Reaksi Redoks

Oxidation-Reduction Reactions
Setting the Stage

The flow of electrons is common It occurs naturally (lightning) and as a result of human activity (electricity) Early electrical experiments involved chemically generated electricity (batteries) This electron flow results from one reactant having a greater affinity for electrons than the other
General Chemistry II 2
Formulating some questions

What is involved in the electron exchange process and what are the terms used? How do we keep track of electrons? Can we predict favorable and unfavorable electron exchange reactions? How can we make unfavorable reactions occur?
Nature of Oxidation and Reduction

Na reacts with Cl2 quite vigorously, such that the piece of Na glows white hot with the heat of the reaction The process forms ordinary table salt 2 Na(s) + Cl2 (g) 2 NaCl(s)
Na +
Cl
General Chemistry II
Na + Cl
Half reactions
Electron exchange reactions can be viewed as the sum of two half reactions Half reactions represent either the loss of electrons or the gain of electrons as a separate balanced equation Sodium half reaction Na Na+ + e Na loses an electron to form a sodium ion
Half reactions
A substance that loses electrons is said to be oxidized Chlorine half reaction 2 e- + Cl2 2 Cl The neutral chlorine molecule has gained two electrons to form chloride ions A substance that gains electrons is said to be reduced
Terminology
Redox or oxidation-reduction reactions are reactions involving the exchange of electrons Oxidizing agent the species that accepts electrons Reducing agent the species that donates electrons
Redox reactions
Electrons are conserved in redox reactions e. g. electrons gained in the reduction process must equal the electrons lost in the oxidation process A common, and unfortunate, redox reaction is the rusting of iron 4 Fe(s) + 3 O2 (g) 2 Fe2O3 (s)
Oxidation states or numbers

The charge that an atom in a molecule or ion would have if all atoms were present as monatomic ions Similar to formal charge, but in this case, both electrons in the bond are assigned to the more electronegative atom sharing the electrons
Rules for assigning OS

1.
2.
OS of an element in its free, natural state is zero (Cu(s), Cl2 (g)) The OS of a monoatomic ion is the same as the charge of the ion alkali metals +1 same as group # alkaline earths +2 same as group # oxygen O2aluminum Al3+
Oxidation state
3.
4.
Halogens are in a -1 oxidation state in binary compounds whether ionic or covalent when bound to a less electronegative element Oxygen is O2- except in peroxides and superoxides. Oxygen is positive when bound to F
Oxidation States
5.
6.
H is usually +1. When bound to a less electronegative atom (usually a metal) it is -1 (as in LiH) The sum of the OS of all of the atoms in a compound must equal the charge of the compound or ion e. g. FeO has Fe2+ and O2General Chemistry II 12
Oxidation state changes

Since oxidation is the loss of electrons, and therefore results in an increase in the oxidation state. Reduction results in the decrease in the oxidation state. Generally, only one element changes oxidation state in a compound, but this is not always true
Balancing redox reactions
The oxidation state method focuses on the atoms of the elements undergoing a change in oxidation state Consider HNO3 (aq) + H2S(aq) NO(g) + S(s) + H2O(l)
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Oxidation state method

1.
2.
Identify the atoms -2 +5 HNO3 + H2S whose OS have changed Draw a bridge between the same +3eatoms whose OS has -2 +5 changed, indicating HNO3 + H2S the electrons gained or lost
+2
NO + S + H2O
+2
NO + S + H2O -2e15

3.
Multiply the two numbers of electrons (in this case +3 and -2) by whole numbers that produce a common number 32=6 23=6 use these multipliers as coefficients of the respective compounds or elements
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+3e 2 = 6
+5 -2
-
+2
HNO3 + H2S
NO + S + H2O -2e 3 = 6
4.
Balance the rest of the elements by inspection 2 HNO3 + 3 H2S 2 NO + 3 S + 4 H2O
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Balancing Redox Reactions

1.
2. 3.
Ion-electron or Half reaction method Separate the total reaction into half reactions Balance the half reactions separately Methodology depends on whether the reactions are done in acidic or basic conditions
Half reaction method
1.
Consider H+(aq) + Cl-(aq) + Cr2O72-(aq) Cr3+ + Cl2(aq) + H2O(aq) Separate the molecule or ion that contains atoms of an element that has changed oxidation state and product containing the atoms of that element. (you dont need to know the actual oxidation state)

1.
2.
3.
Cont. Cr2O72- Cr3+ Balance the atoms other than hydrogen or oxygen Cr2O72- 2Cr3+ Balance the oxygen by adding H2O on the side missing the oxygen

3.
4.
5.
Cont Cr2O72- 2Cr3+ + 7 H2O Balance the hydrogens by adding H+ on the other side of the equation from the H2O 14 H+ + Cr2O72- 2Cr3+ + 7 H2O The atoms in the half reaction should now be balanced.

