Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation...

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Electrochemistry

description

Oxidation number The charge the atom would have in a molecule (or an ionic compound) if electrons were completely transferred. 1.Free elements (uncombined state) have an oxidation number of zero. Na, Be, K, Pb, H 2, O 2, P 4 = 0 2.In monatomic ions, the oxidation number is equal to the charge on the ion. Li +, Li = +1; Fe 3+, Fe = +3; O 2-, O = -2 3.The oxidation number of oxygen is usually –2. In H 2 O 2 and O 2 2- it is –1.

Transcript of Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation...

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Electrochemistry

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2Mg (s) + O2 (g) 2MgO (s)

2Mg 2Mg2+ + 4e-

O2 + 4e- 2O2-

Oxidation half-reaction (lose e-)

Reduction half-reaction (gain e-)

Electrochemical processes are oxidation-reduction reactions in which:

• the energy released by a spontaneous reaction is converted to electricity or

• electrical energy is used to cause a nonspontaneous reaction to occur

0 0 2+ 2-

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Oxidation number

The charge the atom would have in a molecule (or anionic compound) if electrons were completely transferred.

1. Free elements (uncombined state) have an oxidation number of zero.

Na, Be, K, Pb, H2, O2, P4 = 0

2. In monatomic ions, the oxidation number is equal to the charge on the ion.

Li+, Li = +1; Fe3+, Fe = +3; O2-, O = -2

3. The oxidation number of oxygen is usually –2. In H2O2

and O22- it is –1.

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4. The oxidation number of hydrogen is +1 except when it is bonded to metals in binary compounds. In these cases, its oxidation number is –1.

6. The sum of the oxidation numbers of all the atoms in a molecule or ion is equal to the charge on the molecule or ion.

5. Group IA metals are +1, IIA metals are +2 and fluorine is always –1.

HCO3-

O = -2 H = +1

3x(-2) + 1 + ? = -1

C = +4

Oxidation numbers of all the atoms in HCO3

- ?

4.4

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Balancing Redox Equations

1. Write the unbalanced equation for the reaction ion ionic form.

The oxidation of Fe2+ to Fe3+ by Cr2O72- in acid solution?

Fe2+ + Cr2O72- Fe3+ + Cr3+

2. Separate the equation into two half-reactions.

Oxidation:

Cr2O72- Cr3+

+6 +3Reduction:

Fe2+ Fe3++2 +3

3. Balance the atoms other than O and H in each half-reaction.

Cr2O72- 2Cr3+

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Balancing Redox Equations

4. For reactions in acid, add H2O to balance O atoms and H+ to balance H atoms.

Cr2O72- 2Cr3+ + 7H2O

14H+ + Cr2O72- 2Cr3+ + 7H2O

5. Add electrons to one side of each half-reaction to balance the charges on the half-reaction.

Fe2+ Fe3+ + 1e-

6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O

6. If necessary, equalize the number of electrons in the two half-reactions by multiplying the half-reactions by appropriate coefficients.

6Fe2+ 6Fe3+ + 6e-

6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O

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Balancing Redox Equations

7. Add the two half-reactions together and balance the final equation by inspection. The number of electrons on both sides must cancel.

6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O

6Fe2+ 6Fe3+ + 6e-Oxidation:

Reduction:

14H+ + Cr2O72- + 6Fe2+ 6Fe3+ + 2Cr3+ + 7H2O

8. Verify that the number of atoms and the charges are balanced.

14x1 – 2 + 6x2 = 24 = 6x3 + 2x3

9. For reactions in basic solutions, add OH- to both sides of the equation for every H+ that appears in the final equation.

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Dichromate ion in acidic solution is an oxidizing agent. When it reacts with zinc, the metal is oxidized to Zn2+, and nitrate is reduced. Assume that dichromate ion is reduced to Cr3+. Write the balanced ionic equation for this reaction using the half-reaction method.

