Krishnarjuna N(Department of chemistry VSPU BLR) Po ¢ \VIDYASOUDHA PU COLLEGE 1 PUC CHEMISTRY NOTES CHAPTER NAME: 0; LECTROCHEMISTRY Electrochemistry is the study of production of electricity from energy released during spontaneous chemical reactions and the use of electrical energy to bring about non-spontaneous chemical transformations. (Or) % Electrochemistry is the branch of physical chemistry which deals with the relationship between electrical energy and chemical changes taking place in redox reactions, ELECTROLYTES AND ELECTROLYSIS: ‘© The substance whose aqueous solution undergoes decomposition into ions when electric current is passed through them are known as electrolytes and the whole process is known as electrolysis or electrolytic decomposition. Ex: Solutions of acids, bases, salts in water and fused salts etc. {a)Strong electrolyte: + A strong electrolyte is an electrolyte that dissociates completely into ions at moderate concentrations of its aqueous solution Ex: acids HCI, H2SOs, HNOs Base NaOH, KOH Salts NaCl, CuSOs (any salt) (b) Weak electrolyte; ‘A weak electrolyte is an electrolyte that dissociates partially into ions in its aqueous solution. Ex: CHsCOOH, NHsOH {c\Non-Electrolytes: % Annon-electrolyte does not dissociate in an aqueous solution into positive and negative ions. Ex: Sugar, ether, urea, methanol, chloroform and benzene. ELECTROCHEMICAL CELL: % Cell converts the chemical energy liberated during the redox reaction to electrical energy. “ Electrochemical Cell has an electrical potential equal to 1.1 V when concentration of Zn®* and Cu?* ions is unity (1 mol dm *)*, Such a device is called a galvanic or a voltaic cell. ‘TYPES OF ELECTROCHEMICAL CELL: 1) Chemical cell; The cells in which electrical energy is produced from the energy accompanying a chemical reaction or a physical process are known as chemical cells. Ex: Daniel cell 2) Concentrated cells; A cell in which electrical energy is produced by the transference of a substance from a system of high concentration to one at low concentration is known as concentration cells. Ex: Two hydrogen electrodes at different gaseous pressures in the same solution of hydrogen ions constitute a cell of this type. Pt| Ho(g,lbar)|HCI(0.002M) || HC1(0.005M)| H(g, 1bar)| Pt ELECTRODE: * Electrode is a metallic rod. * A conductor through which electricity enters or leaves an object, substance, or region. a) Inert electrode: “Electrode which do not take part in chemical change involved in a cell are known as inert electrode. It provides surface for oxidation or reduction but doesn’t participate in cell reaction. tacts as a source or sink for electrons. Ex: Graphite, Platinum, Mercury, Gold(Au), Rhodium. b) Active electrode; Electrodes which take part in chemical change involved in a cell known as active electrode. Ex: Cu, Zn, Ni electrodes etc.Krishnarjuna N(Department of chemistry VSPU BLR) Po ge (2 Note: For metal ions to be deposited on the cathode during electrolysis, the voltage required is almost the same as the standard electrode potential. However, for liberation of gases, some extra voltage is required than the theoretical value of the standard electrode potential (E°).This extra voltage is called over voltage or bobble voltage. Ce To prepare Daniel cell get a zinc electrode by dipping zinc rod in 1M ZnSOs solution. Get a copper electrode by dipping a copper plate in 1M CuSO, solution. Couple these two electrodes using a salt bridge to get Daniel cell. Reactions taking place Okidation ‘Avamode: Zn + Zn?" 420° At cathode : Cu?