HISTORY OF ELECTROCHEMICAL CELL

The first Electrochemical Cell which is the Voltaic Pile was invented in 1800 after observing the famous 'frogs leg' experiments of Luigi Galvani. Galvani had noticed that the leg of a deceased frog would twitch when exposed to an electrical current. Galvani then reproduced this effect without the use of the frogs legs by creating the "Galvanic cell". This cell was a simple set of reactive metals submerged in their respective sulphate solution. Alessandro Volta saw the potential of the "Galvanic Cell" and set about making a practical version that could produce a greater source of electricity. Using cardboard soaked in vinegar instead of jars of liquid, he separated each piece of cardboard with a reactive metal. The result was the "Voltaic Pile", a series of compact "Galvanic cells" connected together which created an electrical current. The battery Volta created was so weak it couldn't even produce a spark but although the technology for producing batteries had improved greatly over the last two centuries, this basic layout of cells has remained virtually unchanged since 1800. He began his work in 1794, by interacting two different metals submerged close to each other in an acidic solution. His very first battery had series of alternating copper and zinc rings in the electrolyte. By 1800, he had created a working cell. After creating his cell, he began to research which metals are produced when exposed to salt water, which helped him demonstrate the voltaic cell in 1801. This led to a great deal of experimentation with different electrode materials, electrolytes and physical construction. Other electrochemical cells were developed by Wollaston, Hare, Daniell, Grove, Bunsen, Callan, Smee, Walker, Davy, Meidinger, Minotto, De la Rive and Mller, Latimer Clark, Leclanche, and doubtless others. The most popular electrochemical cell that are known are Voltaic cell, Daniel cell and Galvanic cell.

Engineering Materials Chemistry EBT 251

In 1836, John F. Daniel invented the Daniel Cell that used two electrolyts which are copper sulphate and zinc sulphate. An advantage of his cell was that it was a little bit safer and less corrosive than voltaic cell.

ELECTROCHEMICAL CELL

An electrochemical cell is an apparatus consisting of electrodes that dip into an electrolyte and in which a chemical reaction either produces electricity or is caused by an electric current. A voltaic, or galvanic, cell is an electrochemical cell in which a spontaneous chemical reaction generates an electric current. An example of a galvanic cell with which you are almost certainly familiar is a flashlight battery. Since an electrical current is a flow of electrons or other charged particles, it should come as no surprise that both electrolytic and galvanic cells involve redox reactions.

When an electrical current flows through matter, permanent chemical changes often occur. In some cases electrical energy supplied from an outside source can cause a chemical reaction to take place. An electrolytic cell is an electrochemical cell in which a nonspontaneous chemical reaction results from the flow of an electric current through the cell and the process is called electrolysis. A typical example of electrolysis is the laboratory preparation of H2(g) and O2(g) by passing electrical current through water. Electrolysis is quite important in chemical industry, being involved in manufacture of aluminum, chlorine, copper, and numerous other substances.

In an electrolytic cell electric energy supplied from an outside source causes a non-spontaneous reaction to occur. A galvanic (or voltaic) cell, on the other hand harnesses a spontaneous reaction to produce electric current. In either kind of cell the electrode at which oxidation occurs is called the anode and the electrode at which reduction occurs is the cathode. Chlorine, sodium hydroxide, hydrogen, aluminum, magnesium, sodium, calcium, and high-purity copper are some of the more important chemicals produced by electrolysis. Electroplating of metals such as chromium, silver,

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nickel, zinc, and tin is also quite important. In any electrolysis reaction the amount of substance consumed or produced can be related to the electric charge which passes through the cell by the Faraday constant F, which is equals to 9.649 104 C mol1. A galvanic cell may be represented by an abbreviated notation such as ZnZn2+ (1 M) Ag2+(1 M)Ag When a cell is written this way, it is always assumed that the left-hand electrode is an anode and an oxidation half-equation occurs there. The right-hand electrode must then be taken as the cathode and a reduction half-equation is assumed to occur there. The cell reaction is the sum of these two half-equations. If it is spontaneous, our assumptions about anode on the left and cathode on the right were correct.

Electrons will be forced into an external circuit on the left and the cell emf is taken to be positive. If the cell reaction written according to the above convention turns out to be nonspontaneous, then its reverse will be spontaneous. Our assumptions about which electrode is the anode and which the cathode must also be reversed, and the cell emf is given a negative sign.

Because cell emf values indicate whether a process is spontaneous, they are quite useful. They are additive and are conventionally reported as standard electrode potentials. These refer to the emf of a cell with a hydrogen- gas electrode on the left and the electrode whose potential is reported on the right. The standard electrode potential is directly related to the standard free energy change for a reaction, thus allowing direct determination of G.

Many galvanic cells are of commercial importance. These include dry cells, mercury cells, rechargeable Ni-Cd batteries, and lead storage cells. Fuel cells, in which a continuous supply of both oxidizing and reducing agent is supplied, may eventually become important because of their high efficiencies.