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First we determine the oxidation numbers of N and Zn:+6 +3 0 +2Cr2O7

2-(aq) Cr3+(aq) and Zn(s) Zn2+(aq)

Cr was reduced from +6 to +3.Zn was oxidized from 0 to +2.

Now we balance the half-reactions.

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Oxidation half-reactionZn(s) Zn2+(aq) + 2e-

Reduction half-reactionFirst we balance Cr and O:

Cr2O72-(aq) 2Cr3+(aq) + 7H2O(l)

Next we balance H:14H+(aq) + Cr2O7

2-(aq) 2Cr3+(aq) + 7H2O(l)

Then we balance e-:6e- + 14H+(aq) + Cr2O7

2-(aq) 2Cr3+(aq) + 7H2O(l)

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Now we combine the two half-reactions by multiplying the oxidation half reaction by 3.

3Zn(s) 3Zn2+(aq) + 6e-

6e- + 14H+(aq) + Cr2O72-(aq) 2Cr3+(aq) + 7H2O(l)

3Zn(s) + 14H+(aq) + Cr2O72-(aq)

3Zn2+(aq) + 2Cr3+(aq) + 7H2O(l)

Check that atoms and charge are balanced.3Zn; 14H; 2Cr; 7O; charge +12

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To balance a reaction in basic conditions, first follow the same procedure as for acidic solution.

Then 1. Add one OH- to both sides for each H+.2. When H+ and OH- occur on the same side,

combine them to form H2O.

3. Cancel water molecules that occur on both sides.

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Lead(II) ion, Pb2+, yields the plumbite ion, Pb(OH)3

-, in basic solution. In turn, this ion is oxidized in basic hypochlorite solution, ClO-, to lead(IV) oxide, PbO2.

Balance the equation for this reaction using the half-reaction method. The skeleton equation is

Pb(OH)3- + ClO- PbO2 + Cl-

try to balance the above as practice

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H+(aq) + Pb(OH)3-(aq) + ClO-(aq)

PbO2(s) + Cl-(aq) + 2H2O(l)

To convert to basic solution, we add OH- to each side, converting H+ to H2O.

H2O(l) + Pb(OH)3-(aq) + ClO-(aq)

PbO2(s) + Cl-(aq) + 2H2O(l) + OH-(aq)

Finally, we cancel the H2O that is on both sides.

Pb(OH)3-(aq) + ClO-(aq)

PbO2(s) + Cl-(aq) + H2O(l) + OH-(aq)

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The next several topics describe battery cells or voltaic cells (galvanic cells).

An electrochemical cell is a system consisting of electrodes that dip into an electrolyte and in which a chemical reaction either uses or generates an electric current.

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A voltaic or galvanic cell is an electrochemical cell in which a spontaneous reaction generates an electric current.

An electrolytic cell is an electrochemical cell in which an electric current drives an otherwise nonspontaneous reaction.

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Physically, a voltaic cell consists of two half-cells that are electrically connected.

Each half-cell is the portion of the electrochemical cell in which a half-reaction takes place.

The electrical connections allow the flow of electrons from one electrode to the other.

The cells must also have an internal cell connection, such as a salt bridge, to allow the flow of ions.

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Galvanic Cells

19.2

spontaneousredox reaction

anodeoxidation

cathodereduction

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A salt bridge is a tube of electrolyte in a gel that is connected to the two half-cells of the voltaic cell. It allows the flow of ions but prevents the mixing of the different solutions that would allow direct reactions of the cell reactants.

In the salt bridge, cations move toward the cathode and anions move toward the anode.

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The electrode at which oxidation takes place is called the anode.

The electrode at which reduction takes place is called the cathode.

Electrons flow through the external circuit from the anode to the cathode.

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Voltaic cell notation is a shorthand method of describing a voltaic cell.

The oxidation half-cell, the anode, is written on the left.

The reduction half-cell, the cathode, is written on the right.

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The cell terminal is written on the outside: left for the anode and right for the cathode.

