REDOX TITRATION METHODS

Permanganometry

This name is given to the set of titrimetric techniques employing the ion
Permanganate as an oxidizing agent, having as fundamental reaction three processes.
Classical REDOX:

SEMI - REACTION IONIC MEANS POTENTIAL

CONDITIONAL STANDARD (V)
-
Manganese Oxide 4+ 8H + 5e Mn (Aq.)+ 4H2O Strongly acidic 1.51
+ - 2+
(Aq.)
-
Manganese Oxide4+ 2H2O + 3e- MnO2+ 4OH- Neutral or slightly 1.68
alkaline
- e- MnO
MnO4+ 2-
4 (Aq.) Strongly alkaline 0.56

This diversity of REDOX behavior, dependent on the ionic medium, can be

explained through the following diagram:

1
 Diagram for the reduced and oxidized forms of manganese

neutral or slightly alkaline neutral or slightly alkaline

MnO2

-2e- -3e-
+1e-
Strongly
acid
Mn Mn2+(Aq.) Mn3+(Aq.) -
Manganese Oxide4
-2e- -1e- +4e-
Strongly
-3e- alkaline
-4e- +1e-

MnO42-
Strongly alkaline Strongly alkaline

2
APPLICATIONS OF PERMANGANOMETRY
The permanganate solutions used for oxymetric dosing must be
standardized. The reducing agent most commonly used as the primary standard

Permanganometric is sodium oxalate: Na2C2O4.

Manganese
- oxide4+ 8H+ + 5e- ⇌ Mn2+(Water)+ 4H2O
(Aq.)

H2C2O4⇌ 2H+ +(Aq.)

2CO2 (g)+ 2e-

Pt, H2C2O4(Cxmol L-1)|CO2(g)(PYatm||MnO4(Czmole L--1), Pt

3
 Multimeter
ANODE
ELECTRONS

pCO21.0 atm
CATHODE
CO2 Salina Bridge

No2C2O4
Potassium permanganate4
1.0 mol L-1 Agar gel-
0.0250 mol L-1
Bubbles of if
CO2 H2SO4 Pt
1.0 mol L-1 Metallic

Platinized platinum blade Galvanic or electrolytic? 4

There is a kinetic order aspect in this reaction. The permanganate reacts slowly with the
oxalate.

With the first drop added, Mn is slowly formed.2+The same goes for others.
reducing species against permanganate in acidic medium.

The ion Mn2+act as a 'promoter' of the system, in a complex reaction involving the ion

Mn3+it is unstable, but it can form a complex ion with oxalate, which by its
sometimes it becomes disproportionate forming CO2, which
- is a very strong reducer.

Mn3++ C2O4⇌2-Mn2++ CO2+ CO2 -

Mn3++ CO2⇌- Mn2++ CO2

2 million3++ C22-O4⇌ 2Mn2++ 2CO2

Thus, the oxidation of oxalate is induced through this cyclic reaction, in

chain.
5
The standardization titration of permanganate should be conducted under the action of the

temperature, heating the reducing agent and the acidic medium but without leaving
accumulate the oxidizer.

A very important aspect, considering permanganate solutions in

acidic medium, it is about the stability of this ion, which tends to oxidize water.

This reaction, although energetically viable, is slow under normal conditions.

being catalyzed by light, presence of Mn2+and MnO2. O MnO2appears in
newly prepared solutions, due to the presence of organic compounds in the water.
A very good alternative is to filter the solution to eliminate MnO.2, what
ensures greater stability by keeping the solution in a light-protected vial.
Obviously, filter paper cannot be used in the filtration of permanganate.
The solution thus stored, carefully, without solids, must be retitled.
periodically, every 7 days at most.
6
The detection of the endpoint in permanganometric titrations is done through
own oxidizing agent, intensely colored purple.

About 0.01 to 0.02 mL of 0.0200 mol L solution-1the KMnO4, dissolved in

100.0 mL of acidic solution gives a noticeable color enough to indicate the
end point of the vast majority of titrations using permanganate.

It is therefore a self-indicating endpoint reagent, making it unnecessary in the

most of the time, to employ indicators.

Another important thing is the need to use a "blank" test.

The accuracy of the full stop greatly depends on the "blank" in which it is corrected.

possible failures in perception of the endpoint.

7
There is another aspect related to the final point, related to the fact that it does not establish itself from

permanent mode. At the final point, there is a high concentration of Mn ions.2+This

excess of Mn ions2+can provoke the following reaction:

2MnO4-+ 3Mn2++ 2H2The⇌ 5MnO2(s)+ 4H+

Thermodynamically this is a viable reaction. The Equilibrium Constant shows a value

of 1047This high value indicates that the concentration may be very small.
permanganate, not the full stop. Fortunately, what is observed is a decrease in visibility
from the final point (disappearance of the color of the MnO ion4, gradually),
- only 30 seconds
after reaching the final point.

