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Electrochemistry
• MuhaMMad Fahad ansari

        • 12iEEM14
Electrochemistry
• One of the major classes of chemical reactions involves an
  electron exchange between the reactants.
• These reactions are called oxidation-reduction reactions or
  electrochemical, reactions. they can be further subdivided
  into two types or classes:
  Reactions those that produce electrical energy and those that
  are produced by electrical energy.
  One-type of reaction is spontaneous and may be used to
  produce electricity;
  The-second must be forced to occur and requires electricity
  to make it take place
Spontaneous Chemical Reactions
      Produce Electrical-Energy
For example:
• The electrical energy used to start a car is
  produced by an oxidation-reduction reaction
  in the car’s battery.
• Similarly, the electricity that causes the light
  in a flash light comes from electrochemical
  reactions in the dry cell of the flashlight.
Non spontaneous Chemical Reaction
  Produced by Electrical-Energy

The type of electrochemical reactions require
electrical energy, or the use of electrical
energy to bring about chemical reactions,
which is called electrolysis.
Electroplating     is    another       important
application in which electricity is used to bring
about a chemical reaction.
Electrolysis
  Many of the active elements (those with strong
  tendency to lose or gain electrons) are available only
  as the result of electrolysis.

For example: Na and Cl found in nature only in the
  form of their ions (Na+, Cl-) in compounds.
• Electricity is used to take an electron away from the
  Cl- ion and their by re-form the atom, (Cl).
• Similarly, electricity is required to force the Na+ to
  gain an electron to become a sodium (Na) again.
Electroplating
• Electroplating involves electrolysis that is carried out
  so that the ions of metal are converted into atoms
  on the surface to be plated.

• Cu (s)  Cu (aq) + 2e- (half equation/reaction)
• Ag+ (aq) + e-  Ag (s) (half equation/reaction)

• Cu(s) + 2Ag+(aq)  Cu2+(aq) + 2Ag(s)

• Cu(s)RA + 2Ag+(aq)OA <===> Cu2+(aq)OA + 2Ag(s)RA
Redox Reactions
• Some common redox reactions are those that
  occur in batteries, when metals rust, when
  metals are plated from solutions, and
• Combustion of organic molecules such as
  hydrocarbons (like methane and gasoline) and
  carbohydrates (like wood).
Basic Oxidation-Reduction Reactions
              Concepts

Chemical reactions involves an electron
exchange between the reactants, in which one
substance loses electrons and another
substance gains electrons.
• Oxidation: is the loss of electrons by atoms, ions, or
  molecules.
• Reduction: is the gain of electrons by atoms, ions, or
  molecules.
• Oxidizing agent: Substance that causes another
  substance to lose electrons
• Reducing agent: Substance that loses electrons in a
  chemical reaction; it reduces another substance by
  losing electrons to it.
Reactions


        Reactants               Product
  2Na       +       Cl2 → 2 Na+ Cl-
Loses               Gains
Oxidized            Reduced
Reducing agent      Oxidizing agent
Electron transfer or oxidation/reduction reactions
Or transfer of charge - an electron - from one
  species to another


• 2Mg(s) + O2(g)  2MgO(s)


• Fe(s) + O2(g)  Fe oxides (s)


• C(s) + O2(g)  CO2(g)
CH4 + O2  H2O + CO2

  Since H has an oxidation # of 1+,
  the oxidation # of C in CH4 is 4-,
  while in CO2 it is 4+.


Clearly C has been oxidized by the oxidizing
  agent O2.
O2 has been reduced to form both products.
Step-wise oxidations of the carbon.
           CH4 + O2  H2O + CO2




the oxidation numbers for the central C in each
molecule are 4-, 2-, 0, 2+, and 4+ as you proceed
from left to right
Oxidation Number or Oxidation State

Simple and Arbitrary Rules:
• The oxidation number of an element in its free or
  uncombined form is zero.
  For example: Na0, Mg0, S0, O20, and so on.


• The oxidation number of mono-atomic ions equals the
  number of electrons it has lost or gained.
  For example: Na1+, Mg2+, Al3+, Cl1-, S2-, and so on.
• The oxidation number of oxygen in compounds is usually -2.
  The exceptions are the peroxides, such as H2O2, and compounds
  of oxygen and fluorine, such as OF2.


• The oxidation number of hydrogen in compounds is usually +1.
  The hydrides, such as NaH, are exceptions.

• In the formula for a compound, the sum of the positive oxidation
  numbers must equal the sum of the negative oxidation numbers.
  For example: Mg2+S2-, Na1+Cl1-, K1+Mn7+O48-, H22+S6+O48-, and so on.


