—the free chlorine
remaining and the consolidated chlorine lingering. The free chlorine leftover
incorporates types of chlorine that are accessible for sanitizing the water supply.
Instances of species adding to the free chlorine remaining incorporate Cl2, HOCl
and OCl–. The consolidated chlorine lingering remembers those species for
which chlorine is in its decreased structure and, hence, not, at this point equipped
for giving sanitization. Species adding to the joined chlorine lingering are
NH2Cl, NHCl2 and NCl3.
At the point when an example of without iodide chlorinated water is blended in
with an abundance of the indicator N,N-diethyl-p-phenylenediamine (DPD), the
free chlorine oxidizes a stoichiometric part of DPD to its red-hued structure. The
oxidized DPD is then back titrated to its dreary structure utilizing ferrous
ammonium sulfate as the titrant. The volume of titrant is relative to the free
leftover chlorine.
Having determined the free chlorine lingering in the water test, a limited quantity
of KI is added, catalyzing the decrease monochloramine, NH2Cl, and oxidizing
a part of the DPD back to its red-hued structure. Titrating the oxidized DPD with
ferrous ammonium sulfate yields the measure of NH2Cl in the example. The
measure of dichloramine and trichloramine are determined likewise.
Organic Analysis
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Redox titrimetry additionally is utilized for the examination of natural analytes.
One significant model is the determination of the synthetic oxygen interest
(COD) of characteristic waters and wastewaters. The COD gives a proportion of
the amount of oxygen important to totally oxidize all the natural issue in an
example to CO2 and H2O. Since no endeavor is made to address for natural issue
that can not be decayed organically, or for moderate deterioration energy, the
COD consistently overestimates an example's actual oxygen interest. The
determination of COD is especially significant in overseeing modern wastewater
treatment offices where it is utilized to screen the arrival of natural rich squanders
into civil sewer frameworks or the climate.
An example's COD is determined by refluxing it within the sight of
overabundance K2Cr2O7, which fills in as the oxidizing specialist. The
arrangement is acidified with H2SO4 utilizing Ag2SO4 to catalyze the oxidation
of low atomic weight greasy acids. Mercuric sulfate, HgSO4, is added to
complex any chloride that is available, forestalling the precipitation of the Ag+
impetus as AgCl. Under these conditions, the proficiency for oxidizing natural
issue is 95–100%. In the wake of refluxing for two hours, the arrangement is
cooled to room temperature and the abundance Cr2O72–is determined by back
titrating utilizing ferrous ammonium sulfate as the titrant and ferroin as the
indicator. Since it is hard to totally eliminate all hints of natural issue from the
reagents, a clear titration should be performed. The distinction in the measure of
ferrous ammonium sulfate expected to titrate the example and the clear is
corresponding to the COD.
Iodine has been utilized as an oxidizing titrant for various builds of drug interest.
Prior we noticed that the response of S2O32–with I3–produces the tetrathionate
particle, S4O62–. The tetrathionate particle is really a dimer comprising of two
thiosulfate particles associated through a disulfide (– S–S–) linkage. In a similar
design, I3–can be utilized to titrate mercaptans of the overall recipe RSH,
shaping the dimer RSSR as an item. The amino acid cysteine likewise can be
titrated with I3–. The result of this titration is cystine, which is a dimer of

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cysteine. Triiodide likewise can be utilized for the examination of ascorbic acid
(nutrient C) by oxidizing the enediol useful gathering to an alpha diketone

and for the analysis of reducing sugars, such as glucose, by oxidizing the
aldehyde functional group to a carboxylate ion in a basic solution.

An organic compound containing a hydroxyl, a carbonyl, or an amine functional

group adjacent to an hydoxyl or a carbonyl group can be oxidized using
metaperiodate, IO4–, as an oxidizing titrant.

A two-electron oxidation cleaves the C–C bond between the two functional
groups, with hydroxyl groups being oxidized to aldehydes or ketones, carbonyl
functional groups being oxidized to carboxylic acids, and amines being oxidized
to an aldehyde and an amine (ammonia if a primary amine). The analysis is
conducted by adding a known excess of IO4– to the solution containing the
analyte, and allowing the oxidation to take place for approximately one hour at
room temperature. When the oxidation is complete, an excess of KI is added,
which converts any unreacted IO4– to IO3– and I3–.

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Application of redox reactions for the determination of
valganciclovir hydrochloride in pharmaceuticals

Two simple, selective and sensitive spectrophotometric methods were developed

and validated for the determination of valganciclovir hydrochloride (VLGH) in
pure drug and tablets. The first method was based on the reduction of iron(III) to
iron(II) by VLGH and subsequent formation of iron(III)-ferricyanide complex
(Prussian blue) in acid medium which was measured at 730 nm (method A). In
the second method (method B), permanganate was reduced by VLGH to bluish
green manganate in alkaline medium and the absorbance was measured at 610
nm. The absorbance measured in each case was related to VLGH concentration.
The experimental conditions were carefully studied and optimized. Beer’s law
was obeyed over the concentration ranges of 2.5-20.0 and 2.0-40.0 µg mL-1 for
method A and method B, respectively, with corresponding molar absorptivity
values of 1.28×104 and 6.88×103 L mol-1 cm-1. The limits of detection (LOD)
and quantification (LOQ) were 0.11 and 0.33 µg mL-1 (method A) and 0.21 and
0.64 µg mL-1 (method B). Within-day and between-day relative standard
deviations (%RSD) at three different concentrations levels were < 2.4%, and the
respective relative errors (%RE) were ≤ 3%. The proposed methods were
successfully applied to the determination of VLGH in tablets, and the results
confirmed that the proposed methods were equally precise and accurate as the
official method.
The redox reactions between VLGH drug and iron(III) in acid medium, and
KMnO4 in alkaline medium were beneficially used for the development of two
methods for the determination of VLGH in pharmaceutical formulations. The