The acidic medium that conditions the reduction reaction of permanganate must also be
carefully chosen.

8
.Hydrochloric acid should preferably be avoided.

.The use of HCl results in the formation of Cl.2or OCl-, by the action of the oxidant
permanganate in acidic medium. This occurs under temperature conditions,
over 70oC. This oxidation can be avoided (if it happens to be the case
the need to use such acid), by the addition of Mn ions2+.

.The phosphoric acid medium is especially recommended for better

definition of the color of permanganate, especially in titrations involving
Fe ions2+in which the phosphate complexes with iron(II), making the color clearer
what becomes colorless-purple and not yellow-purple.

9
 IODOMETRY AND IODIMETRY

Periodimetry is understood as a set of titrimetric techniques used in

iodine as an oxidizing agent in direct titrations.

Iodometry is the set of titrimetric techniques using others

species as oxidizing agents, added in excess and that by the addition
In NaI (Sodium iodide), the iodine generated is titrated upon return with the agent.

sodium thiosulfate reducer.

Iodine is a moderate oxidizing agent, being used in aqueous medium.

like triiodide ions or I3, the- most soluble form of the oxidizer.
I2+ I- ⇌ I3 -

I3-+ 2e- ⇌ 3I-

I2+ 2e- ⇌ 2I- 10

 Dichromatometry

DICROMATOMETRY is understood as the classic titration technique using the ion

dichromate as an oxidizing agent, having this reagent, special characteristics in
REDOX titration.

This reagent has a REDOX characteristic, also dependent on the ionic medium.

Its oxidizing power depends on the acidity of the reaction medium, as well as different
species with oxidation state +6 of chromium can exist in equilibrium, provided that
condition the medium to a certain value of adequate hydrogen ion concentration
for a given REDOX process.

2- 14H+ + 6e- ⇌ 2Cr3++ 7H O

Cr2O7+ 2

The dichromate, like K2Cr2O7it is an excellent oxidizing agent, with high potential
REDOX also has primary pattern characteristics.

11
 MULTIMETER

ELECTRONS

ANODE SALINA BRIDGE

CATADE

GEL OF
Fe3+ Agar-agar K2Cr2O7
1.0 mol L-1
1,000 mol L-1

Pt Pt
Metallic Metallic

H2SO41.0
mol L-1
12
REPRESENTATION ????
 CERIMETRY

Cerimetry is understood as the classical titration technique using the ion

Ce(IV) as an oxidizing agent.

This4++ e- ⇌ This3+

Cerium has characteristic chemical behavior as an ion with an oxidation state.

+4. Parallel reactions can occur with the Ce(IV) ion, due to its state of
maximum oxidation, with typical hydrolyses, such as:

This4++ H2The⇌ Ce(OH)3++ H+

Ce(OH)3++ H2O⇌ Ce(OH)2+2+H+

The acidic medium serves to discourage these hydrolysis reactions and should be maintained.
quite high for the equilibrium displacement towards maintaining the state
This4+.

13
 OTHER SYSTEMS

Fe(CN)6Fe(CN)
4-
6(permanganate reducer in strongly alkaline medium)
3-

Iodated in acidic medium (the analysis of indices, such as unsaturation in compounds

organic, especially of oils
Bromate in acidic medium (determination of hydrazine, N2H4, a reducer that has
important technological applications
Calcium hypochlorite (ammonia analysis)
Potassium persulfate in acidic medium
Hydrogen peroxide in acidic medium
Perchloric acid
Chlorine water and bromine water as pre-oxidant reagents
-Fe(II)
Sodium thiosulfate
Sodium oxalate
Among others

14
 REDOX TITRATION CURVES
Variation of the electrode potential as a function of the volume of titrant used.

Consider the titration of 50.00 mL of Fe(II) 0.0500 mol L-1with Ce(IV)

0.1000 mol L-1in a medium of H2SO41.0 mol L-1constant throughout the
titling.
This4++ e- ⇌ This3+ E = 1.44 V (1 mol L-1, H2SO4)
Fe3++ e- ⇌ Fe2+ E = 0.68 V (1 mol L-1, H2SO4)

Initial Potential:
The solution does not contain Ce species before we add the titrant. It is
likely that there is a very small, yet unknown amount
of Fe(III) present due to the oxidation of Fe(II) caused by the air.
15
Before P.E. (VCe4+added = 5.00 mL

When the oxidant is added, Ce3+and Fe3+are formed and the solution
contains appreciable and easily calculable concentrations of three of the
participants.
The amount of Ce4+it's very small.