* +2e" 3--—--— Cu Reduction Net cell reaction : Zn(s) + Cu’* (aq) > Zn** (aq)+ Cuts) ELECTRODE POTENTIAL: % A potential difference develops between the electrode and the electrolyte which is called electrode potential. ¢ When the concentrations of all the species involved in a half-cell is unity then the electrode potential is known as standard electrode potential. * Ina galvanic cell, the half-cell in which oxidation takes place is called anode and it has a negative potential with respect to the solution. ¢ The half-cell in which reduction takes place is called cathode. % The direction of current flow (cathode to anode) is opposite to that of electron flow(anode to cathode). SALT BRIDGE; % Salt bridge is U-shaped glass tube filled with a gelly like substance, agat-agar mixed with an electrolyte like KCI, KNO3,NHANOs etc % The elecirolyte is selected in such a way that both ( cation and anion) should have the same ionic mobility. Salt bridge maintains the electrical neutrality within the internal circuit. % Salt bridge prevents diffusion: If no salt bridge were present, the solution in one half cell would accumulate negative charge and the solution in the other half cell would accumulate positive charge as the reaction proceeded. Without salt bridge the circuit will be incomplete. It prevents liquid-liquid junction potential i.e the potential difference which arises between two solutions when they contact with each other. REPRESENTATION OF CEL! Anode || Cathode ‘Metal | Electrolyte Solution(aq) || Electrolyte Solution(aq) | Metal Ex: Cu(s) + 2Ag‘(aq) —* Cu’"(aq) + 2 Ag(s) The cell can be represented as: Cu(s)|Cu2*(aq)|Ag'(aq)iAg(s)Krishnarjuna N(Department of chemistry VSPU BLR) Po ¢ Metal | Metal insoluble salt | Solution(aq) || Solution(aq) | Metal insoluble salt | Metal Ex: Calomel electrode Cell representation (cathode): Cj HgoClo| Hg/Pt TYPES OF HALF CELL: 1), Metal-Metal ion half cell(M"*/M): ‘* In this half cell metal electrode is dipped in a solution containing metal ions. 2) Gas electrode(Hydrogen electrode): ‘In this half cell, the Pt electrode is dipped in a solution containing ions of gas species. * Gas is introduced on Pt surface from outside source. © Cell representation(Anode) for hydrogen electrode is Pt(s) | Ho(g) | H'(aq) 3) Metal-Metal insoluble salt anion half cell; ‘© In this half cell metal electrode is coated with metal insoluble salt and dipped in a solution containing anion common to that of metal insoluble salt. Calomel electrode(Reference electrode): Cell representation __ C| HgxCh| Hg/Pt Silver-Silver chloride half cell: Cell representation Cl" | AgCl | Ag CELL POTENTIAL: The cell potential is the difference between the electrode potentials (reduction potentials) of the cathode and anode. Ecait = Eni ~ Bet Ecatt = Beathode ~ Eanode CELL REACTION; Cu(s) + 2Ag"(aq) — Cu**(aq) + 2 Ag(s’ (a) Half-cell reactions: Cathode (reduction): 2Ag"(aq) + 2e 2Ag(s) wo (1) Anode (oxidation): Cus) —» Cu(ag) + 26 (2) It can be seen that the sum of (1) and (2) leads to overall reaction (a) in the cell and that silver electrode acts as a cathode and copper electrode acts as an anode. The cell can be represented as: Cu(s)fCu2“@q)| Ag aqlAg(s) Ecett = Eright — Etett = Eage/ag — Ecuzsicu MEASUREMENT OF ELECTRODE POTENTIAL ; ‘© The potential of individual half-cell cannot be measured. © We can measure only the difference between the two half-cell potentials that gives the emf of the cell. © If we arbitrarily choose the potential of one electrode (half-cell usually Standard hydrogen electrode) then that of the other can be determined with respect to this. STANDARD HYDROGEN