Electrochemistry is that branch of chemistry which deals with 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. Importance of Electrochemistry 1. Production of metals like Na, Mg. Ca and Al. 2. Electroplating. 3. Purification of metals. 4. Batteries and cells used in various instruments. Conductors Substances that allow electric current to pass through them are known as conductors.Metallic Conductors or Electronic Conductors Substances which allow the electric current to pass through them by the movement of electrons are called metallic conductors, e.g.. metals. Electrolytic Conductors or Electrolytes Substances which allow the passage of electricity through their fused state or aqueous solution and undergo chemical decomposition are called electrolytic conductors, e.g., aqueous solution of acids. bases and salts. Electrolytes are of two types: 1. Strong electrolytes The electrolytes that completely dissociate or1. Strong electrolytes The electrolytes that completely dissociate or ionise into ions are called strong electrolytes. e.g,, HCl, NAOH, K,SO, 2. Weak electrolytes The electrolytes that dissociate partially (ex < 1) are called weak electrolytes, e.g., CH,COOH, H,COg, NH,OHH.S§, etc. Electrochemical Cell and Electrolytic ae oe1, | Definition A cevice used to convert]A device used to comied out chemical chemical energy into electrical] non-spontaneous enerry. reactions by electrical energy. 2. [Assembly i combination ota k& 2 re ek containg the hratl-celts, containing the same ox| same clecades pet in the electrodes in the same| same or different 3. | Nature of |Anode is negative, canode s|Anode is positive, cathode is | sectrodes positive. negative. 4, |Movernert ot [From anode to cathode in| Blectons enter through cathode electrons, extemal circuit. and leave by anode. 5. |Spontanety (Cell reaction is spontaneous | Cell reaction is non- spontaneous. 6. . | Salt bridge [Sat bridge &s requred ‘Salt oridge is not required. A cell of almost constant emf is called standard cell. The most common is Weston standard cell. Galvanic cell is also called voltaic cell. General Representation of anGeneral Representation of an Electrochemical Cell Ms) MP"(aq) IL Mz "(ag) | M(e) Anode Oxidation Sah = Reduction Cathode halfcell bridge half-celll ve de tconsenston Negative. due te reease of _ elections _ ‘Sen Reaction __ _Oneation _ _ Movemert of elections into the Out of celt Other features of the electrochemical cell are 1. There is no evolution of heat. 2. The solution remains neutral on both sides. 3. The reaction and now of electrons stops after sometime. Daniell Cell An electrochemical cell of zinc and copper metals is known as Daniell cell. It is represented asnay es 8: Daniell Cell An electrochemical cell of zinc and copper metals is known as Daniell cell. It is represented as Cell diagram, Zn(s)| Zn™* (ag)|| Cu** (aq)| Cu(s) LHS oxidation, Zn —+ Zn + 2c" RUS reduction, Cu* +2e° —> Cu Overall reaction, Zn +Cu*(aqg) —+ Zn*(ag)+Cu By convention cathode is represented on the RHS and anode on the LHS. Function of salt bridge 1. It completes the circuit and allows the flow of current. 