Elektrokimia

Electrolytic Cell Menukarkan tenaga elektrik kepada tenaga kimia

Voltaic Cell Menukarkan tenaga kimia kepada tenaga elektrik

Elektrolisis

Chemical/Voltaic Cell

Kegunaan - Extraction of metals - Purification - Electro-plating

Teori Ionik (Faktor) - Position of ions in Electrochemical Series - Concentrations of ions - Type of electrode

Primary cell

Secondary cell

Electrochemical Series

Uses

Voltaic Cell

Process
It involves the changes in chemical energy to electrical energy.

Reaction
The chemical reactions that take places inside the cell cause the flow of electron. So, electricity is produced

Example
Danielle Cell: Zinc and copper are used as electrode. Each of the metals is immersed into a solution of its ions. The two solution are connected through a salt bridge/ a porous pot.

Products
Products from voltaic cell (for a simple source of portable electricity): Dry cell Lead-acid accumulator Mercury cell Alkaline cell Nickel-cadmium cell.

Structure
2 different metals being immersed into an electrolyte and connected by wire. The potential difference detected by the voltmeter indicates the production of electricity.

Other names
Galvanic Cell Chemical Cell

Primary Cells
In primary cells this electrochemical reaction is not reversible. During discharging the chemical compounds are permanently changed and electrical energy is released until the original compounds are completely exhausted. Thus the cells can be used only once.

Secondary Cell
In secondary cells this elecrochemical reaction is reversible and the original chemical compounds can be reconstituted by the application of an electrical potential between the electrodes injecting energy into the cell. Such cells can be discharged and recharged many times.

Cell E.M.F

The electromotive force (EMF) is

An electric current flows from the anode to the

the maximum potential difference between two electrodes of a

galvanic or voltaic cell.

There

is

difference

in

This quantity is related to the tendency for an element, a

electrical

potential

energy

between the electrodes.

compound or an ion to acquire (i.e. gain) or For release example, (loss) the

electrons.

maximum potential between Zn and Cu of a well known cell.

The

difference

in

electrical

potential between the anode (Zn) and cathode (Cu) is measured by a voltmeter or galvanometer.

The reading (in volts) is called cell voltage. If the cell potential is negative, the reaction is reversed. In this case, the electrode of the galvanic cell should be written in a reversed

Two other terms, electromotive

force (emf) and cell potential are also used to donate cell voltage.

STANDARD REDUCTION POTENTIAL

Ions are arranged according to their electrode potentials. The order shows the tendency of one metal to reduce the ions of any other metal below it in the series.

All the reduction potential is tabulated by referring to the standard hydrogen electrode (SHE). The standard hydrogen electrode undergoes the reaction.

Standard electrode potentials are usually tabulated as reduction potentials. However, the reactions are reversible and the role of a particular electrode in a cell depends on the relative oxidation/reduction potential of both electrodes.

Strengths of Oxidizing and Reducing Agents

Cathode (Reduction) Half-Reaction Li+ (aq) + e- --> Li(s) K+ (aq) + e- --> K(s) Ca2+ (aq) + 2e- --> Ca(s) Na+ (aq) + e- --> Na(s) Zn2+ (aq) + 2e- --> Zn(s) 2H+ + 2e- --> H2 Cu2+ (aq) + 2e- --> Cu(s) O3+ (g) + 2H+ (aq) + 2e- --> O2 (g) + H2O(l) F2 (g) + 2e- --> 2F- (aq) Standard Potential E (volts) -3.04 -2.92 -2.76 -2.71 -0.76 0 0.34 2.07 2.87

The values for the table entries are reduction potentials, so lithium at the top of the list has the most negative number, indicating that it is the strongest reducing agent. The strongest oxidizing agent is fluorine with the largest positive number for standard electrode potential.

Temperature
Concentration

A cell's standard state potential is the potential of the cell under standard state conditions, which is approximated with:
i) concentration of 1 mole per liter (1 M) ii) pressure of 1 atmosphere at 25oC.

Gas partial pressure.

The cell potential (voltage) for an electrochemical cell can be predicted from half-reactions and its operating conditions.

STANDARD CELL POTENTIAL

To calculate the standard cell potential for a reaction. Write the oxidation and reduction half-reactions for the cell. Look up the reduction potential, Eoreduction, for the reduction half-reaction of reduction potentials.