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DANIELL CELL

An electrochemical cell which causes external electric current flow can be created using any two different metals since metals differ in their tendency to lose electrons. Zinc more readily loses electrons than copper, so placing zinc and copper metal in solutions of their salts can cause electrons to flow through an external wire which leads from the zinc to the copper. Solutions are connected by a salt bridge or a porous pot where its function is to complete the circuit by allowing the movement of ions and prevent two aqeous solution from mixing. As a zinc atom provides the electrons, it becomes a positive ion and goes into aqueous solution, decreasing the mass of the zinc electrode. On the copper side, the two electrons received allow it to convert a copper ion from solution into an uncharged copper atom which deposits on the copper electrode, increasing its mass. The two half reactions are typically written as: Zn(s) -> Zn2+(aq) + 2e- : The zinc is classified as oxidation since it loses electrons. The terminal is called the anode. For a battery, this is negative terminal. Cu2+ (aq) + 2e- -> Cu(s) : The cooper is classified as reduction since it gains electrons. The

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terminal is called the cathode. For a battery, this is positive terminal. The letters in parentheses are just reminders that the zinc goes from a solid (s) into a water solution (aq) and vice versa for the copper. It is typical language of electrochemistry to refer to these two processes as "half-reactions" which occur at the two electrodes. In order for the daniell cell to continue to produce an external electric current, there must be a movement of the sulphate ions in solution from the right to the left to balance the electron flow in the external circuit. The metal ions themselves must be prevented from moving between the electrodes, so some kind of porous membrane or other mechanism must provide for the selective movement of the negative ions in the electrolyte from the right to the left. Energy is required to force the electrons to move from the zinc to the copper electrode, and the amount of energy per unit charge available from the voltaic cell is called the electromotive force (emf) of the cell. Energy per unit charge is expressed in volts (1 volt = 1 joule/coulomb). The cell can yield a finite amount of energy from this process, the process being limited by the amount of material available either in the electrolyte or in the metal electrodes. For example, if there were one mole of the sulphate ions SO42- on the copper side, then the process is limited to transferring two moles of electrons through the external circuit. The amount of electric charge contained in a mole of electrons is called the Faraday constant, and is equal to Avogadro's number times the electron charge: Faraday constant = F = NAe = 6.022 x 1023 x 1.602 x 10-19 = 96,485 Coulombs/mole The energy yield from a voltaic cell is given by the cell voltage times the number of moles of electrons transferred times the Faraday constant. Electrical energy output = nFEcell

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The cell emf Ecell may be predicted from the standard electrode potentials for the two metals. For the zinc/copper cell under the standard conditions, the calculated cell potential is 1.1 volts.

ELECTROLYTIC CELL
To accomplish this, one must make the water conductive by using an electrolyte that does not react under the conditions of the experiment. Sodium sulfate (Na2SO4) or dilute sulfuric acid (H2SO4) can be used; keep the concentrations low, especially when using sulfuric acid. Magnesium sulfate ("Epsom salt", MgSO4) is also suitable. Electrolysis of water will begin around a minimum of 1.2 volts and will increase in rate as the voltage is increased. Typically, the electrolysis is carried out around 6 volts. Remember that lower voltage (V) across a given resistance (R) equates to lower current (I). That may seem counter-intuitive, but V=IR really works. Update / Correction: we had accidentally typed "higher" voltage where "lower" was meant. If you do a few calculations with V=IR where R is set at 1 ohm, you will see that a higher voltage across a resistance of fixed value leads to a higher current. 12 volts across a 1ohm resistor will give 12 amperes of current; 6 volts across a 1-ohm resistor will lead to 6 amperes. The "counter-intuitive" reference refers to those who've had experience with transformers, power inverters, and the like. For example, a step-up transformer produces an increase in voltage but a decrease in current output. The anode is where oxidation takes place. Oxidation involves the loss of electrons. The cathode is where reduction takes place; reduction involves gain of electrons. Now, which gas will be produced at which electrode? If we think of water as hydrogen oxide (which it is), we can consider each hydrogen portion of water as H+. These would have to gain electrons to become neutral hydrogen; therefore, this must happen at the cathode. We can consider the oxygen part of water as O2- (the oxide ion, which always has a -2 charge); this would have to lose electrons to become neutral. Thus, oxygen gas should form at the anode. Finally, remember that there are three components that could theoretically

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participate in the electrolysis: the water, the dissolved electrolyte, and the electrodes. In this experiment our choice of electrodes (platinum) and electrolyte (sodium sulfate) has ensured that these don't participate in the chemical reaction. Remember the five variables we listed in the beginning of this article.

http://staff.prairiesouth.ca/~chemistry/chem30/graphics/6_graphics/electrolysis_w ater.gif

http://img.sparknotes.com/figures/0/02480ae8fc1a41b131a3fdb5a698e9a3/lyticcell.gif

Engineering Materials Chemistry EBT 251

APPLICATION

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CONCLUSION
A voltaic, or galvanic, cell is an electrochemical cell in which a spontaneous chemical reaction generates an electric current. An electrolytic cell is an electrochemical cell in which a nonspontaneous chemical reaction results from the flow of an electric current through the cell. Clearly, to get energy from the cell, is to get more energy released from the oxidation of the zinc than it takes to reduce the copper.

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REFERENCES
http://physics.kenyon.edu/EarlyApparatus/Electricity/Electrochemical_Cell/Electrochemi cal_Cell.html http://www.dummies.com/how-to/content/electrochemical-cells-the-daniell-cell.html http://chemed.chem.wisc.edu/chempaths/GenChem-Textbook/GalvanicCells/chemprime/CoreChem3AElectrochemical_Cells-699.html http://www.ukbatteries.co.uk/technical/battery-info image 1 http://hyperphysics.phy-astr.gsu.edu/hbase/chemical/imgche/cellabel.gif http://hyperphysics.phy-astr.gsu.edu/hbase/chemical/electrochem.html

English chemist John Frederick Daniell developed a voltaic cell in 1836 which used zinc and copper and solutions of their ions. The Daniell cell is a kind of copper-zinc battery which employs a porous barrier between the two metals. It was invented in 1836 by British chemist John Frederic Daniell. Once used widely in the European telegraph industry, it was supplanted in the late 19th century by more modern battery designs. Today, it is primarily used in the classroom to demonstrate how batteries work.

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