2. It maintains the electrical neutrality on both sides.2. It maintains the electrical neutrality on both sides. Salt-bridge generally contains solution of strong electrolyte such as KNO,, KCL etc. KCl is preferred because the transport numbers of K+ and Cl- are almost same. Transport number or Transference number The current flowing through an electrolytic solution is carried by the ions. The fraction of the current carried by an ion is called its transport number or transference number. Thus. Transport number of cation. n, = (current carried by cation/total current)Transport number of cation. n, = (current carried by anion/total current) Evidently n, +n, = 1 Electrode Potential When an electrode is in contact with the solution of its ions ina half-cell, it has a tendency to lose or gain electrons which is known as electrode potential. It is expressed in volts. It is an intensive property, i.e., independent of the amount of species in the reaction. Oxidation potential The tendency to lose electrons in the above case is known as oxidation potential. Oxidation potential of a half-cell is inversely proportional to the concentration of ions in the solutionconcentration of ions In the solution. Reduction potential The tendency to gain electrons in the above case is known as reduction potential. According to IUPAC convention, the reduction potential alone be called as the electrode potential unless it is specifically mentioned. ° - ° E red ~~ E oxidalion It is not possible to determine the absolute value of electrode potential. For this a reference electrode [NHE or SHE] is required. The electrode potential is only the difference of potentials between two electrodes that we can measure by combining them to give a complete cell. _Standard electrode notentialStandard electrode potential The potential difference developed between metal electrode and solution of ions of unit molarity (1M) at 1 atm pressure and 25°C (298 K) is called standard electrode potential. It is denoted by E°. Reference Electrode The electrode of known potential is called reference electrode. It may be primary reference electrode like hydrogen electrode or secondary reference electrode like calomel electrode. Standard hydrogen electrode (SHE) Standard hydrogen electrode (SHE). also known as normal hydrogen electrode NILE . er ,Standard hydrogen electrode (SHE) Standard hydrogen electrode (SHE). also known as normal hydrogen electrode (NHE), consists of platinum wire, carrying platinum foil coated with finely divided platinum black. The wire is sealed into a glass tube. placed in beaker containing 1 M HCI. The hydrogen gas at 1 atm pressure is bubbled through the solution at 298K. Half-cell is pt H, (1 atm) H+ (1M) L. H. gas at + bar pressure Connecting wire »1M HCI solution Platinum fail coated with Pt black In SHE. at the surface ofIn SHE. at the surface of plantinum, either of (he following reaction can take place 2H+(ag) + 2e- = H,G Reduction H,(g) > 2H*(ag) + 2e- Oxidation The electrode potential of SHE has been fixed as zero at all temperatures. Its main drawbacks are L It is difficult to maintain 1 atm pressure of H, gas. 2. It is difficult to maintain H+ ion concentration 1 M. 3. The platinum electrode is easily poisoned by traces of impurities. Hence, calomel electrodes are conveniently used as reference a —_—"*Hence, calomel electrodes are conveniently used as reference electrodes, It consists of mercury in contact with Hg, Cl, (calomel) paste in a solution of KCI. Electromotive Force (emf) of a Cell It is the difference between the electrode potentials of two half- cells and cause flow of current from electrode at higher potential to electrode at lower potential. It is also the measure of free energy change. Standard emf of a cell, Fira = Ecxtnodo ~ Benote = Etigny ~ Ey = Ety + E°. Potential difference between two ep, etl ierence of he two hat electrodes when no current is flowing cells when electric curren in the creuit is called emt. = through the cells is caled a potential. Ent is the maximum voloae which can] tis always less than the maximum be obtained trom the voltage obtainable from the cell. 3 [Ents rmeuret bo maaan tis measured by a votmeter, 2.Potential difference between two electrodes when no current is flowing in the circuit #s called emt. : cilTputertial ‘The potential difference of the two hatf- cells when electric cument flows through the ceils is called cell potential. 