REDUCTION - OXIDATION TITRATION

REDOX TITRATION
References

1- Fundamentals of analytical chemistry, Skoog.

2- Analytical chemistry, Gary D. Christian.

3- ‫هادي حسن جاسم‬.‫الكيمياء التحليلية الجامعية تأليف د‬

Oxidation is defined as a loss of electrons to give a higher oxidation state

(more positive).

Reduction is defined as a gain of electrons to give a lower oxidation state

(more negative).

OXIDATION NUMBERS The following rules predict the oxidation

number for each of the atoms/ions in a compound or ion.
General Rules (Always applicable–No exceptions)
1. For any uncombined element, the oxidation number is zero.
Examples: Fe, Xe, O2, H2 (0 for all of these)
2. For any monatomic ion, the oxidation number is equal to the charge on
the ion. Examples: Fe2+, F-, O2-, H+ (+2, -1, -2, and +1 respectively)
3. For any compound, the sum of the oxidation numbers must be zero.
Examples: NaCl = Na+ + Cl- = +1 + (-1) = 0
MgF2 = Mg2+ + 2 F- = +2 + 2(-1) = 0
K2(Cr2O7)3 = 2 K+ + 6 Cr + 21 O2-
= 2(+1) + 6(X) + 21(-2) = 0 ---- X = +6

Special Rules These rules only apply to certain columns on the Periodic
Table.
1. Column IA +1 (Except H with a metal, then H = -1)
2. Column IIA +2
3. Column IIIA +3 (Normally, however +1 possible near the bottom of the
table)
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4. Column IVA +4
5. Column VA +5 to -3
6. Column VIA -2 (Oxygen is -2 except when combined with F, or in O22-)
7. Column VIIA -1 (Fluorine is -1 in compounds)
8. Column VIIIA (Usually only 0)
9. Transition Metals (3-12)

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Oxidizing agent an oxidizing substance which tend to take on an
electron or electrons and be reduced to a lower oxidation state. For
-
example - Ma+ + ne M (a - n) +

Ce4+ + e- Ce3+

 Oxidizing ability depends strongly on pH value.

KMnO4 in presence of dil. H2SO4

MnO4-1 +8H+ +5e- Mn+2 + 4H2O E0red = + 1.52 V

3
Q – Calculate the oxidation number for the central atom in the
following compounds.

KMnO4, K2Cr2O7, H2O2, HNO3, H2SO4, KIO3, CdCl2.

H2SO4 : (+12)+(S)+(-24) = 0 S=+6

Reducing agent an reducing substance which tend to give up an

electron or electrons and be oxidized to a higher oxidation state. For
-
example - Ma+ M (a + n) + + ne

Fe2+ Fe3+ + e-

Oxalic acid H2C2O42H2O ::: C2O42- = CO2 +2e-

Q – Calculate the oxidation number for the central atom in the

following compounds.

H2C2O42H2O, H2S, SnCl2

REDUCTION - OXIDATION REACTION

Is one that occurs between a reducing and an oxidizing agent,

For example Ox1 + Red2 Red1 + Ox2

Ce 4+ + Fe 2+ Ce3+ + Fe 3+
2H+ +Zn(s) H2(g) + Zn2+
Electro chemical cells:
There are two kinds of electrochemical cells, galvanic (voltaic) and
electrolytic cell.

1- galvanic cells In this type of cells the chemical reaction spontaneously

occurs to produce electrical energy for example , zinc - copper cell, lead
storage battery , copper - silver cell.

4
 Copper - Silver cell

2- Electrolytic cell electrical energy is used to force a nonspontaneous

chemical reaction to occur, that is to go in the reverse direction it would in a
galvanic cell. An example is the electrolysis of water
2H2O H2(g) + 2O2(g) (acid solution)

An electrochemical cell consists of two conductors called electrodes each

of which is immersed in an electrolyte solution .
Anode is the electrode at which oxidation occurs.
Cathode is the electrode at which reduction occurs.
The solutions surrounding the two electrodes are different and must be
separated to avoid direct reaction between the reactants.
The most common way of avoiding mixing is to insert a salt bridge.
Salt bridge allows charge transfer through the solution but prevent
mixing of the solution .
Q- The equation that is not represented as a redox reaction is,

a- AgNO3+ NaCl AgCl + NaNO3

b- 2H2 + O2 2H2O

c- 2H2O2 2H2O + O2 (g)

d- Cu(s) +2 AgNO3 Cu(NO3)2 + 2Ag(s)

5
Redox reaction as two half reaction As a redox reaction involves
both oxidation and reduction components, it is possible to divide the total
reaction , these clearly demonstrate which species gains electrons and
which losses them .
This can be suitably illustrated by the reaction between iron ( III ) and tin (II).

