B.E Il Sem (AICTE Model Curriculum) Chemistry notes (Group -A: ECE, IT, Mech, AE) (2019-20) Unit-1 Electrochemistry and Battery Chemistry Electrochemical cells: Electrolytic cell: The cell which converts electrical energy into chemical energy is called as electrolytic cell. An electrolytic cell consists of two metallic or graphite rods dipping in solution of electrolyte and connected to a battery. The rod connected to a positive terminal of the battery acts as anode while that connected to negative terminal acts as cathode. It is to be noted that in an electrolytic cell anode is of positive sign (+) but the cathode is of negative sign (-). Galvanic Cell: Galvanic cell is a device which converts chemical energy into electrical energy by means of a spontaneous redox reaction. It consists of two electrodes immersed in the solution of their respective electrolytes. The two electrodes called, half cells, are connected by a salt bridge. The electrodes are connected to potentiometer or voltmeter by a electrical wire. The electrode at Which oxidation occurs is called as anode (Negative (-) Electrode). The electrode at which reduction occurs is called as Cathode (Positive (+) Electrode). Eg: Daniel cell Salt bridge & Its Role: Beate Voltmeter v Anode satbridge -—)) fa mow mz" ANG IM2n80, 1M CuSO. Daniel cell Salt bridge is an inverted U-tube consists of a concentrated solution of electrolytes like KCI, KNOs, and NH.Cl.These electrolytes are preferred because the mobilities of cation and anion are almost equal. 1. It connects the solutions of two half-cells and completes the cell circuit. 2. It prevents diffusion of the solutions from one half-cell to the otherB.E II Sem (AICTE Model Curriculum) Chemistry notes (Group -A: ECE, IT, Mech, AE) (2019-20) 3. It keeps the solutions in two half-cells electrically neutral. 4, It prevents liquid-liquid junction-potential. Representation of celll Or Cell Notation: /‘ndicates > TS) anaacy) _ ( besenceat e LHS) ( Anode(-)) — \ salt bridge / Gathode()) RHS) Se ee \u— See Zn(s)IZn *(aq,1M) [| (Cu*? (ag,1m) [Cu(s) ites boundary between “Indicates boundary between electrode & electrolytic solution eae & electrolytic solution Difference between Electrolytic cell and Galvanic Cell ElectrolyticCell (cre Electrical energy (from an external source) Chemical energy (of a redox reaction) is is converted into chemical energy. converted into electrical energy. The electrodes may be made of same or The electrodes are made of dissimilar different metals. metals, At the electrodes, non-spontaneous At the electrodes , spontaneous redox reaction take place only when the electrical reaction take place. energy is supplied . Anode — Positive ; Cathode - Negative Anode - Negative ; Cathode - Positive lons are discharged on both the electrodes ons are discharged only on the cathode. Both electrodes are inserted in the same Each electrode is dipped in electrolytic electrolytic solution. solution of its own ions. EMF of a cell: When two electrodes are combined current flows from higher potential to lower potential, the potential difference which is responsible for the flow of current is called EMF of the cell.B.E Il Sem (AICTE Model Curriculum) Chemistry notes (Group -A: ECE, IT, Mech, AE) (2019-20) Ecen= E cathode E Anode Where, E catnode and E anode are reduction potentials of cathode and anode respectively. Electrode potential: When a metal is placed in its electrolytic solution, the metal acquires either positive or negative charge with respect to electrolytic solution which results a potential difference is developed at the interface between electrode and electrolytic solution. This potential difference is called electrode potential. Or Tendency of an electrode to lose or gain electrons when it is in contact with its own ionic solution is called as electrode potential The tendency of an electrode to lose electrons i.e. to get oxidised, is called Oxidation potential, whereas, the tendency of an electrode to gain electrons i.e.to get reduced, is called Reduction potential. Standard electrode potential: The potential of an electrode, at a given temperature, depends upon the concentration of solution of its ions. “The tendency of a pure metal or pure gas at 