Electrochemistry

Applications of Redox

Review
Oxidation

reduction reactions involve a transfer of electrons. OIL- RIG Oxidation Involves Loss Reduction Involves Gain LEO-GER Lose Electrons Oxidation Gain Electrons Reduction

Solid lead(II) sulfide reacts with oxygen in the air at high temperatures to form lead(II) oxide and sulfur dioxide. Which substance is a reductant (reducing agent) and which is an oxidant (oxidizing agent)? A. PbS, reductant; O2, oxidant B. PbS, reductant; SO2, oxidant C. Pb2+, reductant; S2- oxidant D. PbS, reductant; no oxidant E. PbS, oxidant; SO2, reductant

Applications
Moving

electrons is electric current. 8H++MnO4-+ 5Fe+2 +5e Mn+2 + 5Fe+3 +4H2O Helps to break the reactions into half reactions. 8H++MnO4-+5e- Mn+2 +4H2O 5(Fe+2 Fe+3 + e- ) In the same mixture it happens without doing useful work, but if separate

 Connected

this way the reaction starts Stops immediately because charge builds up.

H+ MnO4-

Fe+2

Galvanic Cell
Salt Bridge allows current to flow
H+ MnO4Fe+2

 Electricity

travels in a complete circuit

H+ MnO4-

eFe+2

Instead

of a salt bridge

Porous Disk

H+ MnO4-

Fe+2

e-

e-

e-

e-

Anode
e-

Cathode
e-

Reducing Agent

Oxidizing Agent

Cell Potential
Oxidizing

agent pulls the electron. Reducing agent pushes the electron. The push or pull (driving force) is called the cell potential Ecell
Also

called the electromotive force (emf) Unit is the volt(V) = 1 joule of work/coulomb of charge Measured with a voltmeter

0.76

H2 in

Anode Zn+2 SO4-2

1 M ZnSO4

Cathode H+ Cl1 M HCl

Standard Hydrogen Electrode

This

is the reference all other oxidations are compared to

H2 in

E = 0

indicates standard + H states of 25C, 1 atm, 1 M Clsolutions. 1 M HCl

Cell Potential
+ Cu+2 (aq) Zn+2(aq) + Cu(s) The total cell potential is the sum of the potential at each electrode.
Zn(s)

Ecell = EZn Zn+2 + ECu+2 Cu

We

can look up reduction potentials in a table. One of the reactions must be reversed, so change it sign.

Cell Potential
Determine

the cell potential for a galvanic cell based on the redox reaction. Cu(s) + Fe+3(aq) Cu+2(aq) + Fe+2(aq)

E = 0.77 V Cu+2(aq)+2e- Cu(s) E = 0.34 V Cu(s) Cu+2(aq)+2eE = -0.34 V 2Fe+3(aq) + 2e- 2Fe+2(aq) E = 0.77 V
Fe+3(aq) +

e- Fe+2(aq)

Reduction potential
More

negative E

more

easily electron is added More easily reduced Better oxidizing agent

More

positive E

more

easily electron is lost More easily oxidized Better reducing agent

Line Notation
solidAqueousAqueoussolid Anode on the leftCathode on the right Single line different phases. Double line porous disk or salt bridge. If all the substances on one side are aqueous, a platinum electrode is indicated.

For

the last reaction Cu(s)Cu+2(aq)Fe+2(aq),Fe+3(aq)Pt(s)

Cu2+

Fe+2

In a galvanic cell, the electrode that acts as a source of electrons to the solution is called the __________; the chemical change that occurs at this electrode is called________. a. cathode, oxidation b. anode, reduction c. anode, oxidation d. cathode, reduction

Under standard conditions, which of the following is the net reaction that occurs in the cell? Cd|Cd2+ || Cu2+|Cu a. Cu2+ + Cd Cu + Cd2+ b. Cu + Cd Cu2+ + Cd2+ c. Cu2+ + Cd2+ Cu + Cd d. Cu + Cd 2+ Cd + Cu2+

Galvanic Cell

1) 2) 3) 4)

The reaction always runs spontaneously in the direction that produced a positive cell potential. Four things for a complete description. Cell Potential Direction of flow Designation of anode and cathode Nature of all the componentselectrodes and ions

Practice
Completely

describe the galvanic cell based on the following half-reactions under standard conditions. MnO4- + 8 H+ +5e- Mn+2 + 4H2O E=1.51 V
Fe+3

+3e- Fe(s)

E=0.036V

Potential, Work and DG

emf

= potential (V) = work (J) / Charge(C)

E = work done by system / charge

E = -w/q
Charge -w

is measured in coulombs.