Phase boundaries are shown with a single vertical bar, |.

For example, at the anode, the oxidation of Cu(s) to Cu2+(aq) is shown as Cu(s) | Cu2+(aq).

At the cathode, the reduction of Zn2+(aq) to Zn(s) is shown as Zn2+(aq) | Zn(s).

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Between the anode and cathode the salt bridge is represented by two vertical bars, ||.

The complete notation for the reaction isCu(s) | Cu2+(aq) || Zn2+(aq) | Zn(s)

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When the half-reaction involves a gas, the electrode is an inert material such as platinum, Pt. It is included as a third substance in the half-cell.

For example, the half-reaction of Cl2 being reduced to Cl- is written as follows:

Cl2(g) | Cl-(aq) | PtBecause this is a reduction, the electrode appears on the far right.

For the oxidation of H2(g) to H+(aq), the notation isPt | H2(g) | H+(aq)

In this case, the electrode appears on the far left.

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To fully specify a voltaic cell, it is necessary to give the concentrations of solutions or ions and the pressures of gases. In the cell notation, these values are written within parentheses for each species.

For example, the oxidation of Cu(s) to Cu2+(aq) at the anode and the reduction of F2(g) to F-(aq) at the cathode is written as follows:

Cu(s) | Cu2+(1.0 M) || F2(1.0 atm) | F-(1.0 M) | Pt

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The cell notation for a voltaic cell isAl(s) | Al3+(aq) || Cu2+(aq) | Cu(s)

Write the cell reaction.

Our strategy is to write and balance each half-reaction, and then to combine the half-reactions to give the overall cell reaction.

The skeleton oxidation reaction is Al(s) Al3+(aq). The skeleton reduction reaction is Cu2+(aq) Cu(s).

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Balanced oxidation half-reactionAl(s) Al3+(aq) + 3e-

Balanced reduction half-reactionCu2+(aq) + 2e- Cu(s)

The common multiple of the electrons is 6. Combine the half-reactions by multiplying the oxidation half-reaction by 2 and the reduction half-reaction by 3.

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2Al(s) 2Al3+(aq) + 6e-

3Cu2+(aq) + 6e- 3Cu(s)

2Al(s) + 3Cu2+(aq) 2Al3+(aq) + 3Cu(s)

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Now we shift our focus to the movement of the electrons in the oxidation–reduction reaction.

To better understand this movement, we can compare the flow of electrons to the flow of water.

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Just as work is required to pump water from one point to another, so work is required to move electrons.

Water flows from areas of high pressure to areas of low pressure. Similarly, electrons flow from high electric potential to low electric potential. Electric potential can be thought of as electric pressure.

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Potential difference is the difference in electric potential (electrical pressure) between two points. Potential difference is measured in the SI unit volt (V).

Electrical work = charge x potential difference

The SI units for this areJ = C × V

CJV

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The magnitude of charge on one mole of electrons is given by the Faraday constant, F. It equals 9.6485 × 103 C per mole of electrons.

1 F = 9.6485 × 103 C

Substituting this into the equation for work:w = –F × potential difference

The term is negative because the cell is doing work in creating the current (that is, electron flow).

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Galvanic Cells

19.2

The difference in electrical potential between the anode and cathode is called:

• cell voltage

• electromotive force (emf)

• cell potential

Cell Diagram

Zn (s) + Cu2+ (aq) Cu (s) + Zn2+ (aq)

[Cu2+] = 1 M & [Zn2+] = 1 M

Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s)anode cathode

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Standard Reduction Potentials

19.3

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

2e- + 2H+ (1 M) H2 (1 atm)

Zn (s) Zn2+ (1 M) + 2e-Anode (oxidation):

Cathode (reduction):

Zn (s) + 2H+ (1 M) Zn2+ + H2 (1 atm)

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Standard Reduction Potentials

19.3

Standard reduction potential (E0) is the voltage associated with a reduction reaction at an electrode when all solutes are 1 M and all gases are at 1 atm.

