VOLTAIC CELLS

More electropositive metal higher position in electrochemical series release electrons acts as ve terminal (anode) Half equation : Mg Mg2+ + 2e Less electropositive metal lower position in electrochemical series accept electrons acts as +ve terminal (cathode) Half equation : Cu2+ + 2e- Cu

Voltaic cells - chemical cells that produce electrical energy from chemical reaction. Simple voltaic cells immersing 2 different types of metals in an electrolyte & connecting the 2 metals by connecting wires in the external circuit. The further the distance in the electrochemical series, the bigger the cell voltage produced.

Types Of Voltaic Cells

Primary Cells

Secondary Cells

Non-rechargeable cells

Rechargeable cells

Eg: Daniell cell, Mercury cell, Dry cell, Alkaline cell

Eg: Lead-acid accumulator, nickel/cadmium cell

Daniell Cells Salt Bridge Porous Pot

Contains inert ion @ salt that does not react with the electrolyte eg: sodium chloride Functions

Has fine pores

To allow the flow of ions so that the circuit is completed To prevent the two aqueous solution from mixing
Reactions -ve terminal : Zn Zn2+ + 2e +ve terminal : Cu2+ + 2e- Cu Overall reaction : Zn + Cu2+ Zn2+ + Cu The copper metal becomes thicker (mass increases), the zinc metal become thinner (mass decrease) The concentration of copper(II) sulphate solution decrease the blue colour becomes paler. The concentration of zinc sulphate solution increases.

OXIDATION & REDUCTION OXIDATION An acceptance (gain) of O2 Donation of H2 Increase in the oxidation number Loss of electron Eg: 1. 2Mg + O2 2MgO Oxidation (addition of O2) Magnesium is oxidized to magnesium oxide. H2S + Cl2 2HCl + S Oxidation (loss of H2) REDOX REACTION A reaction in which both oxidation and reduction take place simultaneously. OXIDISING AGENT A substance that causes oxidation in another substance, and it itself reduced. Example : 2 CuO + C 2Cu + CO2 Oxidising agent Reduction (loses O2) OXIDATION NUMBER The oxidation number of an element is an arbitrary charge assigned to the element according to a set of rules. Oxidation number is also known as the oxidation state. Metals usually have positive oxidation number. For example, the oxidation number of Group 1 element in a compound is always +1. The oxidation number of a Group 2 element in a compound is always +2. Non-metals usually have negative oxidation numbers. RULES FOR ASSIGNING OXIDATION NUMBER The oxidation number of an element is zero. The sum of the oxidation states of all the atoms present in the formula of a compound is zero. Eg : In Aluminium Oxide Al2O3 2(+3) + 3(-2) = 0 For polyatomic ion, the sum of the oxidation numbers of all the atoms equals the charge of the ion. Eg : In Sulphate Ion SO42(+6) + 4(-2) = -2 - Sum of the oxidation numbers is the same as the charge on sulphate ion. REDUCING AGENT A substance that causes reduction in another substance, and it itself oxidized. Example : 2 CuO + C 2Cu + CO2 Reducing agent Oxidation (gains O2) REDUCTION Loss of O2 Gain of H2 Decrease in the oxidation number Gain of electron Eg: 1. ZnO + CuO ZnO + Cu

2.

2.

Reduction (loss of O2) Copper oxide is reduced to copper. H2 + Cl2 2HCl Reduction (addition of H2)

Element
Oxygen

Formula
O2

Oxidation Number
0

For monatomic ions, the oxidation number equals to the charge of the ion. Element Sodium ion Oxide ion Formula Na+ O2Oxidation Number +1 -2

BATTERIES
Definition : Cells in a series

TYPES OF CELLS
Primary Cells
Cannot be recharged. Examples : Alkaline cell, lithium battery, button cell, dry cell

Secondary Cells
Can be recharged by applying voltage greater than that of the spontaneous cell reaction which reverses the half reactions. Examples : Lead-acid battery, nickelcadmium cell, vanadium redox battery

Fuel Cells
Those that function continuously due to continued supply of reactants. Examples : Hydrogen-oxygen fuel cell Characteristics : Promising future More efficient than coal or gas-fired power stations Non-polluting Porous electrodes lined with catalysts Systems required to continuously supply reactants & remove products.