1 atm pressure to undergo oxidation or reduction when it is in contact with 1M solution of its ions at 25°C, is called as standard electrode potential”. SRP: It is the tendency of a pure metal or pure gas at 1 atm pressure to undergo reduction when itis in contact with 1M solution of its ions at 25° C. ‘SOP: It is the tendency of a pure metal or pure gas at 1 atm pressure to undergo oxidation when it is in contact with 1M solution of its ions at 25° C. ‘Thermodynamics of EME of cells (1) Relationship between Enthalpy change and EMF: From Gibbs-Helmholtz equation, we have We know, AG = AH -TAS - (2) From equation (1) & (2), we getB.E II Sem (AICTE Model Curriculum) Chemistry notes (Group -A: ECE, IT, Mech, AE) (2019-20) Nemst Equation & Its derivation: The Nemst Equation helps us to determine cell potential or electrode potential under non- standard and non-equilibrium conditions. It relates the measured cell potential/electrode potential to the reaction quotient. Cconsider a redox reaction, aA + DB & cC + dD cit 4)*[B)" Q= ‘AG° — 2.030RT Q The decrease in the free energy of such equilibrium is given as, —AG = When a system is operating reversibly the work done by the system is equal to the decrease in the free energy of the system. If the charge associated with a redox process is “nF coulombs” and potential generated is E Volts, the net electrical work done by the reversible cell is “nFE Joules” AG? = FE con & — AG = NF Econ FE co = NFE fey — RTIn Q RT =F, - Fcout = Baan 7g Q 2.303RT Eeeu = Even — Te — lt up log @ 2.303RT. D4 tog SIU2I nF lale[B)P At T= 25°C = 298 K, R- Gas Constant = 8.314//mole, F - Faraday = 96500 Coulombs ferspye arse Eeeu = Egon — Therefore, Econ = Edo — 0.0591 log: Applications of Nernst Equation: 1. Nernst equation is used to study the effect of electrolyte concentration on electrode potential. 2. Nernst equation can be used to calculate cell potentials / Electrode potentials under non-standard and non-equilibrium condition. 3. Determination of unknown concentration of one of the ionic species involved in a redox reaction is possible with help of Nernst equation provided E2.,, and concentration of other ionic species is known.B.E Il Sem (AICTE Model Curriculum) Chemistry notes (Group -A: ECE, IT, Mech, AE) (2019-20) 4. The pH of a solution can be calculated from the measurement of EMF and Nernst equation. 5. Itcan also be used to find the valency (n) of reactive species 6. It can be used to calculate equilibrium constant of redox reaction. Types of Electrodes: (1) Metal ~ Metal ion Electrode: It consists of a pure metal in contact with a solution of its ions. It is constructed by dipping a pure metal in a electrolytic solution of metal. Representation of the electrode: M/ M'" E.g. Zn rod dipped in ZnSO«. (2) Gas Electrode Gas electrode consists of a gas bubbling about an inert metal wire or foil immersed in a solution containing ions to which the gas is reversible. Inert metal wire or foil, usually platinum, helps to attain the equilibrium between the gas & ions and also serve as electric contact for the electrode. Example: Hydrogen electrode Hyarogen electrode (3) Metal - insoluble salt eectrove: It consists of a pure metal in contact with one of its sparingly soluble salts and a solution of a soluble salt having a common anion with the sparingly soluble satt E.g. Calomel electrode: Construction and working of Calomel electrode:B.E II Sem (AICTE Model Curriculum) Chemistry notes (Group -A: ECE, IT, Mech, AE) (2019-20) Calomel electrode is an example of metal -metal insoluble salt electrode, which consists of a glass tube containing two side arms. One of the arms is to connect to salt bridge and the other one is to introduce the components of electrode. Pure Mercury is placed at the bottom of the glass tube. Mercury is covered with a paste of Mercury and Mercurous chloride, over which a solution of potassium chloride is placed. A platinum wire sealed in a thin glass tube, dipping into the mercury, layer, is used for making electrical contact with the external circuit. Paste of Calomel electrode is represented as Pt-Hg/ Hg2Ch/KCI (aq). Calomel electrode acts as either anode or cathode w.r-to the other electrode to which it is connected. If it acts as anode, it involves oxidation. If it acts as cathode it involves reduction. 