2Fe 3+ + Sn 2+ Sn4+ + 2 Fe 2+
This reaction can be divided into two half reactions show below

2Fe 3+ + 2e- 2 Fe 2+ (reduction)

Sn 2+ Sn4+ + 2e- (oxidation)

Total 2Fe 3+ + Sn 2+ + 2e- Sn4+ + 2 Fe 2+ + 2e-

This method of expressing a redox reaction as two half reactions provide a

kind of flexibility to the concept of redox reaction.
No half reaction occur by itself there must be an electron donor (reducing
agent ) and an electron accepter (an oxidizing agent ) Fe3+ oxidizing agent
Sn2+ reducing agent .
(SHE) standard hydraogen electrode: the electrode potential of the
half reaction 2H+ + 2e-  H2 E0 = 0.00 V

This figure show the (SHE)

6
The potential have differences between this half reaction and other half
reactions have been measured and arranged in increasing order.
Table - standard potentials of some element

7
The electrochemical cell by convention a cell is written with the anode on
the left

anode /solution /cathode

For example C4+ + Fe2+ Ce3+ + Fe3+

Pt/ Fe2+(C1) , Fe3+(C2) // C4+(C3) , Ce3+(C4) /Pt

C1 C2 C3 and C4 represent the concentration of the different species , the
double line represents the salt bridge.
Since oxidation occurs at the anode and reduction occurs at the cathode, the
stronger reducing agent is placed on the left and the stronger oxidizing
agent is placed on the right.
The potential of the cell is given by
Ecell = Ecathode - Eanode
So a positive potential difference provides the necessary negative free
energy. For example Electro chemical cells

Fe3+ + e- = Fe2+ Eored = +0.771V

Sn4++2e- = Sn 2+ Eored = +0.154V

Eocell = Eocathode - Eoanode = 𝐄 𝐨 𝐅𝐞𝟑+/ 𝐅𝐞𝟐+  𝐄 𝐨 𝐒𝐧𝟒+ / 𝐒𝐧𝟐+

= 0.771 – (0.154) = 0.617V

Example - determine the reaction between the following half-reaction and

calculate the corresponding cell voltage:
Fe3+ + e- = Fe2+ Eored = +0.771V
I3- + 2e- = 3I- Eored = +0.5355V

Solution: since the Fe3+ / Fe2+ potential is the more positive, Fe3+ is a
better oxidizing agent than I3-. Fe3+ will oxidize I- and
Eocell = Eocathode - Eoanode = Eocell =𝐄 𝐨 𝐅𝐞𝟑+/ 𝐅𝐞𝟐+ − Eo I3-/ I-

8
In the some fashion, the second half-reaction must be subtracted from the
first (multiplied by 2) to give the overall cell reaction,
2Fe3+ + 3I- = 2Fe2+ +I3- Eocell = 0.771 V- 0.536 V = +0.235 V
* That multiplying a half-reaction by any number does not change its
potential.

Balancing Redox Equations

Knowing how to balance oxidation- reduction reactions is essential to
understanding all the concepts covered in this course .
Q- Complete and balance the following equation after adding H+ OH-,
or H2O as needed
MnO4- + NO2- Mn2+ + NO3-
1- We write and balance the two half-reaction involved.
For MnO4, we write MnO4- Mn2+
To account for the 4 oxygen atoms on the left-hand side of the equation we
add 4H2O on the right-hand side of the equation, which means that we must
provide 8H+ on the left.
MnO4- + 8H+ Mn2+ +4H2O
To balance the charge, we need to add 5 electrons to the left side of the
equation. Thus
MnO4- + 8H+ +5e- Mn2+ +4H2O
For the other half-reaction
NO2- NO3-

