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Review: Balancing REDOX reactions Balance the following redox reactions: 1. MnO4-(aq) + Cl-(aq) Mn2+(aq) + Cl2(aq) acidic solution

Electrochemistry
Oxidation-Reduction reactions.
LEORA (loose electron oxidation reducing agent) GEROA (gain electron reduction oxidizing agent)

ELECTROCHEMISTRY

2. H2O2(aq) + ClO2(aq) ClO2-(aq) + O2(g) basic solution 3. NO2-(aq)

solution

Cu2+ + Zn
+ Cr2O72-(aq) Cr3+
(aq)

Zn2+ + Cu

NO3-(aq) acidic
Reduction: Cu2+ + 2e- Cu Oxidation: Zn Zn2+ + 2e(Half-reactions of the redox process)

The two parts of the reaction can be physically separated.

The oxidation reaction occurs in one cell . The reduction reaction occurs in the other cell. A cell is a compartment for the half-reaction
The cell must contain all physical forms of the species involved
Reduction half-reaction cell contains aqueous Cu2+ and solid Cu Oxidation half-reaction cell contains aqueous Zn2+ and solid Zn

Electrochemistry
There are two kinds electrochemical cells. 1. Electrochemical cells containing in nonspontaneous chemical reactions are called electrolytic cells. 2. Electrochemical cells containing spontaneous chemical reactions are called voltaic or galvanic cells.

The combination of two cells (reduction and oxidation cell) is called an electrochemical cell

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Electrical Conduction
Metals conduct electric currents well in a process called metallic conduction. In metallic conduction there is electron flow with no atomic motion. In ionic or electrolytic conduction ionic motion transports the electrons.
Positively charged ions, cations, move toward the negative electrode (cathode) Negatively charged ions, anions, move toward the positive electrode (anode)

Electrodes
The surface in which oxidation or reduction halfreaction occurs is called the ELECTRODE.
Electrode part of reaction: active electrode Electrode not a part of reaction: INERT electrode

Voltaic or Galvanic Cells

Electrochemical cells in which a spontaneous chemical reaction produces electrical energy. Cell halves are physically separated so that electrons (from redox reaction) are forced to travel through wires and creating a potential difference. Examples of voltaic cells include:

Convention for electrodes (correct for either electrolytic or voltaic cells):

Cathode : reduction
Negative in electrolytic cells and positive in voltaic cells.

Anode : oxidation
Positive in electrolytic cells and negative in voltaic cells.

Construction of Simple Voltaic Cells

The Zinc-Copper Cell

Cell components for the Zn-Cu cell are:
1. 2. 3. A metallic Cu strip immersed in 1.0 M copper (II) sulfate. A metallic Zn strip immersed in 1.0 M zinc (II) sulfate. A wire and a salt bridge to complete circuit

The Zinc-Copper Cell

Short hand notation for voltaic cells.
The Zn-Cu cell provides a good example.
Single vertical bar: electrode Single vertical bar: electrode

Voltaic cells consist of two half-cells which contain the oxidized and reduced forms of a substances in contact with each other. A simple half-cell consists of:
A piece of metal immersed in a solution of its ions. A wire to connect the two half-cells. And a salt bridge to complete the circuit, maintain neutrality, and prevent solution mixing.

The cells initial voltage is 1.10 volts

Zn | (1.0 M) Zn2+ || Cu2+ (1.0 M) | Cu

Oxidation half-reaction Reduction half-reaction Double vertical bar : Salt bridge

In all voltaic cells, electrons flow spontaneously from the negative electrode (anode) to the positive electrode (cathode).

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The Copper - Silver Cell

Cell components:
1. 2. 3. A Cu strip immersed in 1.0 M copper (II) sulfate. A Ag strip immersed in 1.0 M silver (I) nitrate. A wire and a salt bridge to complete the circuit.

The Copper - Silver Cell

The Copper - Silver Cell

These experimental facts demonstrate that Cu2+ is a stronger oxidizing agent than Zn2+.

The initial cell voltage is 0.46 volts.

In other words Cu2+ oxidizes metallic Zn to Zn2+.

Similarly, Ag+ is is a stronger oxidizing agent than Cu2+.

Because Ag+ oxidizes metallic Cu to Cu 2+.

Compare the Zn-Cu cell to the Cu-Ag cell
The Cu electrode is the cathode in the Zn-Cu cell. The Cu electrode is the anode in the Cu-Ag cell. If we arrange these species in order of increasing strengths, we see that:

Whether a particular electrode behaves as an anode or as a cathode depends on what the other electrode of the cell is.