5.
6.
7.
Add e- to balance the charge on both sides of the equation 6 e- + 14 H+ + Cr2O72- 2Cr3+ + 7 H2O Do the same for other half reaction 2 Cl- Cl2 + 2 eMultiply each equation by a coefficient so that the number of electrons is the same in both half reactions

Cont 3 (2 Cl- Cl2 + 2 e-) 6 Cl- 3 Cl2 + 6 e8. 6 e- + 14 H+ + Cr2O72- 2Cr3+ + 7 H2O 6 Cl- 3 Cl2 + 6 e_________________________________ 14 H+ + Cr2O72- + 6 Cl- 3 Cl2 + 2Cr3+ + 7 H2O
7.
Half reaction method basic soln

In basic solution, OH- is the predominant species (besides water) The simplest way to adjust for basic solution is to balance the reaction as if it occurred in acid, then neutralize the H+ by adding OH- to both sides. The H+ will combine with the OH
Example
1. 2.
3. 4.
2 e- + 2 H+ + ClO- Cl- + H2O 2 e- + (2 H+ + 2 OH-) + ClO- Cl- + H2O + 2 OH2 e- + 2 H2O + ClO- Cl- + H2O + 2 OH2 e- + H2O + ClO- Cl- + 2 OH-
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Spontaneous Redox Reactions

A spontaneous reaction occurs between the stronger oxidizing agent and the stronger reducing to form weaker oxidizing and reducing agents By testing reactions between pairs of atoms and molecules, we can determine a relative order of strength of oxidizing or reducing ability
Spontaneous redox reactions

Why does K react spontaneously with water? (Grxn = -407 kJ) 2 K(s) + 2 H2O(l) 2 K+(aq) + 2 OH-(aq) + H2(g) Yet Ag does not (Grxn = +314 kJ) 2 Ag(s) + 2 H2O(l) 2 Ag+(aq) + 2 OH-(aq) + H2(g)
Spontaneity
K is easily oxidized while Ag resists oxidation. The main factor is the first ionization energies IE1(K) = 419 kJ/mol IE1(Ag) = 731 kJ/mol
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Direct and indirect electron transfer

Note that Ag and K represent extremes in the spontaneity of electron transfer Consider Cu2+(aq) + Zn(s) Cu(s) + Zn2+(aq) Grxn = -213 kJ Re: Cu2+(aq) + 2 e- Cu(s) Ox: Zn(s) Zn2+(aq) +2 e
Direct electron transfer

This is an example of direct electron transfer (Cu2+ collides with the Zn surface and accepts two electrons) Scan p 869 Bottom Figure
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Indirect electron transfer

Separate the oxidation and reduction reactions into two compartments Arrange for the electrons to flow through and external circuit Connect the two compartments with a barrier that only allows inert ions to pass (to yield charge transfer)
The Danielle Cell

e-
Zn
-2e-
Cu Zn
2+ Membrane Permeable to to KCl only
Cu
2+ +2e-
Cl
aqueous KCl
Electrodes
Anode the electrode at which the oxidation takes place Cathode the electrode at which the oxidation takes place Active electrodes, such as the Zn and Cu strips, participate in the redox reaction Inert electrodes merely provide a surface at which the reaction occurs
Salt bridge
Since negative charge is flowing through the external circuit, a means must be provided to keep charge balanced The salt bridge allows inert ions to pass between the two compartments while preventing the species involved in the redox reaction from mixing
Voltaic or galvanic cells

Use a favorable redox reaction to generate electrical energy through an external circuit First practical example was the Danielle cell Zn(s) + Cu2+ Zn2+ + Cu was used to power telegraphs and other early electrical devices
35
The Danielle Cell

A Zn strip is immersed in a Zn2+ solution and in a separate compartment, a Cu strip is immersed in a Cu2+ solution. Electrodes are the surfaces in a cell at which the reactions take place The Zn and Cu strips serve as electrodes
36
Common voltaic cells

Dry cells (flashlight batteries) Lead-acid car batteries Keep in mind that a battery is a collection of one or more separate cells joined together in one unit
37
Cell potentials and current