• In complex ions such as SO42-, PO43-, ClO31-, the algebraic sum of
  the oxidation numbers of the individual atoms in the ion equals
  the charge on the ion.
Examples
The oxidation number of S in SO42- , Cl in ClO31- and P in PO43- are


• SO42-                x +4(-2) = -2 (net charge on ion)
                       x -8 = -2
                       x = 8 -2 = 6
• ClO31-               x + 3(-2) = -1 (net charge on ion)
                       X-6=-1
                       X=6–1=5
• PO43-                x + 4(-2) = -3 (net charge on ion)
                       X-8=-3
                       X= 8 – 3 = 5
Table-Oxidation States of Some Chemical Elements
 Element    Oxidation state   Species                Formula
                  -2          Hydrogen sulfide       H2S
                   0          Elemental sulfur       S
 Sulfur           +4          Sulfur dioxide         SO2
                  +6          Sulfate ion            SO42-
                  -4          Methane                CH4
                   0          Soot, graphite         C
 Carbon           +2          Carbon monoxide        CO
                  +4          Carbon dioxide         CO2
                  -3          Ammonia                NH3
                   0          Nitrogen gas           N2
                  +2          Nitric oxide           NO
Nitrogen          +3          Nitrite ion            NO2-
                  +4          Nitrogen dioxide       NO2
                  +5          Nitrate ion            NO3-
                  -2          Almost all compounds   -
Oxygen            -1          Hydrogen peroxide      H2O2
                   0          Oxygen gas             O2
                   0          Hydrogen gas           H2
Hydrogen          +1          Hydrogen ion           H+
                  -1          Chlorine ion           Cl-
                   0          Chlorine gas           Cl2
Chlorine          +1          Hypochlorous acid      HOCl
                  +7          Perchloric acid        HClO4
Microbial Redox Process

• Important redox reactions that are carried out by
  microorganisms are summarized here:

  The notation [CH2O] is used to denote a fragment of
  an arbitrary carbohydrate.
Photosynthetic Production of Biomass
• Photosynthetic microorganisms (algae and some bacteria)
  carryout photosynthesis reactions, in these reactions,
  energy-rich carbohydrate molecules are produced by
  combining carbon dioxide and water, using energy derived
  from sunlight.
• From a Redox Perspective:


            CO2 + H2O          [CH2O] + O2

  Carbon is reduced from oxidation state +4 to 0, and
  oxygen is oxidized from -2 to 0
Aerobic Respiration:
In the presence of oxygen, microorganisms degrade
biomass to form carbon dioxide and water.
Chemical energy that is released can be used by the
organisms.


        [CH2O] + O2           CO2 + H2O

This process is the reverse of photosynthesis, carbon
is oxidized and oxygen is reduced.
Sources of Nitrogen
•   Atmosphere   N2 gas
•   Water        NH3, NH4, NO2, NO3 ions
•   Soil         NH4+ , NO2, NO3      ions
•   Plants       Proteins contains
                       (-NH2) Amino group
                        (O=C-OH) Carboxyl group
• Animals        Proteins, Urea, and Amines
                 Urea contains (NH2-C=O-NH2)
Nitrogen Fixation
• In the atmosphere, nitrogen is almost entirely in the
  form of N2 and is in oxidation state 0.


• The nitrogen in biological system is mostly in the form
  of an amine –NH2, Which is very closely related to
  ammonia (NH3) and ammonium ion (NH4+) here
  nitrogen is in oxidation state -3.

• Nitrogen in water and soil is in form of nitrate (NO3-)
  in which nitrogen is in oxidation state +5.
Microorganisms play an essential role in the movement of
nitrogen among these oxidation states.


Compounds such as ammonia and nitrate contain a
single nitrogen atom as fixed nitrogen species.

Certain groups of bacteria are capable of converting gaseous
nitrogen to fixed nitrogen, in the form of the ammonium ion.

Energy from the oxidation of biomass to CO2 is used to reduce
the nitrogen in N2 to ammonium.


3[CH2O] + 2N2 + 3H2O + 4H+  3CO2 + 4NH4+
Nitrification
In the nitrification, nitrogen in the ammonium ion is
oxidized from -3 to +5, with oxygen as oxidizer.


       NH4+ + 2O2  NO3- + 2H+ + H2O

Plants absorb nitrogen more efficiently in the form of
nitrate than an ammonium, so redox reaction can
enhance the effectiveness of ammonia-based
agricultural fertilizers.
Nitrate Reduction or Denitrification
When oxygen is not available as the oxidizer to
degrade biomass, microorganisms can use nitrate as
the oxidizer (electron acceptor).