Dry cell Anode (-) = Zinc case Cathode (+) = Carbon rod in contact with carbon & MnO2 Electrolyte = Paste of NH4CL, ZnCl Voltage = 1.5 volts Uses : Low drain appliances such as radios, torches, toys

Lead-acid battery (accumulator) Anode (-) = Lead plates Cathode (+) = Lead plates covered with PbO2 Electrolyte = 4M H2SO4 Voltage = 2.1 volts per cell Uses : Motor vehicle batteries

Alkaline fuel cell Anode (-) = Porous carbon anode with catalyst in contact with H2(g) Cathode (+) = Porous carbon cathode with catalyst in contact with O2(g) Electrolyte = Hot KOH Voltage = ~1 volt

Alkaline cell Anode (-) = brass rod in contact with powdered zinc Cathode (+) Steel case in contact with carbon & MnO2 Electrolyte = Paste of 7M KOH Voltage = 1 volt Uses : High total capacity appliances, eg, tape recorders, shavers.

Nickel-cadmium cell Anode (-) = Grid covered with cadmium Cathode (+) = Grid covered with nickel (III) hydroxide Electrolyte = KOH Voltage = 1.25 volts Uses : Video cameras, phones, cordless drills, laptop computers.

Acid fuel cell Anode (-) = Porous carbon anode with catalyst in contact with H2(g) Cathode (+) = Porous carbon cathode with catalyst in contact with O2(g) Electrolyte = Hot H3PO4 Voltage = ~1 volt

Mercury button cell Anode (-) = Steel cap in contact with powdered zinc Cathode (+) = Steel case in contact with powdered HgO Electrolyte = Paste of KOH Voltage = 1.3 volts Uses : Watches, pacemakers, hearing aids, microphones

Half-Reaction Li+(aq) + e- -----> Li(s) K+(aq) + e- -----> K(s) Ba2+(aq) + 2 e- -----> Ba(s) Sr2+(aq) + 2 e- -----> Sr(s) Ca2+(aq) + 2 e- -----> Ca(s) Na+(aq) + e- -----> Na(s) Mg2+(aq) + 2 e- -----> Mg(s) Be2+(aq) + 2 e- -----> Be(s) Al3+(aq) + 3 e- -----> Al(s) Mn2+(aq) + 2 e- -----> Mn(s) 2 H2O + 2 e- -----> H2(g) + 2 OH-(aq) Zn2+(aq) + 2 e- -----> Zn(s) Cr3+(aq) + 3 e- -----> Cr(s) Fe2+(aq) + 2 e- -----> Fe(s) Cd2+(aq) + 2 e- -----> Cd(s) PbSO4(s) + 2 e- -----> Pb(s) + SO42-(aq) Co2+(aq) + 2 e- -----> Co(s) Ni2+(aq) + 2 e- -----> Ni(s) Sn2+(aq) + 2 e- -----> Sn(s) Pb2+(aq) + 2 e- -----> Pb(s) 2 H+(aq) + 2 e- -----> H2(g) Sn4+(aq) + 2 e- -----> Sn2+(aq) Cu2+(aq) + e- -----> Cu+(aq) SO42-(aq) + 4 H+(aq) + 2 e- -----> SO2(g) + 2 H2O AgCl(s) + e- -----> Ag(s) + Cl-(aq) Cu2+(aq) + 2 e- -----> Cu(s) O2(g) + 2 H2 + 4 e- -----> 4 OH-(aq) I2(s) + 2 e- -----> 2 I-(aq) MnO4-(aq) + 2 H2O + 3 e- -----> MnO2(s) + 4 OH-(aq) O2(g) + 2 H+(aq) + 2 e- -----> H2O2(aq) Fe3+(aq) + e- -----> Fe2+(aq) Ag+(aq) + e- -----> Ag(s) Hg22+(aq) + 2 e- -----> 2 Hg(l) 2 Hg2+(aq) + 2 e- -----> Hg22+(aq) NO3-(aq) + 4 H+(aq) + 3 e- -----> NO(g) + 2 H2O Br2(l) + 2 e- -----> 2 Br-(aq) O2(g) + 4 H+(aq) + 4 e- -----> 2 H2O MnO2(s) + 4 H+(aq) + 2 e- -----> Mn2+(aq) + 2 H2O Cr2O72-(aq) + 14 H+(aq) + 6 e- -----> 2 Cr3+(aq) + 7 H2O Cl2(g) + 2 e- -----> 2 Cl-(aq) Au3+(aq) + 3 e- -----> Au(s) MnO4-(aq) + 8 H+(aq) + 5 e- -----> Mn2+(aq) + 4 H2O Ce4+(aq) + e- -----> Ce3+(aq) PbO2(s) + 4 H+(aq) + SO42-(aq) + 2 e- -----> PbSO4(s) + 2 H2O H2O2(aq) + 2 H+(aq) + 2 e- -----> 2 H2O Co3+(aq) + e- -----> Co2+(aq) O3(g) + 2 H+(aq) + 2 e- -----> O2(g) + H2O F2(g) + 2 e- -----> F-(aq)