We add one H2O to the left side of the equation to supply the needed
oxygen and 2H+ on the right to balance hydrogen
NO2- + H2O NO3- + 2H+
Then we add two electrons to the right-hand side to balance the charge
NO2- + H2O NO3- + 2H+ + 2e-
Before combining the two equation, we must multiply the first by 2 and

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 the second by 5 so that the number of electrons lost will be equal to the
number of electrons gained. We then add the two half-reactions to obtain
2MnO4-+16H++ 10e-+ 5NO2-+5 H2O 2Mn2++8H2O+5NO3- +10 H+ +10e-
Which then rearranges to the balanced equation
2MnO4- + 6H+ + 5NO2- 2Mn2+ + 5NO3- + 8H2O
-------------------------------------------------------------
Q - Complete and balance the following equation after adding H+ OH-,
or H2O as needed
MnO4- + Fe2+ Mn2+ + Fe3+
---------------------------------------------------------------------------------------
The effect of concentration on electrode potential

Nernst equation :

A mathematical expression that related the potential of an electrode to the

activities of those species in solution that is responsible for potential. For a
cell with the following general equation

aA + bB + ------ + ne cC + dD + -------

The electrode potential for this reaction is given by the equation

𝑹𝑻
𝟎
[𝑪]𝒄 [𝑫]𝒅 − −
𝑬=𝑬 − 𝒍𝒏
𝒏𝑭 [𝑨]𝒂 [𝑩]𝒃 —
Where

E0 = the standard electrode potential which is characteristic for each half-

reaction, R= the gas constant 8.314 K-1 mol-1 ,T= temperature K, n =
number of moles of electrons that appear in the half –reaction for the
electrode process as written, F = faraday constant = 96485 C, In = natural
logarithm = 2.303 log,
If we substitute numerical values for the constants convert to bas 10
logarithms and specify 25 0C for the temperature, we gat

𝟎. 𝟎𝟓𝟗𝟐
𝟎
[𝑪]𝒄 [𝑫]𝒅 − −
𝑬=𝑬 − 𝒍𝒐𝒈
𝒏 [𝑨]𝒂 [𝑩]𝒃 —

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Examples : Typical half-cell reactions and their corresponding nernst
expressions follow.
𝟎.𝟎𝟓𝟗𝟐 𝟏
1- Zn2+ +2e Zn(s) E = E0 – log Zn(s)
𝟐 [𝒁𝒏𝟐+ ]
is not included in the logarithmic because it is a pure solid. Thus, the
electrode potential varies linearly with the logarithm of the reciprocal of the
zinc ion concentration [Zn2+].

𝟎.𝟎𝟓𝟗𝟐 [𝑭𝒆𝟐+ ]
2- Fe 3+ + e Fe2+ E = E0 – log
𝟏 [𝑭𝒆𝟑+ ]
the potential for this couple can be measured with an inert metallic
electrode immersed in a solution containing both iron species.
The potential depends on the logarithm of the ratio between the molar
concentrations of these ions.

𝟎.𝟎𝟓𝟗𝟐 𝒑𝑯𝟐
3- 2H+ + 2e H2 (g) E = E0 – log
𝟐 [𝑯+ ]𝟐
ln this example PH2 is the pressure of hydrogen (in atm) at the surface of
the electrode.

0 𝟎.𝟎𝟓𝟗𝟐 [𝑴𝒏𝟐+ ]
4- MnO4- + 5e +8H+ Mn2+ + 4H2O, E = E – log
𝟓 [𝑴𝒏𝑶𝟒 − ][𝑯+ ]𝟖
Here, the potential depends not only on the concentration of manganese
species but also on the pH of the solution.

𝟎.𝟎𝟓𝟗𝟐
5- AgCl(s) + e Ag(s) + Cl- E = E0 – log [𝑪𝒍− ]
𝟏
This half-cell reaction describes the behavior of silver electrode immersed
in a chloride solution that is saturated with AgCl.
Example: calculate the electrode potential of a silver electrode immersed
in a 0.05 M solution of NaCl using (a) E0 Ag+/Ag = 0.776 V
(b) E0 AgCl/Ag =0.222 V. Ksp (AgCl) =1.82 x 10-10.