ELECTRODE(SHE): ‘Standard Hydrogen Blectrode (SHE)Krishnarjuna N(Department of chemistry VSPU BLR) Po ge|4 It consists of a platinum electrode coated ‘The electrode is dipped in 1M HCI. Pure hydrogen gas is bubbled through it under a pressure of 1bar. S.HLE is represented as Pt(s) | Ho(g)(Lbar) | H'(aq)(1M) ‘The reduction reaction taking place is H'(aq) +e" > % Ho(g) S.HLE is assigned an electrode potential of 0.0 V at all temperatures. platinum black. Use of standard hydrogen electrode in measuring the standard electrode potentials of copper And zinc electrode, * * * Construct a standard electrode of the given metal by dipping the pure metal in 1M solution of its own ion at 25°C Couple this standard electrode with SHE using a salt bridge to get galvanic cell. Measure the emf of the cell using suitable instrument like potentiometer. Bo = BE. One of the electrodes of the cell is SHE and its electrode potential is 0.0V. So the electrode potential of the given electrode will be the emf of the cell in magnitude. If reduction takes place at the given electrode its E? will be +ve but if oxidation takes place at the given electrode is E° will be -ve. eg if SHE is coupled with standard copper electrode reduction takes place at copper electrode cell can be represented Pu(s) | Ha(B, Iba) | H’(aq,1M) || Cu?*(aq, 1M) |Cu(s) Beat = Evcwasicu~ E° ean 0.34 = E®cw2-icu- 0 Therefore E°cu2+.cu = 0.34V If SHE coupled with standard zinc electrode oxidation takes place at zinc electrode. Cell can be represented as 2Zn°"(aq, 1M) | Zn(3) || H"(aq, 1M) Ha( tbar) | PA(s) Xen = E°esnta ~ E°zn2vtn 0.76 = 0 - E°zn2 Therefore E2922 Bea = 0.34 -(-0.76) EL Gls hd Copper discves at coer ected a » © If the standard electrode potential of an electrode is greater than zero then its reduced form is more stable compared to hydrogen gas. Similarly, if the standard electrode potential is negative then hydrogen gas is more stable than the reduced form of the species. A negative E° means that the redox couple is a stronger reducing agent than the H’/H, couple, A positive E® means that the redox couple is a weaker reducing agent than the H/H2 couple. The standard electrode potential for fluorine is the highest in the Table indicating that fluorine gas () has the maximum tendency to get reduced to fluoride ions (F-) and therefore fluorine gas is the strongest oxidising agent and fluoride ion is the weakest reducing agent.Krishnarjuna N(Department of chemistry VSPU BLR) Po ge|5 ¢ Lithium has the lowest electrode potential indicating that lithium ion is the weakest oxidising agent while lithium metal is the most powerful reducing agent in an aqueous solution, % Highly reactive metals with lower reduction potential than hydrogen are not obtained by electrolysis of an aqueous solution of their salts because their cations cannot be reduced at the cathode in the presence of water * Generally, d-block elements are less reactive and hence can be prepared by electrolysis of their salt solution. DISPLACEMENT OF METAL BY ANOTHER METAL FROM ITS SALT SOLUTION: % A metal higher in the series will displace the metal from its salt solution which is lower in the series. That is the metal having low standard reduction potential will displace the metal from its salt solution which has higher value of standard reduction potential. + A metal higher in the series has greater tendency to provide electrons to the cations of the metal to be precipitated. % Tron and the metals above iron are capable of liberating hydrogen from water. This tendency decreases from top to bottom in electrochemical series. % The