E0 = 0 V

Standard hydrogen electrode (SHE)

2e- + 2H+ (1 M) H2 (1 atm)

Reduction Reaction

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The maximum potential difference between the electrodes of a voltaic cell is called the cell potential or electromotive force (emf) of the cell, or Ecell.

Ecell can be measured with a digital voltmeter. The anode of a voltaic cell has negative polarity; the cathode has positive polarity.

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The maximum work is given by the following equation:

Wmax = –nFEcell

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The emf of a particular cell is 0.500 V. The cell reaction is 2Al(s) + 3Cu2+(aq) 2Al3+(aq) + 3Cu(s)Calculate the maximum electrical work of this cell obtained from 1.00 g of aluminum.

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To determine the value of n (that is, the number of moles of electrons involved in either half-cell reaction), we need to examine the half-reactions.

2Al(s) 2Al3+(aq) + 6e-

3Cu2+(aq) + 6e- 3Cu(s)n = 6F = 96,485 C/molEcell = 0.500 V = 0.500 J/C

wmax = –nFEcell wmax = –(6 mol)(96,485 C/mol)(0.500 J/C)

wmax = 2.89 × 105 J

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J 10 5.36 Alg 26.98

Almol 1 Almol 2

J 10 x 2.89 35

max w

wmax = 5.36 kJ

This is the energy corresponding to the balanced reaction, so we need to convert to one gram of aluminum.

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A cell potential is a measure of the driving force of the cell reaction. It is composed of the oxidation potential for the oxidation half-reaction at the anode and the reduction potential, for the reduction half-reaction at the cathode.

Ecell = oxidation potential + reduction potential

But since we are using only the Chart of Reduction Potentials, Ecell = reduction potential of cathode – reduction potential of anode

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Ecell = Eoxidation + Ereduction

Because the electrode potentials are for reduction: Eoxidation = –Eanode

We can rewrite the equation for the cell:Ecell = - Eanode + Ecathode

Ecell = Ecathode – Eanode

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Let’s find Ecell for the following cell:

Al(s) | Al3+(aq) || Cu2+(aq) | Cu(s)

At the cathode, Cu2+(aq) is reduced to Cu(aq).E = 0.34 V

At the anode, Al is oxidized to Al3+. E = –[electrode potential for Al3+(aq)]

E = –(–1.66 V) = 1.66 V

Ecell = 0.34 V + 1.66 V

Ecell = 2.00 V

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A fuel cell is simply a voltaic cell that uses a continuous supply of electrode materials to provide a continuous supply of electrical energy. A fuel cell employed by NASA on

spacecraft uses hydrogen and oxygen under basic conditions to produce electricity. The water produced in this way can be used for drinking. The net reaction is

2H2(g) + O2(g) 2H2O(g)

Calculate the standard emf of the oxygen–hydrogen fuel cell.2H2O(l) + 2e- H2(g) + 2OH-(aq) E° = –0.83 VO2(g) + 2H2O(l) + 4e- 4OH-(aq) E° = 0.40 V

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Anode reaction:2H2O(l) + 2e- H2(g) + 2OH-(aq) E°red = –0.83 V

Cathode reaction:O2(g) + 2H2O(l) + 4e- 4OH-(aq) E°red = 0.40 V

Overall reaction:Ecell = Ecathode – Eanode

Ecell = 0.40 V – (–0.83 V)

Ecell = 1.23 V

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19.3

E0 = 0.76 Vcell

Standard emf (E0 )cell

0.76 V = 0 - EZn /Zn 0 2+

EZn /Zn = -0.76 V0 2+

Zn2+ (1 M) + 2e- Zn E0 = -0.76 V

E0 = EH /H - EZn /Zn cell0 0

+ 2+2

Standard Reduction Potentials

E0 = Ecathode - Eanodecell0 0

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

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Standard Reduction Potentials