=qE Faraday = 96,485 C/mol e q = nF = moles of e- x charge/mole ew

= -qE = -nFE = DG

Potential, Work and DG

DG = -nFE

E > 0, then DG < 0 spontaneous if E< 0, then DG > 0 nonspontaneous

if

In

fact, reverse is spontaneous. Calculate DG for the following reaction: Cu+2(aq)+ Fe(s) Cu(s)+ Fe+2(aq)
Fe+2(aq) +

e-Fe(s)

Cu+2(aq)+2e- Cu(s)

E = 0.44 V E = 0.34 V

Cell Potential and Concentration

Qualitatively

- Can predict direction of change in E from LeChtelier. 2Al(s) + 3Mn+2(aq) 2Al+3(aq) + 3Mn(s) if Ecell will be greater or less than Ecell if [Al+3] = 1.5 M and [Mn+2] = 1.0 M if [Al+3] = 1.0 M and [Mn+2] = 1.5M +3 +2 if [Al ] = 1.5 M and [Mn ] = 1.5 M
Predict

 DG

= DG +RTln(Q)

The Nernst Equation

-nF

E = -nFE + RTln(Q)

E = E - RTln(Q)

nF 2Al(s) + 3Mn+2(aq) 2Al+3(aq) + 3Mn(s) E = 0.48 V Always have to figure out n by balancing. If concentration can gives voltage, then from voltage we can tell concentration.

The Nernst Equation

As

reactions proceed concentrations of products increase and reactants decrease. Reach equilibrium where Q = K and Ecell = 0
0

E - RTln(K)
nF RTln(K)
nF

E =

nF E = ln(K) RT

Batteries are Galvanic Cells

Car

batteries are lead storage batteries. Pb +PbO2 +H2SO4 PbSO4(s) +H2O

Batteries are Galvanic Cells

Dry

Cell Zn + NH4+ +MnO2 Zn+2 + NH3 + H2O + Mn2O3

Batteries are Galvanic Cells

Alkaline

Zn +MnO2 ZnO+ Mn2O3 (in base)

Batteries are Galvanic Cells

NiCad

NiO2 + Cd + 2H2O Cd(OH)2 +Ni(OH)2

Corrosion
Rusting

- spontaneous oxidation. Most structural metals have reduction potentials that are less positive than O2 .
Fe O2

Fe+2 +2e+ 2H2O + 4e- 4OH-

E= 0.44 V E= 0.40 V

+ O2 + H2O Fe2O3 + H+ Reactions happens in two places.

Fe+2

Salt speeds up process by increasing conductivity Water Fe2+

Rust

Iron DissolvesFe Fe+2

eO2 + 2H2O +4e- 4OH-

Fe2+ + O2 + 2H2O Fe2O3 + 8 H+

Preventing Corrosion
Coating

to keep out air and water. Galvanizing - Putting on a zinc coat Has a lower reduction potential, so it is more easily oxidized. Alloying with metals that form oxide coats. Cathodic Protection - Attaching large pieces of an active metal like magnesium that get oxidized instead.

Electrolysis
Running

a galvanic cell backwards. Put a voltage bigger than the potential and reverse the direction of the redox reaction. Used for electroplating.