metal placed above Mg in the series decomposes water at ordinary temperature ‘The metal placed from Mg to Cr decomposes water at higher temperature. % Fe decomposes with steam. REDUCING POWER(REDUCING AGENT) OF METALS: * Reducing nature depends on the tendency of losing electron or electrons, More the negative reduction potential, more is the tendency to lose electron or electrons(oxidation). % Reducing nature decreases from top to bottom in the electrochemical series. Ex: Reducing power: Na > Zn> Fe Reduction potential : -2.72 -0.76 -0.44 Oxidising nature depends on the tendency of accept electron or electrons. More the positive reduction potential, more is the tendency to accept electron or electrons(reduction). Oxidising nature increases from top to bottom in the electrochemical series. Ex: Oxidisingpower: ob < Bm < Ch Manufacture of heavy water D2O. * The metals like Na, K, Mg, Al, etc are obtained by electrolysis of fused electrolytes. > Non-metals like hydrogen, Fluorine, Chlorine are obtained by electrolysis. > In this method pure metal is deposited at cathode from a solution containing the metal ions Ag, Cu etc. “» Compounds like NaOH, KOH, NazCOs, KCIOs,White lead, KMnOsetc are synthesised by electrosythesis method. ELECTROPLATING: The process of coating an inferior metal with a superior metal by electrolysis is known as electroplating. The aim of electroplating is to prevent the inferior metal from corrosion and to make it more attractive in appearance. The object to be plated is made the cathode of an electrolytic cell that contains a solution of ions of the metal to be deposited For electroplating of Gold (Au) the electrolyte is used is K[Au(CN)2] and for Ag is, K[Ag(CN)o} 7 7 vKrishnarjuna N(Department of chemistry VSPU BLR) Po ge |6 NERNST EQUATION; The concentration of all the species involved in the electrode reaction is unity. This need not be always true. ‘Nernst showed that for the electrode reaction: M™(aq) + ne + M(s) The electrode potential at any concentration measured with respect to standard hydrogen electrode can be represented by: Bont) = © ar ime urs) 10 =e lta wm) 6 1 Tag] but concentration of solid, it is taken as unity and we have Bama 8 — carta = 4 R is gas constant (8.314 Jk” mol", F is Faraday constant (96487 C mol"), T is temperature in kelvin and [M™]is the concentration of the species, M™” In Daniell cell, the electrode potential for any given concentration of Cu** and Zn** ions, we write Forcathode Frowion -E cate “go For anode (Cu? few FR (Cu24¢agy) 1 Bezn*yzny = BP — ent fen) ~ 26 ™ tan? *aqy) ar 1 The cell potential Bean = Eccuetyeu)~ Etzn2+/2n) a fr 0 Beat = E%ex2tjc49 pre Bantam + Eg ety? ae UE exee ean” Pent oan | ct cay Sp ne Substituting the values of R, F and T= 298K it reduces to BoB bas an] cat Geet Bia] For a general electrochemical reaction of the type Nernst equation can be written as: Ecet = E° (cour) - $F 1NQ E =E Ty, fer(0y" cat (eat “ak aoe 0059) fcle1D}4 Ecat = E%cety “108 tapers EQUILIBRIUM CONSTANT FROM NERNST EQUATION ; * If the circuit in Daniell celt is closed then we note that the reaction takes place and as time passes, the concentration of Zn” keeps on increasing while the concentration of Cu" keeps on decreasing. + Atthe same time voltage of the cell as read on the voltmeter keeps on decreasing. * After some time, we shall note that there is no change in the concentration of Cu?* and Zn?