E0 (V) -3.05 -2.93 -2.90 -2.89 -2.87 -2.71 -2.37 -1.85 -1.66 -1.18 -0.83 -0.76 -0.74 -0.44 -0.40 -0.31 -0.28 -0.25 -0.14 -0.13 0.00 +0.13 +0.13 +0.20 +0.22 +0.34 +0.40 +0.53 +0.59 +0.68 +0.77 +0.80 +0.85 +0.92 +0.96 +1.07 +1.23 +1.23 +1.33 +1.36 +1.50 +1.51 +1.61 +1.70 +1.77 +1.82 +2.07 +2.87

CELL EMF

The overall electrochemical cell reaction can be written as 2 half-equation : 1 equation for reduction reaction, & another one for oxidation reaction.

The number of electrons gained in the reduction half reaction must equal to the number of electron lost in the oxidation half reaction.

Eo is a type of energy per electron, so it remains unchanged even if we double the numbers of reactants and products in the reaction.

If an equation is reversed (so that the reactants become the products), the sign of Eo is also reversed.

The cell;s emf is calculated by adding together the Eo values for each half reaction : Eo cell = Eo reduction + Eo oxidation

The reaction is spontaneous in the direction as written if Eo cell is positive.

The reaction is spontaneous in the reverse direction to that written if Eo cell is negative.

A galvanic cell produces electricity so the overall cell reaction must have a positive Eo cell value.

Cell emf depends on temperature and concentration of reactants & products.

An electrolytic cell requires an input of electricity, so the overall cell reaction must have a negative Eo cell value.

If an electrolytic cell is operating in aqueous solution, then the water is also being reduced at the cathode @ formed at the anode, so these equations must also be incorporated into the calculation of Eo cell.

STANDARD REDUCTION POTENTIAL SERIES

Ease of oxidation increase

Ease of reduction increase

All ions involved are aqueous ions

The more negative the value of SEP, the stronger the reducing agent
STANDARD ELECTRODE POTENTIAL The more positive the value of SEP, the stronger the oxidizing agent Reducing agents are found on the right of the half-cell equations

All half-cell reactions are written as reduction

Oxidizing agents are found on the left of the half-cell equations

CORROSION
Introduction

is a redox reaction metal is oxidized naturally by releasing electrons to form positive metal ions.
M Mn+ + metal metal ion ne-

The higher the position of metal in electrochemical series, the more electropositive it is, the easier it will corrode by losing electrons rusting Factors required for rusting : air water

Example : when iron rusts, iron lose electrons to form iron(II) ions. The electrons are accepted by O2 and H2O to form hydroxide ions. Situation : A drop of water on the iron surface ANODE The surface of metal in the middle of the water droplet (lack of oxygen). Oxidation occurs. Fe Fe2+ + 2eOVERALL REACTION CATHODE The surface of metal at the edge of water droplet (rich of oxygen) Reduction occurs. O2 + 2H2O + 4e- 4OH-

2Fe + O2 + 2H2O 2Fe(OH)2

The iron(II) hydroxide is further oxidized by oxygen to form hydrated iron(III) oxide, Fe2O3xH2O, known as rust (brown in colour Factors Influencing The Rate Of Rusting

Purity of the iron

Amount of stress

Electrolyte composition

Oxygen concentration

Pure iron rusts very, very slowly. Rusting occurs very quickly if a less active metal impurity is present, eg, copper or tin.

Bending, cutting and sharpening the iron place it under stress which distorts the arrangement of metal ions in the lattice. Fe2+ ions can escape from the metal lattice more easily, so rusting occurs faster.

Pure water is a poor electrical conductor so rusting occurs more slowly. Salt water is a much better electrical conductor so rusting occurs more rapidly.

A large concentration of oxygen at the surface of iron will speed up the corrosion of another area with lower oxygen concentration if there is a path for electrons and ions to follow between the two areas.