Nitrate Reduction is used in some wastewater
treatment systems to convert fixed nitrogen to N2 gas,
which can then be safely released to the atmosphere.
This process is called denitrification, since nitrogen is
removed from the aqueous system.

Nitrogen in municipal wastewater begins in a reduced
state (-3), the overall process involved two steps:
Nitrification         in an aerobic reactor, followed by
denitrification in an anaerobic reactor, four nitrogen atoms,
being reduced from +5 to 0, can fully oxidize five carbon
atoms from 0 to +4


        NH4+ + 2O2  NO3- + 2H+ + H2O
                    (aerobic reaction)


5[CH2O] + 4NO3- + 4H+  5CO2 + 7H2O + 2N2
                  (anaerobic reaction)
Sulfate Reduction
• Some environments that contain biodegradable materials
  lake both oxygen and nitrate to serve as the oxidizing agent,
  in such cases, sulfate may serve that role.
• The conversion of one sulfur atom from +6 in sulfate to -2, in
  hydrogen sulfide oxidizes two carbon atoms from 0 to +4
  oxidation states.


    2[CH2O] + 2H+ + SO42-  2CO2 + 2H2O + H2S

• This reaction can occur in stagnant anaerobic marine
  sediments that are supplied with decaying biomass, algae or
  seaweed accumulation.
Methane Formation (Methanogenesis)
• In the absence of oxygen, nitrate, and sulfate, biomass can
  still be converted to carbon dioxide as:


                2[CH2O]  CO2 + CH4

• This is an interesting redox reaction, since the two carbon
  atoms begins in oxidation state zero (0). One carbon atom is
  oxidized to +4, and the other is reduced to -4.

• Methane generation process is exploited in seawater
  treatment to convert excess microbiological material to
  gases, which are more easily handled for disposal.
Sequence Of Redox Reactions
     (CH2O = Unidentified Organic Matter With Zero-valent Carbon)



Aerobic respiration         CH2O + O2 ↔ CO2 + H2O

Denitrification             5CH2O + 4NO3– ↔ 2N2 + 4HCO3– + CO2 + 3H2O

Manganese (IV)
                            CH2O + 2MnO2 + 3CO2 + H2O ↔ 2Mn2+ + 4HCO3–
reduction

Iron (III) reduction        CH2O + 4Fe(OH)3 + 8H+ ↔ 4Fe2+ + 8HCO3– + 3H2O


Sulphate reduction          2CH2O + SO42– + H+ ↔ H2S + 2HCO3–


Methane fermentation        2CH2O ↔ CH4 + CO2
Thank you,
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Oxidation reduction reactions BY Muhammad Fahad Ansari 12IEEM14