Solution : (a) Ag+ + e Ag(s) E0 Ag+/Ag = 0.776 V

The [Ag+ ] concentration of this solution is given by

𝑲𝒔𝒑 𝟏.𝟖𝟐 𝐱 𝟏𝟎−𝟏𝟎
[𝐀𝐠 + ] = = = 𝟑. 𝟔𝟒 × 𝟏𝟎−𝟗 𝐌
[𝑪𝒍− ] 𝟎.𝟎𝟓

Substitution into nernst expression gives:

𝟏
𝐄 = 𝟎. 𝟕𝟕𝟔 – 𝟎. 𝟎𝟓𝟗𝟐 𝐥𝐨𝐠 = 0.299 V (b) Here we may write
𝟑.𝟔𝟒 ×𝟏𝟎−𝟗

E = 0.222 – 0.0592 log [Cl-] = 0.222 – 0.0952 log 0.05 = 0.299 V

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Oxidation-reduction (redox) Titration: In redox titrations the
concentration of the substances or ions involved in the reaction
continuously keeps changing in the course of the titration. Hence the redox
potential of the solution must also change (the phenomenon may be
compared to the change of the pH of solution during acid-base titration) by
plotting the redox potential corresponding to different points in the
titration, a titration curve similar to the curve obtained in an acid-base
method is obtained. The titration curve in redox reactions can be drawn by
plotting the potential of half cell against the volume in millimeter of the
titrant.
Points in the redox titration
1- Before titration
2- Prior to the equivalence point
3- At the equivalence point
4- After the equivalence point
Example: consider the titration of 50.0 ml of 0.05 M Fe2+ with 0.10 M
Ce4+ in a medium that is 1.0 M in H2SO4 at all time.
Ce4+ + e- Ce3+ Eo = 1.44 V (1M H2SO4)
Fe3+ + e- Fe2+ Eo= 0.68 V (1M H2SO4)
Solution:
At all times during the titration this reaction is rapid and reversible and in
equilibrium hence
Esystem is the potential of the titration and is the value plotted on the y-axis.
Esystem represents the potential of the electrochemical cell:
Ce4+ + Fe2+ Ce3+ + Fe3+

SHE// Ce4+, Ce3+, Fe3+, Fe2+/Pt

We can follow either 𝐄𝐂𝐞𝟒+ ,𝐂𝐞𝟑+ or 𝐄𝐅𝐞𝟑+,𝐅𝐞𝟐+
12
Esystem = 𝐄𝐂𝐞𝟒+,𝐂𝐞𝟑+ = 𝐄𝐅𝐞𝟑+,𝐅𝐞𝟐+
(a) At Volume [Ce4+ ]solution = 0 mL
In the beginning of the titration the solution would contain only Fe2+ ions
and may have traces of Fe3+ due the aerial oxidation of the solution.
As the concentration of the Fe3+ ion is too small the calculation of the
potential has no meaningful significance.
(b) At Volume [Ce4+ ]solution = 5 mL
Excess of Fe2+ concentration of (Fe2+ / Fe3+) are measurable.
𝟎.𝟎𝟓𝟗𝟐 [𝐅𝐞𝟐+ ]
Esystem = 𝐄𝐅𝐞𝟑+ ,𝐅𝐞𝟐+ = 𝐄 𝐨 𝐅𝐞𝟑+,𝐅𝐞𝟐+ − 𝐥𝐨𝐠
𝒏 [𝐅𝐞𝟑+ ]
𝟓𝟎×𝟎.𝟎𝟓−𝟓×𝟎.𝟏 𝟓𝟎×𝟎.𝟎𝟓−𝟓×𝟎.𝟏 𝟐.𝟎
[Fe2+]= + [𝐂𝐞𝟒+ ] ≈ = 𝐌
𝟓𝟎+𝟓 𝟓𝟎+𝟓 𝟓𝟓
𝟓×𝟎.𝟏 𝟎.𝟓 𝟎.𝟓
[Fe3+]= − [𝐂𝐞𝟒+ ] ≈ = 𝐌
𝟓𝟎+𝟓 𝟓𝟎+𝟓 𝟓𝟓
𝟐.𝟎
𝟎.𝟎𝟓𝟗𝟐 ( )
𝟓𝟓
Esystem = 𝐄𝐅𝐞𝟑+ ,𝐅𝐞𝟐+ = 𝟎. 𝟔𝟖 − 𝐥𝐨𝐠 𝟎.𝟓 = 𝟎. 𝟔𝟒 𝐕
𝟏 ( )
𝟓𝟓