Standard Electrode Potential

Potential means the tendency to transfer electrons To measure relative electrode potentials, we must establish an arbitrary standard. That standard is the Standard Hydrogen Electrode (SHE). The SHE is assigned an arbitrary voltage of 0.00000000 V To determine the ability of a reaction to transfer or accept electrons relative to the SHE

The Zinc-SHE Cell

For this cell the components are:
1. 2. 3. A Zn strip immersed in 1.0 M zinc (II) sulfate. The other electrode is the Standard Hydrogen Electrode. A wire and a salt bridge to complete the circuit.

The Zinc-SHE Cell

The initial cell voltage is 0.763 volts.

The cathode is the Standard Hydrogen Electrode.

In other words Zn reduces H+ to H2.

The anode is Zn metal.

Zn metal is oxidized to Zn2+ ions.
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The Copper-SHE Cell

The cell components are:
1. 2. 3. A Cu strip immersed in 1.0 M copper (II) sulfate. The other electrode is a Standard Hydrogen Electrode. A wire and a salt bridge to complete the circuit.

The Copper-SHE Cell

Uses of Standard Electrode Potentials

Electrodes that force the SHE to act as an anode are assigned positive standard reduction potentials. Electrodes that force the SHE to act as the cathode are assigned negative standard reduction potentials. Standard electrode (reduction) potentials tell us the tendencies of half-reactions to occur as written.
Potassium (K0 ) has greater tendency to give electrons (to be OXidized relative to SHE)

The initial cell voltage is 0.337 volts.

In this cell the SHE is the anode

The Cu2+ ions oxidize H2 to H+.

The Cu is the cathode.

The Cu2+ ions are reduced to Cu metal.
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Fluorine (F20 ) has greater tendency to accept electrons (to be REDuced relative to SHE)

Uses of Standard Electrode Potentials

Standard electrode potentials are used to predict whether an electrochemical reaction (at standard state conditions) will occur spontaneously.
1. Strongest Oxidizing Agent

Uses of Standard Electrode Potentials

Choose the appropriate half-reactions from a table of standard reduction potentials. 2. Write the half-reaction equation with the more positive E0 value first, along with its E0 value. 3. Write the other half-reaction equation as an oxidation (reverse the tabulated reduction half-reaction) and change the sign of the tabulated E0. 4. Balance the electron transfer. Do not multiply the E0 values by the coefficient! (E0 values are INTENSIVE properties) 5. Strongest Reducing Agent Add the reduction and oxidation half-reactions and their potentials. This produces the equation for the reaction for which E0cell is positive, which indicates that the forward reaction is spontaneous (galvanic). If the system has a negative E0cell , the system must be nonspontaneous (electrolytic).

Standard electrode potentials are used to predict which redox couple (if there are many) will occur at the specified standard conditions

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Will silver ions (Ag+) oxidize metallic zinc (to Zn2+) or will zinc ions (Zn2+) oxidize metallic Ag (to Ag+)? (Which is more spontaneous?)

Gibbs Free Energy and Electrical Potential at Standard Conditions

For a redox reaction at standard states G0 = -nFE0cell
96 485 J G 0 = - 2 mole e - + 1.5662 V V mole e G 0 = - 302230 J/mol rxn or - 302.23 kJ/mol

Will permanganate ions, oxidize iron (II) ions to iron (III) ions, or will iron (III) ions oxidize manganese(II) ions to permanganate ions in acidic solution? (Which is more spontaneous?)

MnO4-,

n F E0cell G0

# of electrons involved in the balanced reaction 96 485 J/Vmol e- (Faradays Constant) cell potential at standard conditions standard Gibbs Free Energy

Relationship of E0cell and Equilibrium constant Keq G0 = -nFE0cell = -RTlnKeq 0 E cell = RTlnKeq / nF or lnKeq = nFE0cell / RT

96 485 J G 0 = - 4 mole e- +0.74 V V mole e G 0 = - 285595 J/mol rxn or - 285.60 kJ/mol

Consider the following reduction half-reactions involving water

+ O 2(g) + 4H (aq) + 4e - 2H 2 O (l)

Electrolytic Cells
Nonspontaneous electrochemical cells E0cell is negative G0 is positive [G0 = -nF(-E0cell value)= + value]
Eletrolysis means forcing a nonspontaneous redox reaction to occur (at the electrodes) by applying potential
+ O 2(g) + 4H(aq) + 4e- 2H2 O(l)