19.3

Pt (s) | H2 (1 atm) | H+ (1 M) || Cu2+ (1 M) | Cu (s)

2e- + Cu2+ (1 M) Cu (s)

H2 (1 atm) 2H+ (1 M) + 2e-Anode (oxidation):

Cathode (reduction):

H2 (1 atm) + Cu2+ (1 M) Cu (s) + 2H+ (1 M)

E0 = Ecathode - Eanodecell0 0

E0 = 0.34 Vcell

Ecell = ECu /Cu – EH /H 2+ +2

0 0 0

0.34 = ECu /Cu - 00 2+

ECu /Cu = 0.34 V2+0

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19.3

• E0 is for the reaction as written

• The more positive E0 the greater the tendency for the substance to be reduced

• The half-cell reactions are reversible

• The sign of E0 changes when the reaction is reversed

• Changing the stoichiometric coefficients of a half-cell reaction does not change the value of E0

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Comparing Oxidizing StrengthsThe oxidizing agent is itself reduced and is the species on the left of the reduction half-reaction.

Consequently, the strongest oxidizing agent is the product of the half-reaction with the largest (most positive) E° value.

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Comparing Reducing StrengthsThe reducing agent is itself oxidized and is the species on the right of the reduction half-reaction.

Consequently, the strongest reducing agent is the reactant in the half-reaction with the smallest (most negative) E° value.

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Which is the stronger reducing agent under standard conditions: Sn2+ (to Sn4+) or Fe (to Fe2+)?Which is the stronger oxidizing agent under standard conditions: Cl2 or MnO4

-?

The stronger reducing agent will be oxidized and has the more negative electrode potential.

The standard (reduction) potentials areSn2+ to Sn4+ E = 0.15 VFe to Fe2+ E = –0.41 V

The stronger reducing agent is Fe (to Fe2+).

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The stronger oxidizing agent will be reduced.

The standard (reduction) potentials areCl2 to Cl- E = 1.36 V

MnO4- to Mn2+ E = 1.49 V

The stronger oxidizing agent is MnO4-.

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Predicting the Direction of ReactionYou can predict the direction of reaction by comparing the relative oxidizing (or reducing) strengths. The stronger oxidizing agent will be reduced. (The stronger reducing agent will be oxidized.)

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Will dichromate ion oxidize manganese(II) ion to permanganate ion in acid solution under standard conditions?

Standard potentialsCr2O7

2- to Cr3+ E° = 1.33 VMnO4

- to Mn2+ E° = 1.49 V

MnO4- has a larger reduction potential; it will oxidize

Cr3+ to Cr2O72-.

Cr2O72- will not oxidize Mn2+ to MnO4

-.

Page 56: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

What is the standard emf of an electrochemical cell made of a Cd electrode in a 1.0 M Cd(NO3)2 solution and a Cr electrode in a 1.0 M Cr(NO3)3 solution?

Cd2+ (aq) + 2e- Cd (s) E0 = -0.40 V

Cr3+ (aq) + 3e- Cr (s) E0 = -0.74 V

Cd is the stronger oxidizer

Cd will oxidize Cr

2e- + Cd2+ (1 M) Cd (s)

Cr (s) Cr3+ (1 M) + 3e-Anode (oxidation):

Cathode (reduction):

2Cr (s) + 3Cd2+ (1 M) 3Cd (s) + 2Cr3+ (1 M)

x 2

x 3

E0 = Ecathode - Eanodecell0 0

E0 = -0.40 – (-0.74) cell

E0 = 0.34 V cell

19.3

Page 57: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

First we determine the oxidation numbers of N and Zn:+6 +3 0 +2Cr2O7

2-(aq) Cr3+(aq) and Zn(s) Zn2+(aq)

Cr was reduced from +6 to +3.Zn was oxidized from 0 to +2.

Now we balance the half-reactions.