* ions and atthe same time, volumeter gives zero reading, This indicates that equilibrium has been attained = Eo (ek1D)" cell (cell) a Sa Tare ° ery lector! E (cell) pa eer But at equilibrium faror faye)"Krishnarjuna N(Department of chemistry VSPU BLR) Po ¢ At 298K the above equation can be written as WB? log Ke Ect Note: For spariggly soluble electrolyte like Silver iodide(Agl) Ecr-pagiae) = Ecags sag) * 0.059log Kop ELECTROCHEMICAL CELL AND GIBBS ENERGY OF THE REACTION: The reversible work done by a galvanic cell is equal to decrease in its Gibbs energy and therefore, if the emf of the cell is E and nF is the amount of charge passed and A, G is the Gibbs energy of the reaction, then If the concentration of all the reacting species is unity, then ArG nFE (ett) If the concentration of all the reacting species is unity, then E(cell) = and we have "(cell) ArG? = —nFE%y Thus, from the measurement of E°ciy we can obtain an important thermodynamic quantity, ArG? , standard Gibbs energy of the reaction. From the latter we can calculate equilibrium constant by the equation: ArG® = —-RT In K Note: 1. Ifthe reaction to be spontaneous then Eca=+ve AG 2. A,Gis extensive property and E.ei is intensive property TEMPERATURE CO-EFFICIENT: The temperature coefficient is defined as the ratios of the relative rates of the reaction at an increase of 10 Kelvin in the temperature. ae ‘Temperature co-efficient = AG = AH-TAS AG = -nFE cot as =n) OH = “FE con + FT (94) ve Key>t Thermal efficiency, 7 of an electrochemical converter is the amount of useful energy produced relative to the change in enthalpy AH between the product and source. __ Useful energy - a AG aH CONDUCTANCE OF ELECTROLYTIC SOLUTIONS: ” ‘The electrical resistance is represented by the symbol ‘R’ and it is measured in ohm (@) which in terms of SI base units is equal to (kg m?)/(S* A). % The electrical resistance of any object is directly proportional to its length, 1, and inversely proportional to its area of cross section, A. That is, Ray (or) R=p) + The constant of proportionality, p(Greek, rho), is called resistivity(specitic resistance). Its ST unit is ohm meter (2 m). *% Physically, the resistivity for a substance is its resistance when it is one meter long and its area of cctoss section is one m*.Krishnarjuna N(Department of chemistry VSPU BLR) Pa ge|8 % The inverse of resistance, R, is called conductance, G, Geis aK Rpt + The SI unit of conductance is Siemens, represented by the symbol ‘S’ an ohm (also known as mho) or Q % The inverse of resistivity, called conductivity (specific conductance) is represented by the symbol, (Greek, kappa). % The ST unit of conductivity is S mv, 4 Conductivity of a material in $ mis its conductance when itis 1 m long and its area of cross section is 1m’, equal to THE ‘TIVITY OF AN ELECTRONK -TOR: The electronic conductance depends on (i) The nature and structure of the metal (ii) The number of valence electrons per atom. (iii) Temperature(Conductivity decreases with increase in the temperature) : In metals, conductivity is due to movement of free electrons. When temperature increases, the vibration of metal ions increases. This results in increase in resistance of metal and hence, decrease in conductivity. THE CONDUCTIVITY OF AN ELECTROLYTIC CONDUCTOR: The conductivity of electrolytic solution Depends upon (i) The nature of the electrolyte (ii) Size of the ions produced and their solvation, (iv) The nature of the solvent and its viscosity. (iv) Concentration of the electrolyte and (v) Temperature (increases with increase in temperature): When temperature increases, the vibration of metal ions increases. In electrolytic conductors, the ions are charge carriers and with increase in temperature, ionization increases and hence, conductivity