Compare water flow and electron flow Water flows from higher elevation to lower Electrons flow from species with greater reduction potential to those of lower Potential is the force of the flow Current is the amount of material (water or electrons) that flows
Electrode equilibrium
Consider a Zn electrode immersed in ZnSO4 aqueous solution Scan p 876
39
At the molecular leve, some the of the Zn atoms on the electrode surface are oxidized and move out into solution, leaving electrons behind Zn(s) Zn2+(aq) + 2 e-(metal surface) An excess of electrons remains on the surface of the Zn electrode
A Zn2+ ion collides with the surface and captures two electrons to become a neutral Zn atom Zn(aq) + 2 e-(metal surface) Zn(s) This dynamic equilibrium results in ca one excess surface electron for every 1014 Zn atoms The same situation applies to the Cu electrode
41
A slight charge imbalance is generated on each surface, but the imbalance is greater for the Zn electrode since Zn is easier to oxidize (e.g. the concentration of excess electrons is greater on the Zn electrode) When two electrodes with different amounts of excess charge are connected, there is a difference in electrical potential between them
42
Scan Fig 18-13 Electrons flow downhill from the Zn to the Cu electrodes
43
Electrode potential
The potential difference is measured in volts (V), given the symbol E and termed the cell potential In a galvanic cell, the electrode with the higher potential is termed the negative electrode. The other is the positive electrode
Standard cell potentials

Recall standard conditions for thermodynamics (1 M concentration, 1 atm pressure, 25 C) Standard reduction potential = E The Zn-Cu galvanic cell generates a 1.10 V potential difference under standard conditions
The reference half-cell

In order to compare redox reactions against each other, it is convenient to measure cell potentials against a common reaction Conventionally, the standard hydrogen electrode is used (SHE)2 H3O+(aq, 1.00 M) + 2 e- H2 (g, 1.00 atm) + 2 H2O(l) E = 0.00 V
Standard reduction potentials

All reactions are written as reductions The Cu reaction Cu2+ + 2 e- Cu(s) E = 0.34 V vs SHE
47
Calculating standard cell potentials

Ecell = Ecathode - Eanode The half reaction with the more positive reduction potential occurs at the cathode as a reduction The half reaction with the more negative reduction potential occurs at the anode as an oxidation
Example
Cu2+(aq, 1.00 M) + 2 e- Cu(s) E = +0.34V Zn2+(aq, 1.00 M) + 2 e- Zn(s) E = -0.76V Ecell = Ecathode - Eanode Ecell = ECu - EZn = +0.34 (-0.76) = 1.10V It is important to note that cell potentials do not depend on the amount of material involved in the reaction (an intensive property)
Free energy and electron transfer

Recall G < 0 for spontaneous reactions E > 0 for spontaneous reactions The total energy change depends on the potential difference (E) and the amount of charge that flows through the cell (n, the number of moles of electrons)
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Free energy and electron transfer

G = -nFE, where F = 96,485.34 C mol-1 G = -nFE G = -nFE and G = -RT ln Keq After some math E = -(RT/nF) ln Keq At STP E = -(0.0592 V/n) log Keq
The Nernst Equation

Relates amounts of material and driving force E = E -(RT/nF) ln Q Q = (products)/(reactants) pH meter is a common device that exploit the Nernst equation to allow us to measure concentration electrically
Electrochemical stoichiometry
Measurement of electricity Charge Coulombs Current rate of electric current flow (measured in amperes) 1 A = 1 C s-1 = I (symbol for current) Charge = I t Moles of electrons = n = (I t)/F
Fuel Cells
Uses the direct reaction of chemicals such as hydrogen and oxygen to produce electricity Must be used in applications where the electrical flow must be continuous (no recharging) Can also be turned on and off by controlling the flow of reagents Very expensive, but much research is going into changing that
Electrolytic cells
Convert electrical energy into chemical energy Electrolysis of H2O (using K2SO4) to yield H2 and O2 2 H2O(l) 2 H2 (g) + O2 (g) Electroplating is another electrolytic cell that uses a base metal object (a spoon) as the cathode and a Ag bar as a cathode
Dry cells
Not rechargeable, but cheap and portable Zn casing serves as the anode and a graphite rod serves as an inert cathode. In between the two is an aqueous paste containing NH4Cl, MnO2 and carbon anode: Zn(s) Zn2+(aq) + 2 ecathode: NH4+ + 2 MnO2 (s) + 2 e- Mn2O3 (s) + 2 NH3 (aq) + H2O(l)
The Dry Cell
The disadvantage of the dry cell creates an acidic solution. This acidic solution slowly dissolves the zinc, so the shelf life of the battery is only a few months Alkaline batteries use NaOH or KOH in place of NH4Cl, which is more expensive but the shelf life is much greater. The anode becomes: Zn(s) + 2 OH-(aq) ZnO(s) + H2O(l) + 2 eGeneral Chemistry II 57
The lead acid car battery