This4++ Fe2+⇌ This3++ Fe3+

VThisadded
4
x[Ce4 ]
[Fe3 ]  [This4 ]nooreacted
VT

(VFe 3 x[Fe3 ])  (VThis4 x[Ce4 ])

Fe ]2 added
 This4 ]nooreacted
VT

0.0592 [Fe2 ]
Esystem 0 .68 log 0.64V
1 [Fe3 ] 16
NoP.E. (VCe4+add. = 25.00 mL

The concentrations of Ce(IV) and Fe(II) are minimal and cannot be

obtained from the stoichiometry of the reaction. The system's potential is
given by:

0.0592 [Ce3 ]
Eeq E 0 This4 /Ce3  log 4
1 [This ]
+
0.0592 [Fe2 ]
Eeq E 0
Fe3 /Fe2  log 3
1 [Fe ]
e
This3 ] [Fe3 ] e [ C e 4 ] [Fe2 ]

E 0ECe/Ce
4 3
0
Fe3 /Fe2
Eeq 1.06V
2 17
After the P.E. (VCe4+add. = 25.10 mL

The concentrations of Ce(III), Ce(IV), and Fe(III) are easily calculated.

at this point, but that of Fe(II) is not.

nThis3
This ]3
 [ Fe 2 ]nooI reacted
VT

(VThisadded
4
x[Ce4 ])  (VFe 2 x[Fe2 ])
This4 ]  [ Fe 2 ]nooreacted
VT

0.0592 [Ce3 ]
Esystem 1 .44 log 1.30V
[This ]
4
1

18
19
 EXERCISE
Calculate the data and build a titration curve for the reaction of
50.00 mL of U4+0.02500 mol L-1com Ce4+0.1000 mol L-1The solution is
1.0 mol L-1in H2SO4during the entire titration. (For the purpose of
simplification, consider that [H+for this solution it is also about
1.0 mol L-1The analytical reaction is:

U4++ 2Ce4++ 2H2The⇌ UO2+2+2Ce3++ 4H+

That4++ e- ⇌ This3+ E0'1.44 V

+ 4H+ + 2e- ⇌ U4++ 2H2The
UO22+ E0= 0.334 V

Volumes: 5.00 /P.E. / 25.10 mL

20
21
 Values
The coefficients what we use for acid-base and complexation equilibria
they are also useful in redox balances. To calculate the values for systems
redox, we need to solve the Nernst equation for the ratio between the
concentrations of reduced species and oxidized species.

2,303RT[R]
E E 0 log
nF[O]

nF(E E 0)
[R]
10 2,303RT

[O]
 Values
The coefficients what we use for acid-base and complexation equilibria
they are also useful in redox equilibria. To calculate the values for systems
redox, we need to solve the Nernst equation for the ratio between the
concentrations of reduced species and oxidized species.

2,303RT[R]
E E 0 log
nF[O]

 n F(E E 0)
[R]
10 2,303RT

[O]

25oC F 1 [R]
f 10 nf(E E 0)
2.303RT0.0592 [O] 23
 0
[R] [R]/[O] 10  nf(E E)
R 0
[R] [O] [R]/[O] 1 10  nf( E E)
1

nfE0
10 x10
 nfE
10 nfE
R
nfE 0 0
(10 x10 )  1 10nfE 10nfE
 nfE

24
 0
[R] [R]/[O] 10  nf(E E)
R 0
[R] [O] [R]/[O] 1 10  nf( E E)
1

nfE0
10 x10
 nfE
10 nfE
R
nfE 0 0
(10 x10 )  1 10nfE 10nfE
 nfE

 nfE0
10  nfE
10
The 1 R 1  nfE0  nfE0
10nfE 10 10  10
 n/a

25
 EXAMPLE
E0’ Fe3+/Fe2+ in H2SO41 mol L-10.68 V
E0'This4+/Ce3+in H2SO41 mol L-11.44 V

0'

2
10  fE
3
10  fE Fe

Fe 0' Fe 0'
10 fE 10 fE Fe
10 fE 10 bE Fe

0'
 fE
3
10  fE
4
10 Iron

This 0' This 0'

10 fE 10 fE This
10 fE 10 fE This

26
1.0

0.8
Fe2+ Fe 3+ This3+
This4+

0.6

0.4

0.2

0,0
0.50 0.75 1.00 1.25 1.50 1.75
E/V

27
 EFFECT OF VARIABLES
Concentration of the reagent:

For a redox titration, usually the Esystemis independent of the dilution.