Page 58: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

19.4

Spontaneity of Redox Reactions

G = -nFEcell

G0 = -nFEcell0

n = number of moles of electrons in reaction

F = 96,500J

V • mol = 96,500 C/mol

G0 = -RT ln K = -nFEcell0

Ecell0 =

RTnF

ln K(8.314 J/K•mol)(298 K)

n (96,500 J/V•mol)ln K=

= 0.0257 Vn ln KEcell

0

= 0.0592 Vn log KEcell

0

Page 59: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

Spontaneity of Redox Reactions

19.4

G0 = -RT ln K = -nFEcell0

Page 60: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

2e- + Fe2+ Fe

2Ag 2Ag+ + 2e-Oxidation:

Reduction:

What is the equilibrium constant for the following reaction at 250C? Fe2+ (aq) + 2Ag (s) Fe (s) + 2Ag+ (aq)

= 0.0257 Vn ln KEcell

0

19.4

E0 = -0.44 – (0.80)

E0 = -1.24 V

0.0257 Vx nE0 cellexpK =

n = 2

0.0257 Vx 2-1.24 V

= exp

K = 1.23 x 10-42

E0 = EFe /Fe – EAg /Ag0 0

2+ +

Page 61: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

Physically, a voltaic cell consists of two half-cells that are electrically connected.

Each half-cell is the portion of the electrochemical cell in which a half-reaction takes place.

The electrical connections allow the flow of electrons from one electrode to the other.

The cells must also have an internal cell connection, such as a salt bridge, to allow the flow of ions.

Page 62: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

•xThe zinc metal atom loses two electrons, forming Zn2+ ions.

The Cu2+ ions gain two electrons,

forming solid copper.

The electrons flow through the external circuit from the zinc electrode to the copper electrode.

Ions flow through the salt bridge to maintain charge balance.

Page 63: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

The Effect of Concentration on Cell Emf

G = G0 + RT ln Q G = -nFE G0 = -nFE 0

-nFE = -nFE0 + RT ln Q

E = E0 - ln QRTnF

Nernst equation

At 298

19.5

- 0.0257 Vn ln QE0E = - 0.0592 V

n log QE0E =

Page 64: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

Dependence of Cell Potential on Concentration: Nernst Equation

G = G° + RT ln Q

Q is the thermodynamic equilibrium constant.

This equation allows us to relate E to E°.

QnFRTEE ln o

cellcell –

Page 65: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

Will the following reaction occur spontaneously at 250C if [Fe2+] = 0.60 M and [Cd2+] = 0.010 M? Fe2+ (aq) + Cd (s) Fe (s) + Cd2+ (aq)

2e- + Fe2+ 2Fe

Cd Cd2+ + 2e-Oxidation:

Reduction:n = 2

E0 = -0.44 – (-0.40)

E0 = -0.04 V

E0 = EFe /Fe – ECd /Cd0 0

2+ 2+

- 0.0257 Vn ln QE0E =

- 0.0257 V2 ln -0.04 VE = 0.010

0.60E = 0.013

E > 0 Spontaneous

19.5

Page 66: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

Commercial Voltaic CellsWe next look at several commercial voltaic cells.

Zinc–Carbon Dry Cell: Leclanché Anode: Zn(s) Zn2+(aq) + 2e-

Cathode: 2NH4+(aq) + 2MnO2(s) + 2e-

Mn2O3(s) + H2O(l) + 2NH3(aq)

The initial voltage is about 1.5 V, but decreases and deteriorates rapidly in cold weather.