  • 2. Electrochemistry • One of the major classes of chemical reactions involves an electron exchange between the reactants. • These reactions are called oxidation-reduction reactions or electrochemical, reactions. they can be further subdivided into two types or classes: Reactions those that produce electrical energy and those that are produced by electrical energy. One-type of reaction is spontaneous and may be used to produce electricity; The-second must be forced to occur and requires electricity to make it take place
  • 3. Spontaneous Chemical Reactions Produce Electrical-Energy For example: • The electrical energy used to start a car is produced by an oxidation-reduction reaction in the car’s battery. • Similarly, the electricity that causes the light in a flash light comes from electrochemical reactions in the dry cell of the flashlight.
  • 4. Non spontaneous Chemical Reaction Produced by Electrical-Energy The type of electrochemical reactions require electrical energy, or the use of electrical energy to bring about chemical reactions, which is called electrolysis. Electroplating is another important application in which electricity is used to bring about a chemical reaction.
  • 5. Electrolysis Many of the active elements (those with strong tendency to lose or gain electrons) are available only as the result of electrolysis. For example: Na and Cl found in nature only in the form of their ions (Na+, Cl-) in compounds. • Electricity is used to take an electron away from the Cl- ion and their by re-form the atom, (Cl). • Similarly, electricity is required to force the Na+ to gain an electron to become a sodium (Na) again.
  • 6. Electroplating • Electroplating involves electrolysis that is carried out so that the ions of metal are converted into atoms on the surface to be plated. • Cu (s)  Cu (aq) + 2e- (half equation/reaction) • Ag+ (aq) + e-  Ag (s) (half equation/reaction) • Cu(s) + 2Ag+(aq)  Cu2+(aq) + 2Ag(s) • Cu(s)RA + 2Ag+(aq)OA <===> Cu2+(aq)OA + 2Ag(s)RA
  • 7. Redox Reactions • Some common redox reactions are those that occur in batteries, when metals rust, when metals are plated from solutions, and • Combustion of organic molecules such as hydrocarbons (like methane and gasoline) and carbohydrates (like wood).
  • 8. Basic Oxidation-Reduction Reactions Concepts Chemical reactions involves an electron exchange between the reactants, in which one substance loses electrons and another substance gains electrons.
  • 9. • Oxidation: is the loss of electrons by atoms, ions, or molecules. • Reduction: is the gain of electrons by atoms, ions, or molecules. • Oxidizing agent: Substance that causes another substance to lose electrons • Reducing agent: Substance that loses electrons in a chemical reaction; it reduces another substance by losing electrons to it.
  • 10. Reactions Reactants Product 2Na + Cl2 → 2 Na+ Cl- Loses Gains Oxidized Reduced Reducing agent Oxidizing agent
  • 11. Electron transfer or oxidation/reduction reactions Or transfer of charge - an electron - from one species to another • 2Mg(s) + O2(g)  2MgO(s) • Fe(s) + O2(g)  Fe oxides (s) • C(s) + O2(g)  CO2(g)
  • 12. CH4 + O2  H2O + CO2 Since H has an oxidation # of 1+, the oxidation # of C in CH4 is 4-, while in CO2 it is 4+. Clearly C has been oxidized by the oxidizing agent O2. O2 has been reduced to form both products.
  • 13. Step-wise oxidations of the carbon. CH4 + O2  H2O + CO2 the oxidation numbers for the central C in each molecule are 4-, 2-, 0, 2+, and 4+ as you proceed from left to right
  • 14. Oxidation Number or Oxidation State Simple and Arbitrary Rules: • The oxidation number of an element in its free or uncombined form is zero. For example: Na0, Mg0, S0, O20, and so on. • The oxidation number of mono-atomic ions equals the number of electrons it has lost or gained. For example: Na1+, Mg2+, Al3+, Cl1-, S2-, and so on.
  • 15. • The oxidation number of oxygen in compounds is usually -2. The exceptions are the peroxides, such as H2O2, and compounds of oxygen and fluorine, such as OF2. • The oxidation number of hydrogen in compounds is usually +1. The hydrides, such as NaH, are exceptions. • In the formula for a compound, the sum of the positive oxidation numbers must equal the sum of the negative oxidation numbers. For example: Mg2+S2-, Na1+Cl1-, K1+Mn7+O48-, H22+S6+O48-, and so on. • In complex ions such as SO42-, PO43-, ClO31-, the algebraic sum of the oxidation numbers of the individual atoms in the ion equals the charge on the ion.
  • 16. Examples The oxidation number of S in SO42- , Cl in ClO31- and P in PO43- are • SO42- x +4(-2) = -2 (net charge on ion) x -8 = -2 x = 8 -2 = 6 • ClO31- x + 3(-2) = -1 (net charge on ion) X-6=-1 X=6–1=5 • PO43- x + 4(-2) = -3 (net charge on ion) X-8=-3 X= 8 – 3 = 5