Consequently, the titration curves for redox reactions are generally
independent of the concentrations of the analyte and the reagent. This characteristic

it contrasts with what is observed in other types of titration curves.

Extent of the reaction:

The variation of the potential in the P.E. region of a redox titration becomes greater at

as the reaction becomes more complete. In this aspect, then, the curves of
Redox titrations are similar to those involving other types of reactions.

28
 REDOX INDICATORS
They are substances that change color when oxidized or reduced.

In contrast to the specific indicators, the changes in color of

true redox indicators are largely independent of
the chemical nature of the analyte and the titrant and depend, on the contrary, on

variations of the electrode potential of the system that occur during the
titration.

Inox+ no- ⇌ Inred

0.0592 [Inred]
E E 0
 log
In/oxIn red
Inox ]
29
Inred1 Color change Inred] 0.0592
10 E E 0
In
[Ino x ] 10 Ino x ] n

30
 ORTOFENANTROLINA
Forms complexes with Fe(II) and some other ions.

(phen)3Fe3++ e- (phen)3Fe2+
light blue red

Of all the redox indicators, ferroin is

that which comes closest to the substance
ideal. It reacts quickly and reversibly,
your color change is pronounced, and your
solutions are stable and easily
prepared. 31
 AMIDO

Blue complex shape with the triiodide ion.

It is a specific indicator widely used in redox reactions.

involving iodine with an oxidizing agent or iodide as a reducing agent.

In the presence of an excess of oxidizing agent, the ratio of

iodine and iodide concentrations are high, providing a blue color for
the solution.

With excess reducer, on the other hand, the iodide ion predominates and binds
blue becomes absent.
32
 SPECIFIC INDICATORS

The best known is starch, which forms a dark blue complex.

with the triiodide ion.

This complex indicates the endpoint in titrations where iodine is

produced or consumed.

•Another specific indicator is the KSCN. The final point involves the
disappearance of the red color of the iron(III)-thiocyanate complex as
a result of the significant decrease in the concentration of iron(III) in
equivalence point.

33
34
 EXERCISE
A sample of 0.2981 g of an antibiotic powder was dissolved in HCl and the
solution was diluted to 100.0 mL. An aliquot of 20.00 mL was transferred to a
flask, followed by the addition of 25.00 mL of KBrO30.01767 mol L-1An excess
KBr was added to form Br2and the bottle was closed. After ten minutes,
during which the Br2reacted with sulfanilamide, an excess of KI was
added. The iodine released was titrated with 12.92 mL of sodium thiosulfate
0.1215 mol L-1The reactions are:

BrO3+
- 5Br- + 6H+ 3Br2+ 3H2O

Br2+ 2I- 2Br- + I2

I2+ 2S2O3 2- 2S4O6+ 2I2--

Calculate the % of sulfanilamide

present in the dust. 35
172.21 g mol-1
 EXERCISE
Aqueous solutions containing approximately 3% (m/m) of H2O2 are
sold in pharmacies as disinfectants. Propose a method for the
determination of the amount of peroxide in these preparations using the
standard solution 0.0100 mol L-1. Consider that you want to use between 30 and 45
mL of the reagent in the titration.

36
 APPLICATION
Determination of water with Karl Fischer reagent

One of the most widely used analytical methods in the industry and in
commerce is the titration procedure of Karl Fischer, used in
determination of water in numerous organic solids and liquids. This
the important titrimetric method is based on an oxidation-reduction that
is relatively specific to water.

The Karl Fischer reaction is based on the oxidation of SO.2hair I2. In a

solvente que não é nem ácido nem básico–um solvente aprótico–a

reaction can be summarized by

I2+ SO2+ 2H2The⇌ 2HI + H2SO4 37

 KARL FISCHER
To stabilize the stoichiometry and shift the equilibrium to the right,
Fischer added pyridine and used anhydrous methanol as the solvent.

A large excess of pyridine was used to complex I.2and that2.

C5H5N I2+ C5H5N SO2+ C5H5N + H2The 2C5H5N HI + C5H5N SO3

C5H5N+ SO-3+ CH3OH C5H5N(H)SO4CH3

Undesirable:

C5H5N+ SO-3+ H2The C5H5NH+SO4H-

It is not specific to H.2The excess MeOH is added

38
 KARL FISCHER

The classic Karl Fischer reagent consists of I2, SO2, pyridine and
anhydrous methanol or another suitable solvent.

The reagent decomposes over time and must be standardized.

frequently.

Endpoint detection: based on the brown color of the reagent in

excess.

39