Add the potentials of the halfcells to get the overall standard cell potential. Eocell = Eoreduction + Eooxidation

Look up the reduction potential for the reverse of the oxidation half-reaction, reverse the sign to obtain the oxidation potential. For the oxidation half-reaction, Eooxidation = - Eoreduction.

A spontaneous electrochemical reaction (change in Gibbs free energy less than zero) can be used to generate an electric current, in electrochemical cells.

Chemical energy is transformed into electrical energy.

A cell is said to be reversible if the reaction which occurs and the direction of current flow through the cell is reversed when an infinitesimally greater opposed electromotive force is applied to the cell.

SPONTANEITY OF REDOX REACTION

Electrochemical reactions are either spontaneous, or nonspontaneous.

A spontaneous redox reaction generates a voltage itself.

A nonspontaneous redox reaction occurs when an external voltage is applied.

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).

The reactions that occur in an electric battery are electrochemical reactions.

When reactant concentrations differ from standard conditions, the cell potential will deviate from the standard potential.

The standard potential of an electrochemical cell requires standard conditions for all of the reactants.

The Nernst equation plays an important role in understanding electrical effects in cells and organelles.

EFFECT OF CONCENTRATION ON CELL EMF (THE NERNST EQUATION)

Consider a cell with the generalized cell reaction.

aA + bB cC + dD G = G + RT lnQ

c d aC aD a b aA aB

-nFEcell = -nFEcell + RT lnQ

or
E cell E cell

and E cell

RT ln Q nF G RT ln K nF nF

The Nernst equation for the reversible potential of a metal ion-metal electrode
E el E el

RT n ln a M nF

APPLICATION OF ELECTROCHEMISTRY

Redox Reaction Electrolysis

Galvanic Cell/ chemical cell

The extraction of metals like aluminium.

One of the more familiar applications of redox chemistry Electro-plating: depositing a thin layer of a metal on another, either for protection or for the sake of appearance. is the galvanic or voltaic cell in the form of a dry-cell battery (a group of galvanic cells in series).

The electro-refining of metals like copper.

BATTERIES

A battery is a number of cells combined and is used to supply electrical energy that is stored chemically.
Danielle Cell

Primary Cell

Chemical cells which cannot be recharged.It stores the chemical substance which react to produce an electric current.

Dry Cell Positive terminal (Carbon rod), Negative terminal (Zinc around the cell), Electrolyte (Manganese IV Oxide, Carbon powder). Alkaline Cell

Mercury Cell (Button Cell)

Mostly found in calculator, watch and cameras. The -ve terminal is zinc, +ve terminal is HgO, electrolyte is KOH + ZnOH2

Negative terminal is zinc powder, positive terminal is manganese (IV) oxide and the electrolyte is NaOH/ potassium paste.

Secondary Cell

Flow Battery
The electrolytes are pumped through a reactor, when the battery is charged. The electrodes are preserved, and the electrolyte combusted.

In secondary cells this elecrochemical reaction is reversible. cells can be discharged and recharged many times.

Llithium Rechargeable Battery

Graphite bar acts as the anode, a bar of lithium cobaltate acts as the cathode, and a polymer, swollen with a lithium salt serves as the electrolyte.

Lead-Acid Battery

Fuel Cell
Each cell has a lead anode and a cathode made from lead dioxide (in a metal plaque). Cathode and anode are submerged in a solution of sulfuric acid acting as the electrolyte.

Two inert electrodes (porous electrodes of nickel and nickel oxide) are placed in an electrolytic solution, in both compartments (anode and cathode).

Iron (III) oxide hydrated is known as rust. The concentration of water associated with iron oxide varies, thus chemical representation is presented as Fe2O3xH2O.

One area on the surface of the metal acts as the anode, which is where the oxidation (corrosion) occurs. At the anode, the metal gives up electrons.

For iron rust to occur the metal has to be in contact with oxygen and water.

Iron Corrosion

CORROSION OF IRON

Term applied to steel rust caused by an electrochemical process in the form of reddish rust.

Corrosion of Common Metal

Prevention of corrosion

Some common metals oxidize extremely rapidly in air.

A non-conducting material covers the metal.

Coating
Metals can be coated with paint or other less conductive metals.

Titanium and aluminium oxidize instantaneously in contact with the oxygen in the air. These metals form an extremely thin layer of oxidized metal on the surface.

Sacrificial Anode

Attach a metal which is more anodic than the metal to be protected. . It is called "sacrificial" because the anode dissolves and has to be replaced periodically.

This thin layer of oxide protects the underlying layers of the metal from the air preventing the entire metal from oxidizing.