increases. Difference between the conductivity of an electronic conductor and electrolytic conductor. S.No Metallic conductor Electrolytic conductor 1__| Conduction due to flow of electrons | Conduction due to flow of ions 2 | Does not cause chemical causes chemical decomposition decomposition 3 | Conductance decreases with increase | Conductance increases with increase in temperature in temperature % The accurate measurement of an unknown resistance can be performed on a Wheatstone bridge. ‘conaugaey 4 It consists of two resistances Ry and Ry, a variable resistance Ry and the conductivity cell having the unknown resistance Ra.Krishnarjuna N(Department of chemistry VSPU BLR) Pa ge|9 The Wheatstone bridge is fed by an oscillator O (a source of a.c. power in the audio frequency range 550 to 5000 cycles per second). P is a suitable detector (a headphone or other electronic device) and the bridge is balanced when no current passes through the detector. Under these conditions: Unknown resistance Ro =!" Rs Once the cell constant and the resistance of the solution in the cell is determined, the conductivity of the solution is given by the equation: Cell constant _ 6" RO OR Cell constant = Ri Note: 1. Electrical conductivity of carboxylic acids is directly proportional to extent of ionisation. 2. Conductivity a —_—___ 4 Y 9c opetelons © Viscosity © Solvation ® Temperature MOLAR CONDUCTIVITY ( Ay): Molar conductivity of a solution at a given concentration is the conductance of the volume V of a solution Containing one mole of electrolyte kept between two electrodes with area of cross section A and distance Of unit length. * The Slunit of Molar conductivity is Sm’mol Molar conductivity = An= x(Sem™*)<1 000 (mol/L) ivi (Sm’motj=_"6™_) Molar conductivity = Am ‘aS Am (Sm’mol") = 10* Am (Sem’mol) Molar conductivity = Am (Scm*mol"): Note: MOLAR CONDUCTANCE= MOBILITY *F EQUIVALENCE CONDUCTIVITY(Aco) * Itis defined as the conducting power of all the ions produced by dissolving one-gram equivalent of an electrolyte in solution. og = xn _ «1000 “a G Normality The SLunit of Molar conductivity is Sm*(equiv)" Equivalent conductance a mobility of ions a Ered a Dilution Size of ions: Lit Na” > K* Size of ions: Li'(aq) >Na‘(aq) >K*(aq) mobility : Li‘(aq) If the electrode is inert (e.g,, platinum or gold), it does not participate in the chemical reaction and acts only as source or sink for electrons. > If the electrode is reactive, it participates in the electrode reaction Ex: 1. When molten sodium chloride is electrolysed using inert electrodes. owitaion At Anode: 2Cr "CL, +26 reduction At Cathode : Na* +e" +—-—-—4Na Thus chlorine gas is liberated at anode and sodium is formed at cathode. 2. When aqueous sodium chloride is electrolysed. NaCl(aq) + Na*(aq) + ne (aq) ‘Na*(aq) + C(aq) Cathode : HzO + &° —+ 4 Ho(g) + OH (aq) Anode: Cl-(aq) > % Ch(g) +e Net reaction: NaCl(aq) + Hz0(1) -NaOH(aq)+ 4H2(g) +Cl(g)Krishnarjuna N(Department of chemistry VSPUBLR) Page| 12 3. Electrolysis of Aq CuSO«: Anode: 20H’ —»%02 +H:0 +2e" Cathode: Cu** 2e > Cu 4, Electrolysis of Aq H2SO, Anode: 20H 402 +20 +2e Cathode: 2H’ + 2e" — Ha(g)Krishnarjuna N(Department of chemistry VSPU BLR) Pa ge | 13 BATTERIES: A container consisting of one or more cells, in which chemical energy is converted into electricity and used as a source of power. ‘There are mainly two types of batteries i.e Primary Batteries and Secondary Batteries. PRIMARY BATTERIES : Primary battery is one in which reaction occurs only once and cannot be recharged. Eg: Dry cell or Leclanche Cell and Mercury cell DRY CELL (LECLANCHE CELL): Anode : Zn(s) — Zn?"