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Redox Tit Rations Only - Final
Redox Tit Rations Only - Final
Redox Reactions
Redox stands for Reduction - Oxidation
These titrations involve the titration of an oxidizing agent (or oxidant) with a
reducing agent (or reductant) or vice versa. There must be a sufficiently large
difference between the oxidizing and reducing capabilities of theses agents for the
reaction to undergo completion with a sharp end point.
Oxidation process involves loss of electrons while reduction process involves gain of
electrons.
Thus an oxidizing agent is one which accepts electrons while a reducing agent is one
which loses the electrons.
An oxidizing agent oxidizes the other substance by stripping off electrons from it.
A reducing agent reduces the other substance by donating electrons to it.
Oxidation and reduction reactions always occur simultaneously. One can not take place
in isolation from the other. During a redox reaction the oxidizing agent itself
undergoes reduction while the reducing agent undergoes its oxidation.
Relative values are only obtained by comparison with the Normal Hydrogen electrode
potential (SEP) when the hydrogen gas at 1 atm. pressure is in contact with a piece of
platinum and with hydrogen ion concentration at 1M.
The standard electrode potential enable us to predict which ions will oxidize or reduce
other ions.
Some of the commonly used oxidizing and reducing agents in the redox titrations are –
Oxidizing agents
i. KMnO4 in presence of dil H2SO4
MnO4 ¯
+ 8H+ + 5e- → Mn2+ + 4H2O E°red = +1.52V
Reducing agents
Redox Indicators
A redox indicator should be such that it produces a sudden change in the electrode
potential in the vicinity of the equivalence point during a redox titration. This is possible
when the indicator itself is redox active i.e., capable of undergoing oxidation or reduction
process which is a reversible one. The oxidized and reduced form of the indicator should
have a contrast difference in the colours.
Inoxd + ne = Inred
At potential E, the ratio of the concentration of two forms is given by the Nernst equation
ET = E0 + RT/nF ln [Inoxd]/[IRed]
Internal indicator Such indicators are added into the reaction mixtures Such indicators
always have reduction potential values lower than the analyte system so that they react
with the titrant only when whole of the analyte has been consumed, producing a readily
detectable color change.
External indicator In case a suitable redox indicator is not available for a given system,
an indicator may be employed which will indicate the completion of reaction by
physically or chemically reacting with the analyte (not through redox reaction). This
reaction between indicator and the analyte may sometimes be an irreversible one and in
some cases may even lead to precipitation. In those case indicators are not added to the
reaction mixture on the whole, rather used externally on a grooved tile. Such indicators
are called external indicators.
Potentiometric Methods The most accurate method to judge the completion of redox
titration is however potentiometric method which deals with the measurement of e.m.f.
between a reference electrode and the indicator (redox) electrode during the stages of
redox titration. This method infact tells us the equivalence point of the reaction and not
the end point
4MnO 4
¯
+ 2H2O → 4MnO2 + 3O2 + 4 OH ¯
2MnO 4
¯
+ 3 Mn2+ + 2H2O = 5MnO2 + 4H+
The reaction is quite slow in acidic medium but attains a fast rate in neutral solutions.
Thus Permanganate solution can not be considered as a primary standard solution by
simply making the calculations based on the amount of permanganate weighed and
dissolved. The permanganate solutions once prepared are either left for a day or two or
the freshly prepared solutions are boiled for an hour. In both the cases the resulting
solution is filtered through sintered glass crucibles. The clear solutions so obtained are
then standardized by titrating with a primary standard solution
The acidity is introduced by addition of dil. H 2SO4 only and no other acid. Conc. H2SO4 ,
Nitric acid (both conc. and dilute) can’t be used as these are oxidizing agent and may
interfere in the reaction of permanganate depending on the reductant’s strength.
In the hydrochloric acid permanganate can oxidize chloride to chlorine, which can be a
source of positive errors as permanganate is consumed in this reaction.
(E°red Cl2/Cl-)= +1.36V)
2MnO 4
¯
+ 16 H+ + 10Cl (aq) →
-
2Mn2+ + 5Cl2 + 8 H2O (l)
Acetic acid is too weak an acid to provide the desired acidity in the solution.
Permanganate acts as self indicator. Since MnO4– is intense purple while Mn2+ is
colourless, the reaction mixture at equivalence point is colourless and even a single drop
of the permanganate would impart sufficient pink colour to the solution acting as self
indicator.
This also leads to precaution that while titrating a reducing agent with KMnO4 , constant
stirring of reaction mixture is must otherwise local reduction in acidity may lead to
precipitation of MnO2 according to this reaction.