(c)- At Volume [Ce4+ ]solution = 25 mL at the eq. point : no excess of [Fe2+]

[Ce4+ ]Vtotal = [Fe2+] Vtotal and [Ce3+ ]Vtotal = [Fe3+] Vtotal
The reaction takes place in one vessel
[Ce4+ ] = [Fe2+] and [Ce3+ ] = [Fe3+]
𝟎.𝟎𝟓𝟗𝟐 [𝐅𝐞𝟐+ ]
Eeq=𝐄𝐅𝐞𝟑+,𝐅𝐞𝟐+ = 𝐄 𝐨 𝐅𝐞𝟑+,𝐅𝐞𝟐+ − 𝐥𝐨𝐠 ------(1)
𝒏 [𝐅𝐞𝟑+ ]

𝟎.𝟎𝟓𝟗𝟐 [𝐂𝐞𝟑+ ]
Eeq=𝐄𝐂𝐞𝟒+,𝐂𝐞𝟑+ = 𝐄 𝐨 𝐂𝐞𝟒+ ,𝐂𝐞𝟑+ − 𝐥𝐨𝐠 ------(2)
𝒏 [𝐂𝐞𝟒+ ]

Summation of eq(1) and eq(2)

𝟎.𝟎𝟓𝟗𝟐 [𝐅𝐞𝟐+ ][𝐂𝐞𝟑+ ]
2Eeq= 𝐄 𝐨 𝐅𝐞𝟑+,𝐅𝐞𝟐+ + 𝐄 𝐨 𝐂𝐞𝟒+ ,𝐂𝐞𝟑+ − 𝐥𝐨𝐠
𝒏 [𝐅𝐞𝟑+ ][𝐂𝐞𝟒+ ]

= 𝐄 𝐨 𝐅𝐞𝟑+,𝐅𝐞𝟐+ + 𝐄 𝐨 𝐂𝐞𝟒+,𝐂𝐞𝟑+

𝐄 𝐨 𝐅𝐞𝟑+ ,𝐅𝐞𝟐+ +𝐄 𝐨 𝐂𝐞𝟒+ ,𝐂𝐞𝟑+ 𝟎.𝟔𝟖+𝟏.𝟒𝟒

Eeq= = = 𝟏. 𝟎𝟔 𝐕
𝟐 𝟐

(d)- At Volume [Ce4+ ]solution = 25.10 mL > Veq = 25 mL

After the eq. point : excess of [Ce4+] and concentration of [Ce3+ ]/ [Ce4+]
Are measurable. Hence Esystem post-eq = 𝐄𝐂𝐞𝟒+,𝐂𝐞𝟑+
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 𝟎.𝟎𝟓𝟗𝟐 [𝐂𝐞𝟑+ ]
Esystem = 𝐄𝐂𝐞𝟒+,𝐂𝐞𝟑+ = 𝐄 𝐨 𝐂𝐞𝟒+ ,𝐂𝐞𝟑+ − 𝐥𝐨𝐠
𝒏 [𝐂𝐞𝟒+ ]

𝟐𝟓.𝟏×𝟎.𝟏−𝟓𝟎×𝟎.𝟎𝟓 𝟐𝟓.𝟏×𝟎.𝟏−𝟓𝟎×𝟎.𝟎𝟓 𝟎.𝟎𝟏

[Ce4+]= + [𝐅𝐞𝟐+ ] ≈ = 𝐌
𝟓𝟎+𝟐𝟓.𝟏 𝟓𝟎+𝟐𝟓.𝟏 𝟕𝟓.𝟏

𝟐𝟓×𝟎.𝟏 𝟐.𝟓 𝟐.𝟓

[Ce3+]= − [𝐅𝐞𝟐+ ] ≈ = 𝐌
𝟓𝟎+𝟐𝟓.𝟏 𝟕𝟓.𝟏 𝟕𝟓.𝟏

𝟎. 𝟎𝟓𝟗𝟐 𝟐. 𝟓
𝐄𝐬𝐲𝐬𝐭𝐞𝐦 = 𝟏. 𝟒𝟒 − 𝐥𝐨𝐠 = 𝟏. 𝟑 𝐕
𝟏 𝟎. 𝟎𝟏

Redox titration methods :

1- Permanganometry
2- Dichromatometry
3- Cerimetry
4- Iodometry and Iodimetry
5- Iodametry
6- Bromatometry
Permanganometrc Titration :

This method is based on reactions of oxidation by permanganate ion.