2. |Em® is the maximum voltage which can bbe obtained from the ceil Itis atways less than the maximum voltage obtainable from the cell. 3. |Emf is measured by a potentiometer. tis measured by a voltmeter, Electrochemical Series It is the arrangement of electrodes in the increasing order of their standard reduction potentials. Standard Electrode Potential at 298 K HO; + 2H* + 2e7 MnO} + 8H = MnO, (s) + 4H? + 26° > - By + 227 = "NO3+ 4Ht + Ze SSCNOKQ) 4 2H, 097 2Hg?* + 2e” 4 He3* 0.92 agi te 2 gts) 0.80 fe +e7 4 Fe?* 0.77 “Of g)+ 2H + 20" = HQ, 0.68 bt ze = er 058Standard Electrode Potential at 298 K Reaction (Oxidised form) + ne~ Fig) + 2e7 Cot+e H,0, + 2H* + 2e" 5 5 Ss © + Oleh aHT + de -~ ~MAOAS) + 4H" + 20° > Br, + 2e~ = NO} + aH? 4 327 > 2Hg?* + 2e" > He3* 0.92 ~ weite > gts) 0.80 - Fe +e > Fee 077 a 0,(g) + 2H" + 2e7 > HA, 0.68 ~ 4 26 > ar 054 - Cue + er > Cuts) 0.52 CP* + 20° > Cuts) 0.34 uit = AgCKs) + e7 => Agts)+ Cr 3 AgBts) + e7 > Agts) + Br 0.103 2H + 267 > Pb?* + 2e7 > Sr?* + 2e- > Sats) - 0.14 N?* +207 > Nis) : 028! Fe? + 2e7 > Fes) - 0.441 ——4 CA + 3e° > Cats) ~ 0.74" Zn + 2e7 + Zn(s) “ord - i +26 20H" ~ 0.83) 20 + 7 + He(g) + 20H (a0! 83) A + Be + Alls) - 1.66] + Mg?’ + 2e° Mats) - 2.36;AGXS) +e” = AgBits) + €7 ~ Agts) + Br 2H* + 2e7 + H,(@) r Poe? 4 2e7 4 PIXs) - OF Sr? + 2e7 3 Sats) - om N?* + 2e7 2 Nis) -0. Fe" + 2e7 2 Fes) - 0.441 C8 4 Be" 2 CAs) ~ 0.7 2* + 2e7 4 Znts) - O71 2H,0 = 2e7 = Hite) + 20H (eat ~ 0.83: AM 4 Be" > Alls) - 1.66; Mg?* + 2e" ” Mats) - 236; Nat en = Nats) ~ 27 Ca?* + 20° 4 Cals) - 2.87 Kee + Kis) - 293) lit +e + re) = 3.08: Appications of Electrochemical Series (ECS) 1. The lower the value of E°, the greater the tendency to form cation. M — Mn + ne- Metals placed below hydrogen in ECS replace hydrogen from dit acids but metals placedMetals placed below nydrogen in ECS replace hydrogen from dil acids but metals placed above hydrogen cannot replace hydrogen from dil acids. Ca +dil.H,80, —» CaSO,+H,T possible, (Ca+2H* —» Ca** +H,) Cu +[Link], —+ CuSO, +H, T not possible, (Cu+2H* —+> Cu” +H,) 3. Oxides of metals placed below hydrogen are not reduced by H, but oxides of iron and metals placed above iron are reduced by H,- =# SnO, PbO, CuO are reduced by H, =» CaO, K,O are not reduced by Hy 4. Reducing character increases down the series. 5. Reactivity increases down the3. Reactivity increases qown the series. 6. Determination of emf; emf is the difference of reduction potentials of two half-cells. Cem = Erus ~ Exus If the value of emf is positive. then reaction take place spontaneously, otherwise not. 7. Greater the reduction potential of a substance, oxidising power. (e.g.. F, > Cl, > Br, > I,) 8. A negative value of standard reduction potential shows that it is the site of oxidation. 9. Oxides of metals having E°,.g 2 0.79 will be decomposed by heating to form O, and metal.J. UXIGES OT MEAS NAVING Coyeg 2 0.79 will be decomposed by heating to form O, and metal. HgO (s) + Hg(|)(1/2)0,(g) (E° seg = 0.79V) Nernst Equation The relationship between the concentration of ions and electrode potential is given by Nernst equation. M"*+ne —> M 2.303 RT 1 Baynes ae = Eyany an ~ ar 6 ["*] 0.0591 toe 1 | n mM" Expres yy = E. Mim For a electrochemical cell, aA+bB —+» cC+dD _p _ 2.3038RT | (CI*[DY* Bent = Ba re appFor a electrochemical cell, aA+bB — cC+dD 2.308RT |, (CI [D\* Bou = Ba — Te (ar er Concentration of pure solids and liquids is taken as unity. Nernst