3.20.1 Primary Cells ‘These type of cells or batteries become dead over a period of time as the chemical reaction stops. Primary cells cannot be recharged or reused. Some common examples are dry cell, mercury cell etc. 3.20.2 Secondary Cells Secondary cell or battery can be recharged after it Metal cap becomes dead by passing direct current and the cell Zinc can be used over and again. Two well known cover ‘examples of this type are, lead storage battery and nickel-cadmium storage cell. [Croat (A) Primary cells M0; Graphite 1. Dry cell. It is actually a compact form of Leclanche Carbon —] cell. The cell consists of a cylindrical zinc container mixture which also acts as anode, The cathode is a carbon Paste of (graphite) rod surrounded by powdered MnO, and NH,CI+ZnCh carbon (Fig. 3.11). The space between electrodes is filled by a moist paste of NH,CI and ZnCl. The ite rod is fitted with a brass cap for better electrical contact and the cylinder is sealed at the top with pitch. The zinc container is covered with cardboard to protect Zn from atmospheric oxidation. ‘Though the electrode reactions are complex, they can be approximated as follows: Anode: Zn (s) —> Zn (aq) + 2 Cathode: MnO, + NHj +e” —+ MnO (OH) +NH, Ammonia produced in the reaction forms a complex ion with Zn?* to give [Zn (NH,),]°*. The cell has. 4 potential of nearly 1.50 volts. During the operation of dry cell, zinc metal (anode) gets consumed up slowly and, after sometime the container may develop holes which are responsible for leakage of the cell. This is avoided by covering. ‘outside of the container with a thin sheet of another metal which is inert to cell reaction. Such a dry cell, is called leak-proof cell. Dry cells find extensive use in torches, transistor radios, clocks etc. 2, Mercury button cell, Itis a miniature cell which finds extensive use in watches, cameras, hearing aids, heart pacemakers and other compact devices. The main advantage of mercury batteries is that they produce constant voltage of 1.35 V during their discharge. In mercury cell zine ~ mercury amalgam is the anode and a paste of HgO and carbon acts as cathode. The electrolyte is a paste of KOH and ZnO. The electrode reactions for the cell are as follows: ‘Anode: ‘Zn(Hg) +2 OH” —+ ZnO + H,0 + 2€ ‘Cathode: HgO + H,0 + 2e —> Hg +20H Net reaction: _Zn(Hg) + HgO(s) —> Zn (s) + Hg(I) ‘The cell potential remains constant during its life as the net reaction does not involve any ion in solution whose concentration might change during the discharge of the cell(B) Secondary cells ‘These batteries are also called storage battery or accumulator because they can be recharged. As already explained, the chemical reactions occurring in a dry cell can not be reversed after the dry cell has run down, therefore, a dry cell can not be recharged. But secondary cells can be recharged and used again and again as a source of electric current. Some examples of storage batteries are: 1. Lead storage battery. It is the most frequently used battery in automobiles. It normally consists of six voltaic cells connected in series. In each cell anode is made of spongy lead and cathode is a grid of lead packed with lead dioxide (PpO,). Electrolyte is H,SO, solution, which is 38% by mass and hence, it is also called acid storage cell. During discharge of battery ie., when current is drawn from the battery, following reactions take place. ‘At anode: Pb(s) + SO} (aq) —> PbSO,(s) + 2e Atcathode: PbO4(s) + SO} (aq) + 4H*(ag) + 2e° —> PdSO,(s) + 2H,0 Overall reaction: bs) + PbO,(s) + 2H,SO,(aq) —+ 2PbSO,(s) + 2H,0(0) It is clear from the cell reaction that sulphuric acid is consumed in the reaction during discharge of the battery and as a result the density of acid falls. The condition of the battery can be easily checked by ‘measuring the density of solution and when the density falls below 1.20 g em’’, battery needs recharging. During charging i.c., when electrical energy is supplied to the battery from an extemal D.C. source, cell operates like an electrolytic cell and chemical reactions take place but now the electrode reactions are reverse from those that occur during the discharge node of the battery and it results in the