The reducing agent in the titration to be discussed is oxalic acid here. The composition of
it is H2C2O4.2H2O. Inspite of being a dehydrate it is a good primary standard as its
composition is unchanged during storage or weighing.
The reaction between oxalic acid and potassium permanganate can be represented as:
This redox reaction can be split apart in two parts- one showing the oxidation and the
other reduction
This titration is carried out in warm conditions (temperature about 60 oC). The reaction at
room temperature is slow because of the equilibrium nature of this reaction. CO 2 is highly
soluble in water and thus heating removes all dissolved carbondioxide out of the solution
driving the reaction in forward direction. Also at low temperature, the reduction of
permanganate may not be complete producing Mn(III) (in the form [Mn(C 2O4)3]3-). The
formation of this species introduce errors in titrations as no. of electrons utilized here are
different as compared to production of Mn2+. This complex however breaks on heating
and hence reaction proceeds smoothly.
While noting the burette readings, it should be taken into account that the solution is so
intensely coloured that the lower meniscus of the solution may not be clear. Thus for
permanganate titrations the upper meniscus in the burette is noted.
Potassium dichromate is also a very strong oxidizing agent (E°red = +1.33V) . However it
is not as strong oxidizing agent as permanganate is (E°red = +1.51V).Still it is widely used
in redox titrations because of several advantages over permanganate. Unlike potassium
permanganate, potassium dichromate is available in high purity and is highly stable upto
its melting point. Its aqueous solutions are not attacked by oxidisable impurities like
rubber or any other organic matter and thus composition of aqueous solution does not
change on keeping. The aqueous solutions are quite stable towards light. It is thus an
excellent primary standard and its standard solutions can be prepared by direct weighing
of an amount of it and dissolving in a known volume of distilled water.
Chromate ions are weaker oxidizing agent than dichromate. Thus oxidizing strength of
dichromate is reduced in neutral solution. The above hydrolysis reaction however can be
reversed by adding acid to the solution and this explains the necessity of acidic medium
for the reaction.
This reaction clearly shows the involvement of H+ in the reduction half reaction.
The medium is generally acidified with dil. H2SO4. Unlike permanganate case, cold HCl
can be used here for acidifying the reaction mixture provided the acid conc. Does not
increase beyond 1 – 2 M.
Though the dichromate solutions are intensely orange coloured solutions and a single
drop of it imparts yellow colour to a colourless solution, it can’t be used as a self
indicator like KMnO4. This is because its reduction product (Cr3+) is green which
hinders in the visual detection of end point by observing dichromate colour. Thus an
indicator is must in this titration. The indicator should be redox active and must be
properly chosen keeping in mind the electrode potential values of the reducing agent
being titrated with dichromate. Suitable indicators for dichromate titrations are
Diphenylamine (specifically sodium diphenylamine sulphonate)(0.2%aq. Soln) in
presence of orthophosphoric acid, and N-phenylanthranilic acid (0.1% soln. in 0.005 M
NaOH).
Mohr’s Salt
The reducing agent used in this titration is Mohr’s salt which is a double salt. Its
composition is FeSO4.(NH4) 2SO4.6H2O. The redox active species in this compound is
Fe2+ whose oxidation can be represented as:
Mohr’s salt is a primary standard and therefore its standard solution can be easily
prepared by direct weighing a known quantity of it and dissolving in a known volume of
distilled water. However The Ferrous ions in aqueous solutions are highly susceptible
towards hydrolysis resulting in precipitation of ferrous hydroxide.
The reaction sequence however can be reversed by adding acid. Hence while preparing
standard solution of Mohr’s salt it is necessary to add about 1 ml of dil. H2SO4 to the
measuring flask. Simple Ferrous sulphate is not a primary standard and hence can never
be used for preparing the standard solution. The solid sample of ferrous sulphate contains
a high percentage of ferric ions produced by aerial oxidation of the ferrous ions. Thus
composition is not accurately known.
The reaction between Potassium dichromate and Mohr’s salt can be represented as:
K2Cr2O7 + 6FeSO4 + 7H2SO4 → K2SO4 + Cr2(SO4)3 + 3Fe2(SO4)3+ 7H2O
This redox reaction can be split apart in two parts- one showing the oxidation and the
other reduction
The end point of the titration as indicated earlier has to be defined with the help of an
indicator.
Diphenylamine is one such indicator (internal indicator as it is added to the reaction
mixture). The end point is marked with an intense blue violet colouration. The reduction
potential value of this system is E°red = +0.76V which is very near to that of ferrous-
ferric system (E°red = + 0.77V). Thus phosphoric acid is required in this titration as it
reacts with the product ( yellow ) Fe3+ ion to form the complex ion [Fe(HPO4)]+, thus
lowering the formal potential of the Fe(III)/Fe(II) system thereby increasing its reducing
power. Thus the end point is sharper.