equation and K, At equilibrium - At equilibrium, E,y = 0 E. 0.0591 mm ‘coll = —— log K, at 298K AG? =- aFEy Here, AG° is the standard Gibbs free energy change. Relationship between freeHere, AG° is the standard Gibbs free energy change. Relationship between free energy change and equilibrium constant AG? = - 2.303RT log K, Concentration Cells (i) Electrode concentration cells Two hydrogen electrodes or different pressures are dipped In the same solution of electrolyte, e.g. Pt, H(p, IH*] Ho(p,)Pt, p, > Pp p__..2-303RT , | Pyeg. Pt, H(p,)|H*1Ha(p,)Pt, p> Pp 2.303RT Eon = VF log 2 (ii) Electrolyte concentration cells Electrodes are the same but electrolyte solutions have different concentrations, e.g. Zn |Zn**(C,) 1Zn?*(C,)|Zn, C, > C, — 2:308RT |, Cy _ 0.0501, Cy Evo ~ nF log CG n log G Conductance (G) It is the ease of flow of electric current through the conductor. It is reciprocal of resistance (R). G = (1/R), units ohm-1 mhos or Q1 Specific Conductivity (K)SPecitic CLONMQUCLIVILY (A) It is the reciprocal of specific resistance. cote | saw) 2G «cell constam iG 9 Ra a (- = cell constant} a Units of x = 42 'om"! =Sem (Q' =S iv. Siemens) Unit of cell constant is cm-1 or m- 1, Specific conductivity decreases on dilution. This is because concentration of ions per cc decreases upon dilution. Molar Conductivity (A,,) The conductivity of all the ions produced when 1 mole of an electrolyte is dissolved in V mL of solution is known as molar conductivity. van ifiIt is related to specific conductance as Am = (kK X 1000/M) where. M = molarity. It units are QO cm2 mol or S cm2 mol. Equivalent conductivity (A,,) The conducting power of all the ions produced when 1 g- equivalent of an electrolyte is dissolved in V mL of solution, is called equivalent conductivity. It is related to specific conductance as Am = (kK X 1000/N) where. N = normality. Its units are ohm cm2 (equiv-’) or mho cm2 (equiv-!) or S cm2 (g-or mho cm? (equiv!) or 5 cm? (g- equiv). Debye-Huckel Onsagar equation It gives a relation between molar conductivity, A,, at a particular concentration and molar conductivity A,, at infinite dilution. A. = Nn, - VC where, b is a constant. It depends upon the nature of solvent and temperature. Factors Affecting Conductivity (i) Nature of electrolyte The strong electrolytes like KNO, KCI. NaOH. etc. are completely ionised in aqueous solution and have high values of conductivity (molar as well as equivalent). The weak electrolytes areThe weak electrolytes are ionised to a lesser extent in aqueous solution and have lower values of conductivity (molar as well as equivalent) . ii) Concentration of the solution The concentrated solutions of strong electrolytes have Slgnificant interionic attractions. which reduce the speed of ions and lower the value of Aj. and Agg. The dilution decreases such attractions and increase the value of A, and Agg. KCl Am CH;GOOH JeThe limiting value, A°,, or A%,,. (the molar conductivity at zero concentration (or at infinite dilution) can be obtained extrapolating the graph. In case of weak electrolytes, the degree of ionisation increases dilution which increases the value of A,, and A,,. The liminting value A°,, cannot be obtained by extrapolating the graph. ~ limiting value, A°,,, for weak electrolytes is obtained by Kohlrausch law. (iii) Temperature The increase of temperature decreases inter- ionic attractions and increases kinetic energy of ions and their speed. Thus, A,, and A,, increase with temperature. Kohlrausch’s LawKohlrausch’s Law At infinite dilution, the molar conductivity of an electrolyte is the sum of the ionic conductivities of the cations and anions, e.g., for A,B, Af, (ApBy) = xA%. + YAS, 0 _ 4G 0 Neq = Ayt + Ar Applications (i) Determination of equivalent/molar conductivities of weak electrolytes at infinite dilution, e.g., Agu,coon = Atu,coona + Atal — ANact AN, on = Ann ct + ANaon — ANeci (ii) Determination of degree of dissociation (a) of an electrolyte at a given dilution.