1.10
ee-

Zn 1.0 M Zn+2 Anode 1.0 M Cu+2 Cathode

Cu

e-

A battery >1.10V

e-

Zn 1.0 M Zn+2 Cathode 1.0 M Cu+2

Cu

Anode

Calculating plating
Have

to count charge. Measure current I (in amperes) 1 amp = 1 coulomb of charge per second q = I x t q/nF = moles of metal Mass of plated metal How long must 5.00 amp current be applied to produce 15.5 g of Ag from Ag+

Calculating plating
1. Current x time = charge 2. Charge Faraday = mole of e3. Mol of e- to mole of element or compound 4. Mole to grams of compound Or the reverse if you want time to plate

Calculate the mass of copper which can be deposited by the passage of 12.0 A for 25.0 min through a solution of copper(II) sulfate.

How long would it take to plate 5.00 g Fe from an aqueous solution of Fe(NO3)3 at a current of 2.00 A?

Other uses
Electrolysis

of water. Separating mixtures of ions. More positive reduction potential means the reaction proceeds forward. We want the reverse. Most negative reduction potential is easiest to plate out of solution.

Redox
Know the table 2. Recognized by change in oxidation state. 3. Added acid 4. Use the reduction potential table on the front cover. 5. Redox can replace. (single replacement)

6. Combination Oxidizing agent of one element will react with the reducing agent of the same element to produce the free element. I- + IO3- + H+ I2 + H2O 7. Decomposition. a) peroxides to oxides b) Chlorates to chlorides c) Electrolysis into elements. d) carbonates to oxides

Examples
1. 2.

3.

A piece of solid bismuth is heated strongly in oxygen. A strip or copper metal is added to a concentrated solution of sulfuric acid. Dilute hydrochloric acid is added to a solution of potassium carbonate.

44

23. 24. 25. 26.

Hydrogen peroxide solution is added to a solution of iron (II) sulfate. Propanol is burned completely in air. A piece of lithium metal is dropped into a container of nitrogen gas. Chlorine gas is bubbled into a solution of potassium iodide.

45

Examples
5.

6.

7.

A stream of chlorine gas is passed through a solution of cold, dilute sodium hydroxide. A solution of tin ( II ) chloride is added to an acidified solution of potassium permanganate A solution of potassium iodide is added to an acidified solution of potassium dichromate.
46

70.

71.

72. 73.

74.

Magnesium metal is burned in nitrogen gas. Lead foil is immersed in silver nitrate solution. Magnesium turnings are added to a solution of iron (III) chloride. Pellets of lead are dropped into hot sulfuric acid Powdered Iron is added to a solution of iron(III) sulfate.
47

A way to remember
Ox anode is where oxidation occurs Red Cat Reduction occurs at cathode Galvanic cell- spontaneous- anode is negative Electrolytic cell- voltage applied to make anode positive
An

A student places a copper electrode in a 1 M solution of CuSO4 and in another beaker places a silver electrode in a 1 M solution of AgNO3. A salt bridge composed of Na2SO4 connects the two beakers. The voltage measured across the electrodes is found to be + 0.42 volt. (a) Draw a diagram of this cell. (b) Describe what is happening at the cathode (Include any equations that may be useful.)

A student places a copper electrode in a 1 M solution of CuSO4 and in another beaker places a silver electrode in a 1 M solution of AgNO3. A salt bridge composed of Na2SO4 connects the two beakers. The voltage measured across the electrodes is found to be + 0.42 volt. (c) Describe what is happening at the anode. (Include any equations that may be useful.)

A student places a copper electrode in a 1 M solution of CuSO4 and in another beaker places a silver electrode in a 1 M solution of AgNO3. A salt bridge composed of Na2SO4 connects the two beakers. The voltage measured across the electrodes is found to be + 0.42 volt. (d) Write the balanced overall cell equation. (e) Write the standard cell notation.

A student places a copper electrode in a 1 M solution of CuSO4 and in another beaker places a silver electrode in a 1 M solution of AgNO3. A salt bridge composed of Na2SO4 connects the two beakers. The voltage measured across the electrodes is found to be + 0.42 volt. (f) The student adds 4 M ammonia to the copper sulfate solution, producing the complex ion Cu(NH3)+ (aq). The student remeasures the cell potential and discovers the voltage to be 0.88 volt. What is the Cu2+ (aq) concentration in the cell after the ammonia has been added?