Page 67: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

Batteries

19.6

Leclanché cell

Dry cell

Zn (s) Zn2+ (aq) + 2e-Anode:

Cathode: 2NH4 (aq) + 2MnO2 (s) + 2e- Mn2O3 (s) + 2NH3 (aq) + H2O (l)+

Zn (s) + 2NH4 (aq) + 2MnO2 (s) Zn2+ (aq) + 2NH3 (aq) + H2O (l) + Mn2O3 (s)

Page 68: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

Batteries

Zn(Hg) + 2OH- (aq) ZnO (s) + H2O (l) + 2e-Anode:

Cathode: HgO (s) + H2O (l) + 2e- Hg (l) + 2OH- (aq)

Zn(Hg) + HgO (s) ZnO (s) + Hg (l)

Mercury Battery

19.6

Page 69: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

Batteries

19.6

Anode:

Cathode:

Lead storagebattery

PbO2 (s) + 4H+ (aq) + SO2- (aq) + 2e- PbSO4 (s) + 2H2O (l)4

Pb (s) + SO2- (aq) PbSO4 (s) + 2e-4

Pb (s) + PbO2 (s) + 4H+ (aq) + 2SO2- (aq) 2PbSO4 (s) + 2H2O (l)4

Page 70: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

Batteries

19.6Solid State Lithium Battery

Page 71: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

Batteries

19.6

A fuel cell is an electrochemical cell that requires a continuous supply of reactants to keep functioning

Anode:

Cathode: O2 (g) + 2H2O (l) + 4e- 4OH- (aq)

2H2 (g) + 4OH- (aq) 4H2O (l) + 4e-

2H2 (g) + O2 (g) 2H2O (l)

Page 72: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

Chemistry In Action: Bacteria Power

CH3COO- + 2O2 + H+ 2CO2 + 2H2O

Page 73: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

Corrosion

19.7

Page 74: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

Cathodic Protection of an Iron Storage Tank

19.7

Page 75: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

19.8

Electrolysis is the process in which electrical energy is used to cause a nonspontaneous chemical reaction to occur.

Page 76: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

Electrolysis of Water

19.8

Page 77: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

Electrolysis and Mass Changes

charge (C) = current (A) x time (s)

1 mole e- = 96,500 C

19.8

Page 78: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

How much Ca will be produced in an electrolytic cell of molten CaCl2 if a current of 0.452 A is passed through the cell for 1.5 hours?

Anode:

Cathode: Ca2+ (l) + 2e- Ca (s)

2Cl- (l) Cl2 (g) + 2e-

Ca2+ (l) + 2Cl- (l) Ca (s) + Cl2 (g)

2 mole e- = 1 mole Ca

mol Ca = 0.452Cs

x 1.5 hr x 3600shr 96,500 C

1 mol e-

x2 mol e-

1 mol Cax

= 0.0126 mol Ca

= 0.50 g Ca19.8

Page 79: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

What electric charge is required to plate a piece of automobile molding with 1.00 g of chromium metal using a chromium(III) ion solution?

If the electrolysis current is 2.00 A, how long does the plating take?

Page 80: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

First, we convert mass to moles Cr; then to moles e-; then, using current, to seconds.

C 2.00s 1

e mol 1C 96,485

Cr mol 1e mol 3

Cr g 52.00Cr mol 1 Cr g 1.00 -

-

= 2.78 × 103 s = 46.4 min

Page 81: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

A solution of nickel salt is electrolyzed to nickel metal by a current of 2.43 A. If this current flows for 10.0 min, how many coulombs is this?

How much nickel metal is deposited in the electrolysis?

Page 82: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

min 1

s 60 min 10.0 sC 2.43

= 1458 C

Given the half-reaction: Ni2+(aq) + 2e- Ni(s)

Ni mol 1g 58.69

e mol 2Ni mol 1

C 96,485e mol 1 C 1458 -

-

= 0.443 g Ni

We first find the charge:

Page 83: Electrochemistry. 2Mg (s) + O 2 (g) 2MgO (s) 2Mg 2Mg 2+ + 4e - O 2 + 4e - 2O 2- Oxidation half-reaction…

Chemistry In Action: Dental Filling Discomfort

Hg2 /Ag2Hg3 0.85 V2+

Sn /Ag3Sn -0.05 V2+

Sn /Ag3Sn -0.05 V2+