= Molar conductance at concentration *C” _ An molar conductance at infinite dilution A}, The dissociation constant (K) of the weak electrolyte at concentration C of the solution can be calculated by using the formula k. = (Ca2/1 - a) where, ais the degree of dissociation of the electrolyte. (iii) Salts like BaSO, .., PbSO,' AgCl, AgBr and Agl which do not dissolve to a large extent in water are called sparingly soluble salts. The solubility of a sparingly soluble salt can be calculated as oo x x 1000 ™ ~~ solubility (in mol L*') solubility (im mol 7!) = £21000Solubility (an mol L7!) = ©%1000 Electrolysis It is the process of decomposition of an electrolyte when electric current is passed through either its aqueous solution or molten state, 1. In electrolytic cell both oxidation and reduction takes place in the same cell. 2. Anode is positively charged and cathode is negatively charged, In electrolytic cell. 3. During electrolysis of molten electrolyte, cations are liberated at cathode. while anions at the anode. 4. When two or more ions —__eamnata oat tho oalactradac4. When two or more ions compete at the electrodes. the ion with higher reduction potential gets liberated at the cathode while the ion with lower reduction potential at the anode. For metals 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. The extra voltage thus required is called over voltage or bubble voltage. How to Predict the Products of Electrolysis? When an aqueous solution of an —alactrahutaciownlaeteahuend_if thaElectrolysis? When an aqueous solution of an electrolyte is electrolysed, if the cation has higher reduction potential than water (-0.83 V), cation is liberated at the cathode (e.g.. in the electrolysis of copper and silver salts) otherwise H, gas is liberated due to reduction of water (e.g., in the electrolysis of K, Na, Ca salts, etc.) Similarly if anion has higher oxidation potential than water (- 1.23 V), anion is liberated (e.g., Br-), otherwise O2 gas is liberated due to oxidation of water (e.g., in caseof F-, aqueous solution of Na,SO, as oxidation potential of SO2-, is - 0.2 V). Discharge potential is defined as the minimum potential that must be applied acrossthe electrodes to bring about the sD ee: Sse ee Ree ee OU el nates agelectrodes to bring about tne electrolysis and subsequent discharge of the ion on the electrode. Faraday’s Laws of Electrolysis 1. First law The amount of the substance deposited or liberated at cathode directly proportional to the quantity of electricity passed through electrolyte. WeIlxt=IxtxZ=QxZ = | current in amp, t = time in sec, =" Q= quantity of charge (coulomb) = Zis a constant known as electrochemical equivalent. VAIL te gl lg si geWhen |=1 amp, t=1 sec then Q = 1 coulomb, then w =Z. Thus, electrochemical equivalent I" the amount of the substance deposited or liberated by passing 1A current for 1 sec (i.e.. 1 coulomb, | x t= Q) 2. Second law When the same quantity of electricity is passed through different electrolytes. the amounts of the substance deposited or liberated at the electrodes arc directly proportional to their equivalent weights, Thus, Mass of A _ eq. wt. of A 0 E. eq. wt. of B o 4 4Q_% @2 Ez, 2Q £E;Hence, electrochemical equivalent « equivalent weight. Batteries These are source of electrical energy which may have one or more cells connected in series. For a good