Oxidation may proceed in acid or in alkaline or neutral solution. When
KMnO4 acts as an oxidizing agent in acidic solution the septivalent Mn in it
reduced to Mn2+ ions and a manganous salt of the acid used formed.
For example if FeSO4 is the reducing agent and if it is oxidized in the
presence of H2SO4 the reaction is represented by the equation;
14
10FeSO4 + 2KMnO4 + 8H2SO4 = 5Fe2(SO4)3 + 2MnSO4 +K2SO4 + 8H2O
Or in ionic form
5Fe2+ + MnO4- + 8H+ = 5Fe3+ + Mn2+ + 4H2O
The decrease of the valence of manganese by 5 shows that the KMnO4
molecule gains 5 electrons this is also very clear from the following
equation:
MnO4- + 8H+ + 5e- = Mn2+ + 4H2O
It follows that in this case the gram-equivalent of KMnO4 is
g-eq =158.03/5 =31.61 g
during oxidation in alkaline or neutral solution the Mn7+ ion is reduced to
Mn4+ with the formation of manganese oxide MnO2 in the form of a brown
precipitate for example
Cr2 (SO4)3 + 2KMnO4 +8KOH = 2K2CrO4 + 2MnO2 + 2K2SO4 + 4H2O
MnO4- + 4H+ + 3e- = MnO2 + 2H2O
Therefore in this case the gram-equivalent of KMnO4 has a different value
namly
g-eq = 158.03/3 = 52.68 g

A redox indicator

(Also called an oxidation-reduction indicator) is an indicator which

undergoes a definite color change at a specific electrode potential. The
requirement for fast and reversible color change means that the oxidation-
reduction equilibrium for an indicator redox system needs to be established
very quickly. Therefore, only a few classes of organic redox systems can be
used for indicator purposes.
There are two common types of redox indicators:
 metal-organic complexes (Ex. phenanthroline)
 true organic redox systems (Ex. Methylene blue)
Sometimes colored inorganic oxidants or reductants (Ex. Potassium
manganate, Potassium dichromate) are also incorrectly called redox
indicators. They can’t be classified as true redox indicators because of their
15
irreversibility. Almost all redox indicators with true organic redox systems
involve a proton as a participant in their electrochemical reaction.
Therefore, sometimes redox indicators are also divided into two general
groups: independent or dependent on pH.
Questions:
1- What is an oxidizing agent? A reducing agent?
2- What is the Nernst equation?
3- What is the standard potential?
4- What is the redox indicator?
4- Complete and balance the following equation after adding H+ OH-, or
H2O as needed
(a) - IO3- + I- I2
(b) - MnO4- + H2SO3 Mn2+ + SO42-
(c) - MnO4- + H2S Mn2+ + S
(d) – Al + NO3- AlO2- + NH3
5- What is the potential of a solution containing 10.0 ml of 0.1 M Fe2+ with
10 mL of 0.05 M Ce4+ in a medium that is 1.0 M in H2SO4 at all time?
𝑹𝑻 [𝑪]𝒄 [𝑫]𝒅 −− 𝟎.𝟎𝟓𝟗𝟐 [𝑪]𝒄 [𝑫]𝒅 −−
6- Prove the - 𝒍𝒏 equal − 𝒍𝒐𝒈
𝒏𝑭 [𝑨]𝒂 [𝑩]𝒃 — 𝒏 [𝑨]𝒂 [𝑩]𝒃 —

Knowing that R = 8.314 K-1 mol-1 and F = faraday constant = 96485 C

7- Describe the types of electrolytic cells with examples.
8- What are the types of electrolytic cells and then explain the difference
between them.
9- Determine the reaction between the following half-reaction and calculate
the corresponding cell voltage:
Cu2+ + 2e- = Cu Eored = +0.34V
Zn2+ + 2e- = Zn Eored = - 0.76V
10 - The element that undergoes oxidation is: H2 +O2 H2 O
11- The element that undergoes reduction is: N2 +3H2 2NH3
Cu + 4HNO3 → Cu (NO3)2 + 2NO2 +2H2O

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