+ 2e" Cathode: MnO: + NH’ +e’ -MnO(OH) +NH3 MERCURY CELL: Anode : Zn(Hg) + 20H — ZnO(s) + FLO +2e Cathode: HgO + H20 + 2e > Hg(1) + 20H" Overall reaction: Zn(Hg) + HgO(s) + ZnO(s) + Hg(1) SECONDARY BATTERIES: Secondary battery is one which can be recharged by passing current through it in opposite direction, so that it can be Re-used. Eg: Lead storage battery and Nickel cadmium cell. LEAD STORAGE BATTERY ; Itconsists of lead anode and a grid of lead packed with lead dioxide (PbO:) as cathode. Electrolyte is 38% solution of sulphuric acid Discharging: «The reactions taking place when the battery is in use are Anode: Pb +SO,7 — PbSOs + 2e° Cathode: PbO: +SO.? + 4H” +2e— PbSO; +2 HO The overall reaction: Pb + PbO2+ 2H2SO4 — 2 PbSO4 +2H20_ Charging: ‘Anode: PbSOs + 2e —Pb +S0s? Cathode: PbSO; +2 HzO — PbO» +SO.* + 4H" +2e Overall reaction : Cd(s) + 2Ni(OH)s (s) —» CdO(s) +2Ni(OH), (s) +20) FUEL CELLS: Galvanic cells that are designed to convert the energy of combustion of fuels like hydrogen, methane, ‘methanol, etc. directly into electrical energy are called fuel cells. Ex: H2-O; fuel cell ‘Hp-O2 FUEL CELL : nade ° Jone # In this hydrogen and oxygen gases are bubbled through porous carbon electrodes into concentrated aqueous Sodium hydroxide solution.Krishnarjuna N(Department of chemistry VSPU BLR) Page| 14 © Catalyst like finely divided platinum or palladium is incorporated into the electrodes for increasing the rate of electrode reaction. + Efficiency of fuel cell is 60-70%, Reactions taking place are Cathode : O2(g) +2H20(I) +4e° + 40H(aq) Anode: 2H,(g) + 40H (aq) > 4H20(1) +4e" Overall reaction: 2F1(g) +O2(g) + 2420(1) (CHi:-02 FUEL CELL : Anode: CHs + 2H20 — CO2 +8 H! + Be" Cathode: | O2 + 4H? + de > 2H20] x2 Overall : CH: + 202 CO2 + 2H20 CORROSION ; ‘% When @ metal is exposed to the atmosphere it is slowly attacked by the constituents of the environment as a result of which the metal is slowly lost in the form of its compound. This is called corrosion. CORROSION OF IRON(RUSTING OF IRON) ‘Anode : 2 Fe(s) +2Fe"* + de Cathode : O2(g)* 4H(aq) + 4e° > 2H200) ‘The overall reaction: 2Fe(s) + Oo(g) + 4H"(aq) — 2 Fe**(aq) +2H2O(1) +H’ are produced from HoCOs formed due to dissolution of carbon dioxide from air into water the Fe” ions are further oxidized by atmospheric oxygen to fertic ion which are ultimately converted to hydrated ferric Oxide called rust. + Composition of rust is (FexOs.xH20). PREVENTION OF CORROSION: ‘© One of the simplest methods of preventing corrosion is to prevent the surface of the metallic object to come in contact with atmosphere. This can be done by covering the surface with paint or by some chemicals (e.g. bisphenol). + Another simple method is to cover the surface by other metals (Sn, Zn, etc.) that are inert or react to save the object. «An electrochemical method is to provide a sacrificial electrode of another metal (like Mg, Zn, etc.) which corrodes itself but saves the object. CORROSIVE SALTS: In the presence of moisture, the metals that are ready to lose its electron and undergoes faster corrosion. «Highly Corrosive salt is Mercutic chloride gCKrishnarjuna N(Department of chemistry VSPU BLR) Page |15 Distinction between Primary, Secondary & Fuel cells Ty Rony acts as galvane | 1) Radie as galvanic or | 7)ifis @ ample galvanic or oF vote cell. be Volts cel while ‘olla eal te, produces. Procuoss alsctrcty ischarsing (produces | alectniety ‘toctricty) ana acte a5 ‘Slectroiytic eal (consumes Stostrety) 2) Goll reaction ie net | 2) Call roaction te 2) Cell reaction '3) Gant be