RUST PREVENTION METHOD

PAINTING

PLATING WITH ANOTHER METAL

CATHODIC PROTECTION

ALLOYING WITH ANOTHER METAL

Prevents oxygen and water coming into contact with the iron so rust can't form. If the paint is scratched or chipped, oxygen and water can come into contact with the iron so rust will then form.

Less Active Metal Plating with a less active metal like tin is just like painting. The tin covering prevents the iron coming into contact with water and oxygen, but, if the tin plate is scratched, rust will readily form.

A Sacrifical Anode is a block of active metal such as zinc or magnesium attached to the hull of a ship, or to tanks and pipelines buried in moist earth. The more active zinc sacrifices itself by corroding in preference to the iron. Sacrifical anodes must be replaced when they have corroded in order for the protection of iron to be maintained.

Alloying iron with chromium produces stainless steel. The chromium readily forms an impermeable (impervious) oxide layer that adheres strongly to the iron surface preventing the formation of rust.

More Active Metal Plating with a more active metal like zinc in the galvanising process, firstly acts like painting in that water and oxygen can not get to the iron surface, but, if the surface is scratched this sets up a new galvanic electrochemical cell: Zn(s) + Fe2+(aq) -----> Zn2+(aq) + Fe(s) The iron is reformed in this process. Zinc ions will form zinc oxide (or carbonate) which is less permeable to water and oxygen than iron oxides so this slows down the rate of corrosion.

The Nernst Equation allows us to calculate the voltage produced by any electrochemical cell given Eo values for its electrodes and the concentrations of reactants and products. The general Nernst Equation: E = Eo -(RT/nF)lnQ Eo = standard electrochemical cell potential (voltage) R = ideal gas constant T = temperature n = moles of electrons F = Faraday constant = 96,485 C mol-1 Q = mass-action expression (approximated by the equilibrium expression)

At 25oC the Nernst Equation is simplified to: E = Eo -(0.0592/n)logQ Eo = standard electrochemical cell potential (voltage) n = moles of electrons Q = mass-action expression (approximated by the equilibrium expression)

For a system at equilibrium at 25oC, E = 0 and the Nernst Equation is simplified to: Eo = (0.0592/n)logK Eo = standard electrochemical cell potential (voltage) n = moles of electrons K = equilibrium expression Example of E Calculation Calculate the voltage produced by the cell Sn(s)|Sn2+||Ag+|Ag(s) at 25oC given: [Sn2+] = 0.15 M, [Ag+] = 1.7 M Write the Nernst Equation for 25oC: E = Eo -0.0592/n x logQ Calculate Eo for the cell: anode:Sn(s)Sn2+ + 2eEo = -0.14V

NERNST EQUATION

cathode:2x [e- + Ag+Ag(s)]Eo = +0.80V

cell:Sn(s) + 2Ag+Sn2+ + 2Ag(s)Eo = +0.66V Wite the expression for Q: Q = [Sn2+]/[Ag+]2 (concentrations of solids = 1) Write the Nernst Equation for this example: E = Eo -0.0592/n x log([Sn2+]/[Ag+]2) Substitute the values: Eo = +0.66V n = 2 (2 moles of electrons transferred during the redox reaction) [Sn2+] = 0.15 M [Ag+] = 1.7 ME = +0.66 -0.0592/2 x log([0.15]/[1.7]2)

Calculate Q: E = +0.66 -0.0592/2 x log[0.0519]

Calculate logQ: E = +0.66 -0.0592/2 x -1.285 Calculate E: E = +0.66 -0.0592/2 x -1.285 E = +0.70V E > Eo, and positive, so the cell reaction has a greater tendency to take place at these concentrations.

SPONTANEITY OF REDOX REACTION

Unfortunately chemists have no reliable theoretical method of determining if a reaction between two substances will be spontaneous. When no theoretical method is available, chemists seek a empirical method or rule they can use to predict spontaneity.

First chemists, through experimentation, develop tables of reduction reactions from strongest to weakest oxidizing agents. Using the table, chemists then develop generalization (rules) for spontaneity.

Chemists can develop generalizations regarding the position of an oxidizing agent and reducing agent in a table of reduction half reactions and using this table predict the spontaneity of the reaction.

Spontaneity Rule :

The redox reaction will be spontaneous if the oxidizing agent in the reaction is higher than the reducing agent (in a table of reduction half reactions).