1.23 V
-

2(H 2(g) + 2OH

(aq)

2H 2 O (l) + 2e )

0.83 V 2.06 V

O 2(g) + 2H 2 (g) 2H 2 O (i)

More spontaneous, but cathode requires H+ (will come from H2 gas)

O 2(g) + 4H + + 4e - 2H 2 O (l) (aq) O 2(g) + 2H 2 O (l) + 4 e - 4OH -(aq) 2H 2 O (l) + 2 e - H 2(g) + 2 OH -(aq)
O 2(g) + 2H 2 O (l) + 4e - 4OH -(aq) 2(H 2(g) + 2OH -(aq) 2H 2 O (l) + 2e - ) O 2(g) + 2H 2 (g) 2H 2 O (i) 0.40 V 0.83 V 1.23 V

1.23 V 0.40 V - 0.83 V

Less spontaneous, but cathode requires H2O

1.23 V 0.83 V 2.06 V

2(H2(g) + 2OH-(aq) 2H 2 O(l) + 2e - ) O 2(g) + 2H2 (g) 2H2 O(l)

Spontaneous, releases 212.3 kJ/mole of energy Nonspontaneous, requires 212.3 kJ/mole of energy

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Electrolytic Cells
Electrolytic cells requires external potential source In electrolytic cells, reduction still occurs at cathode, oxidation at anode Polarity is reversed o cathode: negative o anode: positive Electrolysis can be done in 1-compartment or 2-compartment cells Two examples of commercial electrolytic reactions are: Electroplating of jewelry and auto parts. Electrolysis of chemical compounds.

Voltaic/Galvanic cells
o Cathode (+): Most Positive E0red o Anode (-): Most Negative E0red o The MOST positive E0cell will occur first

Electrolytic cells
o Cathode (-): Least Negative E0red o Anode (+): Least Positive E0red o The LEAST negative E0cell will occur first

Electrolytic Cell: 1-compartment

A container for the reaction mixture. Two electrodes immersed in the reaction mixture. A voltage source of direct current.
The motion of the ions through the solution = electric current. Electrolytic conduction o Positive ions migrate toward the negative electrode (cathode). o Negative ions migrate toward positive electrode (anode).

In both cases, REDUCTION occurs at CATHODE, OXIDATION occurs at ANODE (REDCAT, OXAN)
+ O 2(g) + 4H (aq) + 4e - 2H 2 O (l)

1.23 V 0.40 V - 0.83 V

O 2(g) + 2H 2 O (l) + 4 e - 4OH -(aq) 2H 2 O (l) + 2 e - H 2(g) + 2 OH -(aq)

O 2(g) + 4H + + 4e - 2H 2 O (l) (aq) 2(H 2(g) + 2OH -(aq) 2H 2 O (l) + 2e - ) O 2(g) + 2H 2 (g) 2H 2 O (i)

1.23 V

4OH -(aq) O 2(g) + 2H 2 O (l) + 4e -

- 0.40 V - 0.83 V - 1.23 V

0.83 V 2( 2 H 2 O (l) + 2 e - H 2(g) + 2 OH -(aq) ) 2.06 V 2H 2 O (i) O 2(g) + 2H 2 (g)

Voltaic/Galvanic conditions

Electrolytic conditions

Electrolytic Cell: Electrolysis of NaCl

Requires molten (melted) NaCl since ions conduct electricity

Consists of Na+ and Cl- ions.

Cathode

Anode

Liquid Na is produced at the cathode (-). 2{Na+ + e Na(l)*} Gaseous Cl2 is produced at the anode (+). 2Cl- Cl2 + 2e--------------------------------2Na++2Cl- 2Na(l)+Cl2(g) *Na(l)

Na(s)

Electrons are used in the cathode half-reaction (reduction) and produced in the anode half-reaction (oxidation). Travel of e- : from ANODE(+) to CATHODE(-). The dc source forces the e- to flow non-spontaneously from the positive electrode to the negative electrode. Na and Cl2 must NOT be allowed to come into contact with each other because they react spontaneously, rapidly and explosively to form NaCl. In Downs Cell, the liquid Na is drained off, cooled and cast into blocks, then stored in inert mineral oil to prevent reaction with atmosphere (O2) or H2O.

If direct current (greater than 3.852 V) is applied (by way of two inert electrodes) through the cell containing the molten NaCl, we observe the following:
Pale green gas (Cl2) is formed in one electrode. Molten, silvery Na forms at the other electrode. The Na particles floats on top of the molten NaCl.