recharged. |3) Can be rechareed——*|8) Eneray canbe sthdrawn cantinuusty [)Gan be used as long [4] Gan be weed again and 4) Reactant shouts be Se thosetive materiale | again by recharging replenished continuoutiy. i ‘ae present ges net store anergy. Uses in Pacemakers [aes i eleckonie ss: Ges een apace zs ‘Squpments,aigtarcameras, | [productot a soures ot heah ‘Stiepe dash tim Sater for astronauls) % Conductometric titration is a laboratory method of quantitative analysis used to identify the concentration of a given analyte in a mixture. * In Conductometric titration one ion is replaced by other ion, since the conductance of both the ions are different therefore conductance(G) of the solution varies as the titration carried out. % Plot the graph conductance(G) v/s volume of titrant(V), 1. Strong Acid V/S Strong Base (or) Strong Base V/S Strong acid Ex: HCl v/s NaOH 2. Weak acid V/S Strong base (or) Weak base V/S Strong acid Ex: CHsCOOH v/s NaOH. 3. Strong acid V/S Weak base (or) Strong base V/S Weak acid Ex: HCI v/s NHsOHKrishnarjuna N(Department of chemistry VSPU BLR) Pa ge |16 Due to common ion (NHa") effect the ionisation of NHsOH get suppressed and therefore remains in undissociated form. 4. Weak acid V/S Weak base Ex: CH,COOH w/s NH;OH (or) Weak base V/S Weak aci Electrochemical series: Element | Electrode reaction(Reduction) Standard electrode reduction potential(E°) Volt Li Lit te Li 3.05 K Kt++e > K -2.925, Ba Ba” +26 —> Ba -2.90 Sr Sr 426° > Sr -2.89 Ca Ca™* +2e° > Ca -2.87 Na Na’ te — Na 2.714 Mg Mg” +2e —> Mg -2.37 AL APY +3e — Al 1.66 Mn Mn” +2e" — Mn 1.18 Zn Zn +2e— Zn -0.7628 cr Cr +36 Cr 0.74 Fe Fe?’ +2e° > Fe 0.44 Cd Cd?" +2e° > Cd -0.403 Co Co” +2e + Co -0.27 Ni Ni?’ +2e€ > Ni -0.25 Sn Sn* +2e° — Sn -0.14 Pb Pb” +2e° — Pb -0.12 Fa 2H" +2e° > Ha 0.00 cu Cu* +2e > Cu +0,337 kh Tp +2e > 2 +0.535 Hg He” +2e > Hg +0.885 Ag Ag’ te > Ag +0.799 Br Br +2e — 2Br~ +108 Pt Pt +2e°— Pt +120, Ch Ch +2e = 2Cr +136 Au Au™ +3e°—> Au +1.50. Fi Fi + 2e > 2F +2.87,NUMERICALS 1. The cell in which the following reaction occurs. 2 Fer aq +t 2a 2Fe?* aq) + 12(5) has E%e = 0.236 V at 298 K. Calculate the standard Gibb’s Free energy (F = 96487C mol) 2. For a given data E®ugzeim = -2.37 V, E°eursieu = + 0.34V Calculate the emf of the cell in which the following reaction takes Place. Mgje) + Cua Mg? (as) + Cs) (0.0001M) (0.001M) 3. Calculate the equilibrium constant for the reaction: Cu(s) + 2Ag*%aq) + Cu*%aq) + 2Agis); E®car= +0.46V 4.Calculate the equilibrium constant of a reaction at 298K Mg («+2Ag*(«a) Mg? aq)+2AQiaq) Given E%wi= +3.16V 5. Calculate AG" for the following reaction: Fe?+ + Agt -----> Fe* + Ag (Given : E%a = 0.03V ) 6. Calculate the mass of aluminium deposited at cathode when 193C of current is passed through molten electrolyte of alumina. (Molar mass of Al=27gmol™ IF = 96500 Cmol" ). 7. Calculate standard free energy change for the reaction. Zn) + 2AQ™ (aa) > ZN*%(aq) + 2AQ(s) : E° cell = 1.56V; 1F = 96500Cmol*8. Calculate EMF of the cell represented below Cu(s) + 2Ag*(0.002M) — Cu?*(0.12M) + 2Ag(s) Given E%cer= 1.1V 9. The cell in which the following reaction occurs: 2Fe** (aq) + 21 (aq) —> 2Fe** (aq) +I? (5) has E’ei=0.236 V at 298 K. Calculate the standard Gibbs energy and the equilibrium constant of the cell reaction. 10.The molar conductivity of 0.025 mol L methanoic acid is 46.1 S cm? mol, Calculate its degree of dissociation and dissociation constant Given \"(H*)=349.6 Sem? mol"! andA°(HCOO-)=54.6S cm? molt 11.If a current of 0.5 ampere flows through a metallic wire for 2 hours, then how many electrons would flow through the wire?