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present work is free from undesirable steps such as heating or extraction steps,
or use of organic solvents. Both systems have wide linear dynamic ranges of
applicability, and method A with an ɛ value of 1.28×104 L mol-1cm-1 is the
most sensitive. The proposed methods use cheap and easily available chemicals
and equipment which is available in most routine industrial quality control
laboratories of developing and under developed countries which would ill-afford
the expensive techniques like HPLC and others.
Determination of Percentage Iron Content by Redox
Titration
Compounds containing iron in the +2 oxidation state can be measured by redox
titration with a strong oxidizing agent.
Potassium permanganate is a strong oxidizing agent that will be reduced and will
oxidize iron (II) in an acidic solution to form iron (III) and manganese (II) ions.
MnO4- + Fe2+ → Mn2+ + Fe3+ (acidic conditions)

Purple colorless
Permanganate ion indicates the titration endpointwhen a faint red/pink color
persists in the solution indicating all of the iron (II) has been used up.
Materials

KMnO4 (aq) potassium permanganate (0.0200 mol dm-3) analytical

balance
unknown iron (II) salt

50 mL graduated cylinder

3 mol dm-3 H2SO4 (aq) funnel

titration burette
ring stand and burette clamp 125 mL Erlenmeyer flask distilled water
Procedure

1. Weigh 0.45_ _ g of unknown iron salt on an analytical balance. This

balance is in the lab room. Carry your salt carefully so it doesn’t spill.
2. Dissolve the unknown in a 50 mL beaker with 15 mL of 3 mol dm-3
sulfuric acid and 25 mL distilled water.

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 3. Properly condition your burette with the titrant. Run a rough titration to
determine the approximate volume of titrant needed.
4. Carefully titrate permanganate solution in your burette to the beaker to
the pink endpoint
5. Complete 4 total trials. Watch to make sure you do not run out of the
solution in the burette.
6. Clean up.
7. Complete the necessary calculations and data analysis to address the
purpose of this lab. Once you have shown your calculations to your
instructor, get the actual value of the % iron.
8. Write a conclusion and evaluation. Use the IB Chemistry Guide to help
you determine what should be included in your conclusion and
evaluation section.
Basic tips:

The purple permanganate in the burette will disappear in analyte as it

oxidizes the Fe 2+ to Fe3+. What will happen to the color of the analyte when
there is no more Fe2+ to convert? (pink color will persist). Many color changes
will occur as iron and permanganate all have different oxidation state colors and
combinations. Since the solution is dark, you can read the top of the meniscus,
this is acceptable, because we are getting the difference in the value, so if you
remain consistent, it doesn’t matter.

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Oxidation-reduction reactions form the basis of many applications of .chemistry
in industry and in our daily life. Some important applications are as follows:
1. Extraction of metals. By using a suitable reducing agent, metal oxides can be
reduced to metals. For example, Fe20 3 is reduced to iron in the blast furnace
using coke as the reducing agent.
Fe2O3 (s) + 3C(s) à 2Fe (s) + 3CO (g)
Similarly, A1p3 is reduced to aluminium by cathodic reduction in an electrolytic
cell.
Other metals such as lithium, sodium, potassium, magnesium, calcium, etc., are
also obtained commercially by electrolytic methods.
2. Electrochemical cells or batteries. Electrochemical cells or batteries based
on redox reactions are widely used in our day-to-day life to run a number of small
and big gadgets and equipments. For example, storage cells are used to supply
all the electrical needs of our cars, trucks, buses, trains, aeroplanes, etc.
Similarly, electrical energy needed in the space capsule is obtained by the
reaction of hydrogen and oxygen in fuel cells which are electrochemical cells
using oxygen and hydrogen electrodes.
3. Photosynthesis. Green plants convert carbon dioxide and water into
carbohydrates in presence of sunlight. This reaction is called photosynthesis and
is sensitized by chlorophyll.

During this reaction, CO2 is reduced to carbohydrates while water is oxidised to

oxygen. The energy needed for the reaction is provided by sunlight.
This reaction is a source of food for plants and animals. It also maintains a
constant supply of 21% of O2 by volume in the atmosphere needed for
combustion of fuels and breathing of all the living creatures in the world.
4. Supply of energy. The energy required for our daily needs is obtained by
oxidation of fuels. For example, oxidation of fuels such as wood, gas, kerosene,

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petrol, etc. produces a large amount of energy which we need for various
purposes in our daily life.
Fuels (wood, petrol, kerosene, gas) + O2 à CO2 + H2O + Other products ,Energy
Human body also needs energy for proper functioning. This is obtained by the
oxidation of glucose in our body to CO2 and water.

5. Production of chemicals. Many chemicals of our daily needs such as caustic

soda, chlorine, fluorine, etc., are produced by electrolysis which is based on
redox reactions.
6. Quantitative analysis. Redox reactions are very useful in quantitative
analysis by redox titrations. These titrations involve the reactions between
oxidising and reducing agents and help in estimating the amount of unknown
substances in solutions.
Conclusion
Redox titrations are based on a reduction-oxidation reaction between an
oxidizing agent and a reducing agent. A potentiometer or a redox indicator is
usually used to determine the endpointof the titration, as when one of the
constituents is the oxidizing agent potassium dichromate. The color change of
the solution from orange to green is not definite, therefore an indicator such as
sodium diphenylamine is used. Analysis of wines for sulfur dioxide requires
iodine as an oxidizing agent. In this case, starch is used as an indicator; a blue
starch-iodine complex is formed in the presence of excess iodine, signalling the
endpoint.

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[4] Harjadi, W. J., A simpler method of chemical reaction balancing, J.
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