Steps : Identify the reductant. Identify the oxidant. If the reductant is lower on the series than the oxidant, then a spontaneous reaction will occurs.

SUMMARY
Factors affecting the products if electrolysis are the Eo value, concentration of the aqueous ions & nature of electrodes.

Oxidation is a process of electron lose.

Anode is the electrode where oxidation takes place.

Cathode is the electrode where reduction takes place.

Faradays first law of electrolysis, Q=It

Reduction is a process of electron gain.

Decreasing the [ ] of the product ions will decrease the value of the electrode potential.

Electrochemical cell converts chemical energy to electrical energy.

In an electrolysis cell, oxidation take place at the anode, reduction takes place at the cathode.

Faradays second law of electrolysis the amount of different substances produced by the same amount of electric charge is inversely proportional to the charge of the ions.

Oxidising agents are electron acceptors.

Increasing the [ ] of the reactant ions will increase the value of the electrode potential.

In an electrochemical cell, the half cell with more +ve Eo value forms the +ve terminal (cathode)

An electrolysis cell converts electrical energy to chemical energy.

One Faraday(F) is the charge carried by one mole of electrons.

Reducing agents are electrons donors.

The more negative the E value, the stronger is the reducing agent.

In an electrochemical cell, the half cell with more -ve Eo value forms the ve terminal (anode)

Electrolysis is the decomposition of an electrolyte by electricity.

Uses of electrolysis : Extraction of aluminium from bauxite Manufacturing of chlorine from brine Purification of copper Electropalating Anodisation Effluent treatment

The standard electrode potential (E) is the potential difference between a metal & its aqueous ion (of concentration 1 mol dm-3) relative to that of the standard hydrogen electrode at 298 K & 101 kPa.

The more positive the E value, the stronger is the oxidising agent.

The e.m.f = Eo (+ve terminal) Eo (ve terminal)

The Eo value depends on concentration of the aqueous ion, temperature, pH & formation of complexes

APPLICATION OF ELECTROCHEMISTRY

Uses of Electrolysis in Industries

Extraction of metals

Purification of metals

Electroplating of metals

Extract metals from their ores.

Metals that have been extracted from their ores are normally not pure & contain impurities which need to be removed.

Many types of metals can be plated with other metals through electrolysis electroplating.

Metals that are more reactive than carbon cannot be extracted through heating of their metal oxides with carbon.

In the purification process, the impure metal is made the anode while the pure metal is made the cathode.

Aims: - making the metal more resistant to corrosion, - making the metal appear more attractive.

Metals that are more reactive need to be extracted from their molten ores using electrolysis process.

The electrolyte is a solution which contains the metal ions.

In this process, the molten ore is the electrolyte and inert electrodes such as carbon are used as +ve & -ve electrodes.

Metals such as silver, gold, nickel, copper, chromium, cadmium, zinc @ tin are frequently used as plating metal.

During electrolysis, impure metal at the anode will release electrons & dissolve into the electrolyte as metals ions.

In the electroplating process, plating metal is used as the anode while metal to be plated is used as the cathode.

These metal ions can receive electrons & form pure metal at the cathode. The electrolyte used is an aqueous solution which contains ions of the plating metal.

The size of impure metal (anode) become smaller & impurities will settle at the bottom of the container, the mass of the impure metal plate decreases.

During electrolysis, plating metal @ the anode releases electrons & dissolves to form metal ions.

The size of pure metal (the cathode) becomes larger due to the deposition of pure metal, the mass of pure metal plate increases.

Ions of the plating metal then move to the cathode, receive electrons there & form a thin layer of metal on the cathode.

BENEFITS OF ELECTROLYSIS IN INDUSTRY

PROCESS BENEFITS Enables metals that are more reactive than carbon to be extracted from their ores.

Metal extraction

Metal purification

Improves the electrical conductivity of substances.

Metal electroplating

Improves the resistance of metal against corrosion.

Electrolyte such as NaOH solution can cause water pollution in rivers & oceans & harm marine life.

Heavy metals, such as mercury , used as electrodes in the electrolysis of sodium chloride, NaCl, is toxic & will pollute the surrounding environment if it is not disposed properly.

HARMFUL EFFECTS OF ELECTROLYSIS IN INDUSTRY

Poisonous gases such as chlorine, Cl2 gas cause air pollution.

Nickel salts & chromium salts, which are used as electrolytes in the purification & electroplating industries, are poisonous to human being.