This is non-spontaneous except at very high T (>801C) Direct current (dc) source supplies energy to force the reaction forward.

Downs Cell Industrial production of Na(s)

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Electrolytic Cells: Electrolysis of Aqueous KI

K+ (aq) + eK(s) 2H2O + 2e- 2H2 (g) + OHI2(s) + 2e- 2I- (aq) O2 (g) + 4H+ +4e- 2H2O -2.924 V -0.828 V +0.535 V +1.229 V

Electrolytic Cells: Electrolysis of Aqueous NaCl

Na+ (aq) + e2H2O + 2eCl2(s) + 2eNa(s) -2.714 V 2H2 (g) + OH- -0.828 V Cl- (aq) +1.360 V

Counting Electrons: Coulometry and Faradays Law of Electrolysis

Faradays Law mole substance oxidized or reduced mole e A faraday is the amount of electricity that reduces one equivalent of a species at the cathode and oxidizes one equivalent of a species at the anode.
A coulomb is the amount of charge that passes a given point when a current of one ampere (A) flows for one second. 1 amp = 1 coulomb/second

Calculations of different redox combinations and the minimum applied voltages required for electrolysis: E1 = E(K+/K) E(I2/I) = (-2.924 V) (+0.535 V) = -3.459V E2 = E(H2O/H2,OH) E(I-/I2) = (-0.828V) (0.535 V) = -1.363V E3 = E(H2O/H2,OH) E(H2O/O2, H+)=(-0.828V) (1.229) = -2.057 2nd case has smallest negative V and hence, this combination will occur first. cathode anode

Calculations of different redox combinations and the minimum applied voltages required for electrolysis: E1 = E(Na+/Na) E(Cl-/Cl2) = (-2.714 V) (+1.360 V) = -4.074 V E2 = E(H2O/H2,OH) E(Cl2/Cl-) = (-0.828V) (1.360 V) = -2.188 V

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Counting Electrons: Coulometry and Faradays Law of Electrolysis

Faradays Law states that during electrolysis, one faraday of electricity (96,487 coulombs) reduces and oxidizes, respectively, one equivalent of the oxidizing agent and the reducing agent.
This corresponds to the passage of one mole of electrons through the electrolytic cell.

Counting Electrons: Coulometry and Faradays Law of Electrolysis

Calculate the mass of palladium produced by the reduction of palladium (II) ions during the passage of 3.20 amperes of current through a solution of palladium (II) sulfate for 30.0 minutes.

Counting Electrons: Coulometry and Faradays Law of Electrolysis

Calculate the volume of oxygen (measured at STP) produced by the oxidation of water.

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Commercial Applications of Electrolytic Cells

Electrolytic Refining and Electroplating of Metals Impure metallic copper can be purified electrolytically to 100% pure Cu.
The impurities commonly include some active metals plus less active metals such as: Ag, Au, and Pt.
The electrolytic solution is CuSO4 and H2SO4 The impure Cu dissolves to form Cu2+. The Cu2+ ions are reduced to Cu at the cathode.

Commercial Applications of Electrolytic Cells

Any active metal impurities are oxidized to cations that are more difficult to reduce than Cu2+.

Effect of Concentrations (or Partial Pressures) on Electrode Potentials

The Nernst Equation

This effectively removes them from the Cu metal.

The Nernst equation describes the electrode potentials at nonstandard conditions.

The Nernst Equation

The Nernst Equation

Substitution of the values of the constants into the Nernst equation at 25o C gives:

The Nernst Equation

For this half-reaction:

The corresponding Nernst equation is:

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The Nernst Equation

Substituting E0 into the above expression gives:

The Nernst Equation

Calculate the potential for the electrode at 250C when the Cu+ ion concentration is 1/3 of the Cu2+ ion concentration. Cu2+/Cu+

The Nernst Equation

Calculate the initial potential of a cell that consists of an Fe3+/Fe2+ electrode in which [Fe3+]=1.0 x 10-2 M and [Fe2+]=0.1 M connected to a Sn4+/Sn2+ electrode in which [Sn4+]=1.0 M and [Sn2+]=0.10 M . A wire and salt bridge complete the circuit.
Calculate the E0 cell by the usual procedure.

If [Cu2+] and [Cu+] are both 1.0 M, i.e. at standard conditions, then E = E0 because the concentration term equals zero.

Substitute the ion concentrations into Q to calculate Ecell.