quality battery it should be reasonably light. compact and its voltage should not vary appreciably during its use. Primary Batteries In the primary batteries. the reaction occurs only once and after use over a period of time battery becomes dead and cannot be reused again. (i) Dry cell or Leclanehe cell Anode-Zinc container —Cathode Granhita radCathode-Graphite rod surrounded by MnO, powder Electrolyte-Paste of NH,Cl + ZnCl, Cathode reaction, 2MnO,(s) + 2 NH+,(aq) + 2e- 5 Mn,03(s) + 2NH,(g) + H,O(1) Anode reaction, Zn(s) = Zn2+(aq) + 2e- Cell potential 1.25 V to 1.5V (ii) Mercury cell Anode-Zn-Hg amalgam Cathode-Paste of (HgO + C) Electrolyte-Moist paste of KOH- ZnO Cathode reaction,Vatnode reacnon, Hg0(s) + H,O() + 2e° —> He(!)+20H™ Anode reaction, Zn (Hg) + 20H"ag —> ZnO(s)+ HQ!) + 2e° Net reaction, Zn(Hg) + HgO(s) —> ZnOs)+ He?) Cell potential 1.35 V Secondary Batteries These cells can be recharged and can be used again and again, e.g., (i) Lead Storage battery Anode-Spongy lead Cathode-Grid of lead packed with PbO, Electrolyte-38% H,SO, by mass Anode reaction, Pb(s) + SO} (ag) —+ PbSO,(s)+ 26” Cathode reaction, PbO, (s) + SOF” (aq)+ 4H’ (ag) + 2e°—+ PbSO,(s) + 2H) Net reaction, Ph(s) + PbO,(s) + 4H* (aq) + 280% (ag) —> 2PbSO,(s)+ 2H,0(!) When recharged the cell reactions are reversed.(ii) Nickel-cadmium storage cell Anode-Cadmium Cathode-Metal grid containing NiO, Electrolyte-KOH solution Anode reaction, Cd(s) + 20H-(aq) + Cd(OH),(s) + 2e- Cathode reaction, NiO,(s) + 2H,O()) + 2e° —»> Ni(OH),(s) + 20H"(aq) Net reaction, Cd(s) + NiO,(s) + 2H,0(F) —+ Cd(OH),(s)+ Ni(OH),(s) Cell potential = 1.4 V Fuel Cells Galvanic cells which use energy of combustion of fuels like H,, CH,, CH3OH, etc., as the source to produce electrical energy are ed fuel cells. The fuel celleare pollution free and have high efficiency. Hydrogen-Oxygen Fuel Cell Electrodes-Made of porous graphite impregnated with catalyst (Pt, Ag or a metal oxide). Electrolyte-Aqueous solution of KOH or NaOH Oxygen and hydrogen are continuously fed into the cell. Oxidation Half-cell reaction. 2H,(4) + 40H (aq) —> 4H,O(/)+ 4e (at anode) [Link] half-cell reaction, O.(g) + 2H,O(D + 4e° —+ 40H (aq) (at cathode) Net reaction, 2H (9) + 0,g) —> 2H,0()) EMF of the cell t V. Thermodynamic efficiency of a fuel cell, AG _-nFE q=—= AH AH Corrosion Slow formation of undesirable compounds such as oxides, —_culnhides or crarhnnatec at thaCOMMPOUTIOS SUCTI ds OAIQES, sulphides or carbonates at the surface of metals by reaction with moisture and other atmospheric gases is known as corrosion. Factors Affecting Corrosion 1. Reactivity of metals 2. Presence of moisture and atmospheric gases like CO,, SO,, etc. 3. Presence of impurities 4. Strains in the metal 5, Presence of electrolyte Rusting of Iron- Electrochemical Theory An electrochemical cell, also known as corrosion cell, is developed at the surface of iron. — Anaordo _DiroiroanAnode- Pure iron Cathode-Impure surface Electrolyte, ‘ CO, +H,0 —> H,CO, =* 2H* +C02- Anode reaction, 2Fe(s) —+ 2Fe™ (ag) + 4e7 Cathode reaction, Oo(g) + 4H* (ag) + 4e" (1) —> 2H,0 (I) Net reaction, 2Fe(8) + 4H" (aq)+0,(g) —> 2Fe* (ag) + 2H,0 (1) At surface, 4Fe" (ag) +02 (g)+ 4H,0(2) —> 2Fe,0,(s) + 8H* (aq) Fe,O, (8) + xH,0(I) —> Fe,0, +xH,0 (Rust) Rusting of iron can be prevented by the following methods : 1. Barrier protection through coating of paints or electroplating. 2. Through galvanisation or coating of surface with tin metal. 3. By the use of antirust solutions (bis phenol). 4. By cathodic protection in4. By cathodic protection in which a metal is protected from corrosion by connecting it to another metal that is more easily oxidised.