deposition of Pbon Cathode the anode and PbO, on the cathode. Such a reversal of reactions is possible because PbSO, formed during discharging of the cell is solid and sticks to the electrodes. To increase current output of the cell, anode and cathode are arranged in alternating manner and are separated from each other by sheets of insulating material. The anode and cathode plates are separately connected to each other (Fig. 3.12). Each voltaic cell has a potential difference of about 2 volts, therefore, to have an output of 12 volts, six cells of the battery are connected in series. Lead (Pb) Dil HsS04 Fig. 3.12 Lead storage batterySicwl eo! Ttis another rechargeable cell where anode is made up of cadmium and the cathode is comprised of a metal grid containing nickel (IV) oxide, The electrolyte is KOH solution. The electrode reactions are: ‘Anode: Cals) + 2 OH” (aq) —+ C(OH),(s) + 26° Cathode: {0,(s) + 2H,0 (1) + 2&° —+ Ni(OH),(s) +2 OH(aq) Overall reaction: __Cd(s) + NiO4(s) —+ CA(OH),(s) + N(OH),(5) ‘The cell has a voltage of about 1.4 volt. ‘There are no gascous products formed during the discharge of battery and solid products formed adhere to the electrodes, which therefore, are reconverted by the charging processes. ‘The cell finds use in electronic watches and calculators . This storage cell is commonly used in laboratories. It can be represented as: Fe | FeO [KOH (20%) | NiO,, NiO | Ni ‘The electrode reactions Atanode: Fe + 20H” —> FeO +H,0 +26 ‘Ateathode: NiO, + H,0 + 2e°-—> FeO + NiO Overall cell reaction: Fe + NiO, —+ FeO-+ NiO In the recharging processes, changes at the electrodes are reversed. Edison cell is alkali storage As it is based on the use of nickel (Ni) and iron (Fe) it is sometimes called NiFe cell. It gives a steady potential of 1.36 volt. It is extremely rugged and has very long service life. ‘The conventional method of conversion of chemical energy of a fuel into electrical energy involves ‘combustion of the fuel to liberate heat. The heat energy thus produced is used to convert water into steam which runs turbines, which are coupled with electric generators. However, this is not a very efficient processes. The most efficient power plant may only convert about 40% of original chemical ‘energy into electrical energy. Fuel cells are electrochemical cells in which the substance oxidised is not electrolyte or electrode ‘material but an externaily supplied substance which can be also used as a fuel in a heat engine. ‘A regulated continuous supply of a conventional fuel like H, CH, etc. is oxidised at anode and a conventional supporter of combustion like air ‘or oxygen is supplied and reduced at cath- Anode of Cathode of ode. Such electrochemical combustion of fuel Porous carbon porous carbon leads to generation of electrical power to do Sonalng containing toc work — suitable catalyst However, for electrochemical oxidation of, the fuel and electrochemical reduction of the oxidant appropriate catalyst is required. For this, platinum, nickel or their alloys are used = Hy —« 0; in porous forms at electrodes which also provide a catalytic surface. Thus, a fuel cell eon eee is a device of converting chemical energy of L_ «fuel directly into electrical energy without ‘A sample of H ell using a heat engine. rample of WO; fuelOne of the most successful fuel cell uses chemical reaction of H, and ,, to form water and is known as H, — O, fuel cell, also called Bacon cell, after the name of its inventor and was used as a primary souree of electrical energy on Apollo moon flights. The product, namely water was utilized by astronaughts for drinking. The cell consists of porous carbon electrodes which are impregnated with catalyst Nickel and Nickel oxide. Both the electrodes are placed in electrolytic solution such as hot caustic potash (KOH) (Fig. 3.13). Hydrogen and oxygen are bubbled through the electrodes into the electrolytic solution. The electrode reactions are: ‘Anode: H,(g) + 40H — 4H,0 (i) + de" Cathode: Ox(g) + 2H,0 (1) + 4e° —> 40H (ag) (Cell reaction: 2H,0 (g) + O,(¢) —> 2H,0 (1) The cell runs continuously as long as the H, and O, gases are supplied into the cell, Also, fuel cells do not cause any pollution problem,