Anode: Pb(s) + H2SO4 (aq) PbSO4 (s) + 2H+(s) + 2 e Cathode: 2 e- + 2 H+(aq) + PbO2 (s) + H2SO4 (aq) PbSO4 (s) + 2 H2O(l) Total reaction Pb(s) + PbO2 (s) + 2 H2SO4 (aq) 2 PbSO4 (s) + 2 H2O
The Lead Storage Battery

The anode is a Pb plate The cathode is Pb impregnated with PbO2 Both electrodes become coated with PbSO4 during the course of the reaction The solution is 1 M H2SO4 No porous separator is needed since both starting materials and products are insoluble in sulfuric acid
Other batteries
Silver: Zn(s) + Ag2O(s) ZnO(s) + 2 Ag(s) Mercury: Zn(s) + HgO(s) ZnO(s) + Hg(l) NiCd: Cd(s) + NiO2 (s) + 2 H2O(l) Ni(OH)2 (s) + Cd(OH)2 (s) (rechargeable)
Corrosion
Scan p 895 Process is the destructive oxidation of metals Turns refined metals into more stable metal oxides
61
Oxygen
O2 is a potent oxidizer, especially in the presence of aqueous acids O2 (g) + 2 H2O(l) + 4 e 4 OH-(aq) E = 0.401 V O2 (g) + 4 H3O+(aq) + 4 e 6 H2O(l) E = 0.401 V
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Atmospheric oxygen
P(O2) in atmosphere is 0.20 atm Atmospheric water vapor is saturated with carbon dioxide, which results in a hydrogen ion concentration of 2 10-6 M Under these conditions, E(O2) = 0.88 V Hence anything with a standard potential reduction potential less than 0.88 V oxidizes spontaneously
Structural material oxidation

4 Fe(s) + 3O2 (g) + 12 H3O+(aq) 4 Fe3+(aq) + 18 H2O(l) E = 0.88 V (-0.037 V) = +0.92 V 4 Al(s) + 3 O2 (g) + 12 H3O+(aq) 4 Al3+(aq) + 18 H2O(l) E = 0.88 V (-1.662 V) = 2.54 V
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Overall reaction
4 Fe(s) + 3 O2 (g) 2 Fe2O3 (s) 4 Al(s) + 3 O2 (g) 2 Al2O3 (s) Ions in aqueous solution (such as rainwater) accelerate the process by facilitating charge transport
65
Preventing corrosion
Paint prevents oxygen from getting to the metal Galvanization coating Fe with a thin film of a more easily oxidized metal like Zn. The Zn protects the Fe even if the Zn is scratched
66
Electrosynthesis
Electrical energy is used to synthesize a wide range of commercial products Na and Mg are common Al and Cl2 are probably the most important
67
Electrolysis
Electrolytic cells use electric current to drive redox reactions (like charging a battery) Apply an external voltage of opposite sign and greater than the redox potential for cell
68
Electrolysis of water
Anode: 6 H2O(l) O2 (g) + 4 H3O+(aq) + 4e Cathode: 4 H3O+(aq) + 4 e 2 H2 (g) + 4 H2O(l) Net reaction: 2 H2O(l) 2 H2 (g) + O2 (g)
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Example
What volume of H2 and O2 is evolved if 0.775 A is applied for 45 minutes n = [(0.775 C/s)(45 min)(60 s/min)]/F = 2.169 10-2 mol of electrons 4 mol of electrons produces 2 mol of H2 and 1 mol of O2
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Oxidation-Reduction Reactions

Setting the Stage

Formulating some questions

Nature of Oxidation and Reduction

Oxidation states or numbers

Rules for assigning OS

Oxidation state changes

Balancing redox reactions

Oxidation state method

Oxidation state method

Oxidation state method

Balance the rest of the elements by inspection 2 HNO3 + 3 H2S 2 NO + 3 S + 4 H2O

Balancing Redox Reactions

Half reaction method

Half reaction method

Half reaction method

Half reaction method

Half reaction method

Half reaction method basic soln

Spontaneous Redox Reactions

Spontaneous redox reactions

Direct and indirect electron transfer

Direct electron transfer

Indirect electron transfer

The Danielle Cell

Voltaic or galvanic cells

The Danielle Cell

Common voltaic cells

Cell potentials and current

Consider a Zn electrode immersed in ZnSO4 aqueous solution Scan p 876

Standard cell potentials

The reference half-cell

Standard reduction potentials

Calculating standard cell potentials

Free energy and electron transfer

Free energy and electron transfer

The Nernst Equation

The Dry Cell

The lead acid car battery

The Lead Storage Battery

Structural material oxidation

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