  • 17. Table-Oxidation States of Some Chemical Elements Element Oxidation state Species Formula -2 Hydrogen sulfide H2S 0 Elemental sulfur S Sulfur +4 Sulfur dioxide SO2 +6 Sulfate ion SO42- -4 Methane CH4 0 Soot, graphite C Carbon +2 Carbon monoxide CO +4 Carbon dioxide CO2 -3 Ammonia NH3 0 Nitrogen gas N2 +2 Nitric oxide NO Nitrogen +3 Nitrite ion NO2- +4 Nitrogen dioxide NO2 +5 Nitrate ion NO3- -2 Almost all compounds - Oxygen -1 Hydrogen peroxide H2O2 0 Oxygen gas O2 0 Hydrogen gas H2 Hydrogen +1 Hydrogen ion H+ -1 Chlorine ion Cl- 0 Chlorine gas Cl2 Chlorine +1 Hypochlorous acid HOCl +7 Perchloric acid HClO4
  • 18. Microbial Redox Process • Important redox reactions that are carried out by microorganisms are summarized here: The notation [CH2O] is used to denote a fragment of an arbitrary carbohydrate.
  • 19. Photosynthetic Production of Biomass • Photosynthetic microorganisms (algae and some bacteria) carryout photosynthesis reactions, in these reactions, energy-rich carbohydrate molecules are produced by combining carbon dioxide and water, using energy derived from sunlight. • From a Redox Perspective: CO2 + H2O  [CH2O] + O2 Carbon is reduced from oxidation state +4 to 0, and oxygen is oxidized from -2 to 0
  • 20. Aerobic Respiration: In the presence of oxygen, microorganisms degrade biomass to form carbon dioxide and water. Chemical energy that is released can be used by the organisms. [CH2O] + O2  CO2 + H2O This process is the reverse of photosynthesis, carbon is oxidized and oxygen is reduced.
  • 21. Sources of Nitrogen • Atmosphere N2 gas • Water NH3, NH4, NO2, NO3 ions • Soil NH4+ , NO2, NO3 ions • Plants Proteins contains (-NH2) Amino group (O=C-OH) Carboxyl group • Animals Proteins, Urea, and Amines Urea contains (NH2-C=O-NH2)
  • 22. Nitrogen Fixation • In the atmosphere, nitrogen is almost entirely in the form of N2 and is in oxidation state 0. • The nitrogen in biological system is mostly in the form of an amine –NH2, Which is very closely related to ammonia (NH3) and ammonium ion (NH4+) here nitrogen is in oxidation state -3. • Nitrogen in water and soil is in form of nitrate (NO3-) in which nitrogen is in oxidation state +5.
  • 23. Microorganisms play an essential role in the movement of nitrogen among these oxidation states. Compounds such as ammonia and nitrate contain a single nitrogen atom as fixed nitrogen species. Certain groups of bacteria are capable of converting gaseous nitrogen to fixed nitrogen, in the form of the ammonium ion. Energy from the oxidation of biomass to CO2 is used to reduce the nitrogen in N2 to ammonium. 3[CH2O] + 2N2 + 3H2O + 4H+  3CO2 + 4NH4+
  • 24. Nitrification In the nitrification, nitrogen in the ammonium ion is oxidized from -3 to +5, with oxygen as oxidizer. NH4+ + 2O2  NO3- + 2H+ + H2O Plants absorb nitrogen more efficiently in the form of nitrate than an ammonium, so redox reaction can enhance the effectiveness of ammonia-based agricultural fertilizers.
  • 25. Nitrate Reduction or Denitrification When oxygen is not available as the oxidizer to degrade biomass, microorganisms can use nitrate as the oxidizer (electron acceptor). Nitrate Reduction is used in some wastewater treatment systems to convert fixed nitrogen to N2 gas, which can then be safely released to the atmosphere. This process is called denitrification, since nitrogen is removed from the aqueous system. Nitrogen in municipal wastewater begins in a reduced state (-3), the overall process involved two steps:
  • 26. Nitrification in an aerobic reactor, followed by denitrification in an anaerobic reactor, four nitrogen atoms, being reduced from +5 to 0, can fully oxidize five carbon atoms from 0 to +4 NH4+ + 2O2  NO3- + 2H+ + H2O (aerobic reaction) 5[CH2O] + 4NO3- + 4H+  5CO2 + 7H2O + 2N2 (anaerobic reaction)
  • 27. Sulfate Reduction • Some environments that contain biodegradable materials lake both oxygen and nitrate to serve as the oxidizing agent, in such cases, sulfate may serve that role. • The conversion of one sulfur atom from +6 in sulfate to -2, in hydrogen sulfide oxidizes two carbon atoms from 0 to +4 oxidation states. 2[CH2O] + 2H+ + SO42-  2CO2 + 2H2O + H2S • This reaction can occur in stagnant anaerobic marine sediments that are supplied with decaying biomass, algae or seaweed accumulation.
  • 28. Methane Formation (Methanogenesis) • In the absence of oxygen, nitrate, and sulfate, biomass can still be converted to carbon dioxide as: 2[CH2O]  CO2 + CH4 • This is an interesting redox reaction, since the two carbon atoms begins in oxidation state zero (0). One carbon atom is oxidized to +4, and the other is reduced to -4. • Methane generation process is exploited in seawater treatment to convert excess microbiological material to gases, which are more easily handled for disposal.
  • 29. Sequence Of Redox Reactions (CH2O = Unidentified Organic Matter With Zero-valent Carbon) Aerobic respiration CH2O + O2 ↔ CO2 + H2O Denitrification 5CH2O + 4NO3– ↔ 2N2 + 4HCO3– + CO2 + 3H2O Manganese (IV) CH2O + 2MnO2 + 3CO2 + H2O ↔ 2Mn2+ + 4HCO3– reduction Iron (III) reduction CH2O + 4Fe(OH)3 + 8H+ ↔ 4Fe2+ + 8HCO3– + 3H2O Sulphate reduction 2CH2O + SO42– + H+ ↔ H2S + 2HCO3– Methane fermentation 2CH2O ↔ CH4 + CO2
  • 30. Thank you, well come for questions