The titrations done here are double titrations. This means in the first titration K2Cr2O7 is
standardized by titrating with a standard solution of Mohr’s salt and in the second
titration this standardized K2Cr2O7 is titrated against a given oxalate ion solution of
unknown strength. So experimental work involves three steps:
Experiment no.1:
AIM: To estimate the strength of given Mohr’s salt solution by titrating against
Potassium dichromate solution. Standardize the Potassium dichromate solution with
(approx. 0.025N) standard Mohr’s salt solution prepared by you.
Take a clean dry weighing bottle. Weigh it when empty with out the bottle lid. (as
demonstrated in lab session) This is weight of empty weighing bottle (w1).
Now put an approximate quantity of Mohr’s salt to be weighed in the weighing bottle.
Weigh again. In case the added amount is too much than required , take out some with
the help of a clean spatula and weigh the weighing bottle. In case the added amount is
less than required, add some more into the weighing bottle. (Never add compound to the
weighing bottle, when it is still placed on the pan of the weighing balance. Always take it
out, and then add or remove the compound). Note down the weighing readings as weight
of weighing bottle with the compound (w2)
Transfer the compound into 100 mL measuring flask with the help of a funnel and keep
the weighing bottle back on the pan of weighing balance. Note down the weight as
weight of weighing bottle after transference of compound (w3). The difference of (w3)
and (w2) gives the amount of compound actually transferred to the measuring flask.
Dissolve the solid in minimum amount of water. Add a few drops of conc. H2SO4 acid.
Shake and make up the volume till the 100 ml mark on the flask. Put the stopper on the
flask and shake a number of times, vigorously to homogenize the solution
1. Weighing observations:
NMohrVMohr = NdichrVdichr
Thus
Ndichr = NMohrVMohr
Vdichr
( Calculations alternatively can also be done using molarity concept
6MdichrVdichr = MMVM
Mdichr = MMVM
6Vdichr )
3. Titration of Standardised K2Cr2O7 soln. Vs Mohr’s salt solution (unkown conc.)
NMohrVMohr = NdichrVdichr
Thus
NMohr = NdichrVdichr
VMohr
( Calculations alternatively can also be done using molarity concept
6MdichrVdichr = MMohrVMohr
MMohr = MdichrVdichr
6VMohr )
Thus strength (g/L) of Mohr’s salt solution (of unknown conc.) = Normality x Eq. Wt
Or = Molarity x Mol.wt.
Result:
The strength of given Mohr’s salt solution was found to be………………..g/L
Experiment no.2:
AIM: To estimate the strength of given oxalic acid solution by titrating against
Potassium permanganate solution. Standardize the Potassium dichromate solution
with (approx. 0.025N) standard oxalic acid solution prepared by you.
Take a clean dry weighing bottle. Weigh it when empty with out the bottle lid. (as
demonstrated in lab session) This is weight of empty weighing bottle (w1).
Now put an approximate quantity of oxalic acid to be weighed in the weighing bottle.
Weigh again. In case the added amount is too much than required , take out some with
the help of a clean spatula and weigh the weighing bottle. In case the added amount is
less than required, add some more into the weighing bottle. (Never add compound to the
weighing bottle, when it is still placed on the pan of the weighing balance. Always take it
out, and then add or remove the compound). Note down the weighing readings as weight
of weighing bottle with the compound (w2)
Transfer the compound into 100 mL measuring flask with the help of a funnel and keep
the weighing bottle back on the pan of weighing balance. Note down the weight as
weight of weighing bottle after transference of compound (w3). The difference of (w3)
and (w2) gives the amount of compound actually transferred to the measuring flask.
OBSERVATION TABLE
2. Weighing observations:
NoxVox = NpermangVpermang
Thus
Npermang = NoxVox
Vpermang
( Calculations alternatively can also be done using molarity concept
5MpermangVpermangr = 2MoxVox
Mpermang = 2MoxVox
5Vpermang )
NoxVox = NpermangVpermang
Thus
Nox = Npermang Vpermang
Vox
( Calculations alternatively can also be done using molarity concept
5MpermangVpermang = 2MoxrVox
Mox = 2 MpermangVpermang
5Vox )
Thus strength (g/L) of Oxalic acid solution (of unknown conc.) = Normality x Eq. Wt
Or = Molarity x Mol.wt.
Result:
The strength of given Oxalic acid solution was found to be………………..g/L