2Hg-—————--> Hg," + 2e" HgaCl: > Hg?" 2c Hgo?*+ 2Ch ——-> HgaCle Hg,** + 2e°—-—-> 2Hg 2Hg + 2Cr——> Hg2Ch + 2e Hg:Ch+2e —--——---> 2 Hg + 2Cl When it acts as anode, mercury is converted to Mercurous ions. Mercurous ions would combine with Cl ions furnished by KCI to form sparingly soluble Hg:Clr which results there is a fall in the concentration of Cl ions. When it acts as cathode, Hg2"* ions, furnished by the sparingly soluble Hg:Ch, would be discharged at the electrode and there is an increase the concentration of Cl ions. Thus, Calomel electrode is said to be reversible to Cl ions.B.E II Sem (AICTE Model Curriculum) Chemistry notes (Group -A: ECE, IT, Mech, AE) (2019-20) The reduction potential of calomel electrode is given by,Ece 9.0591 15 4 [tal (ct“12 2 Teaactal Ece = 0.280V —0.0591log[Cl-] Since [Hg] = [Hg.Cla]=1and Eg, = 0.280V The potential of the calomel electrode depends upon the concentration of the chloride ion. if the concentration of KCI is 0.1 N, 1.0 N and saturated, calomel electrode is called as Decinormal, Normal and Saturated calomel electrode and their electrode potentials at 25°C are 0.333V, 0.28 V and 0.242V respectively. ‘Advantages: Its construction is very easy, potential measurements are reproducible. Disadvantages: Since Hg.Cl: breaks at 50°C, it can’t be used above this temperature. (4) Redox Electrodes: ‘A Redox electrode consists of an inert material like Pt or Au dipped into a solution containing solution of a chemical species in two different oxidation states. E.g. Quinhydrone Electrode: Construction and working of Quinhydrone electrode: The Quinhydrone electrode an example of redox electrode, which is Ba Quinhydrone powder, which is an constructed by ad ich of equimolar mixture of quinone and hydroquinone to a acid solution, under test, taken in a beaker. An en inert Pt electrode is dipped into the ees solution for making electrical Quinhydrone Electrode contact. The electrode is represented as Haq); Q.; QH2/Pt. It will either act as anode or cathode depending on the other electrode to which it is connected.B.E II Sem (AICTE Model Curriculum) Chemistry notes (Group -A: ECE, IT, Mech, AE) (2019-20) If it acts as cathode, then the electrode reaction is, cy we The electrode potential is calculated by using Nernst equation, 0.0591 {Ha} Eque = Egue -~ “log ‘ane = Eque ~ 3109 gee 201 Jog (H*}? (Since [AH =[0] =1) Foue = EQue + Eque = Ene + 0.0591log[H*] Eoue = ESne — 0.0591pH Egue = 0.699V —0.0591pH (On Hydrogen Scale E9¢ = 0.699V) Potential of Quinhydrone electrode depends on pH of the solution with which it is in contact. Therefore, Quinhydrone electrode can also be used to measure the pH of solution. ‘Advantages: The electrode setup is very easy, pH values obtained are accurate, small quantities of solution are sufficient for the measurement. Disadvantages: It cannot be used in the solutions that would react with quinone or hydroquinone. Since it is a weak acid, cannot be used above pH 8.5 at which the dissociation of Quinhydrone becomes appreciable. It is oxidized by air in strongly alkaline medium: (5) lon selective electrode: lon-selective electrode possesses the ability to respond only to certain specific ions, thereby developing a potential with respect to that specific ions in a solution and ignoring the other ions totally. in other words, the potential developed by an ion selective electrode depends only on the concentration of ions of interest. Eg; Glass electrode Glass electrode is made up of a special type of glass having low melting point and high electricalB.E Il Sem (AICTE Model Curriculum) Chemistry notes (Group -A: ECE, IT, Mech, AE) (2019-20) conductance. The bottom of the glass electrode is blown in the form a bulb, which is filled with a 0.1 N HCI solution to provide constant hydrogen ion pao concentration. A silver wire coated with AgCl is inserted into the bulb for making electrical contact. HeI(o.aNy Glass electrode The representation of glass electrode is, Ag/AgCI/0.1N HCV/Glass membrane. The potential of the glass electrode is given as, Ez = E? — 0.0591pH Determination of pH of a solution using quinhydrone electrode: The electrode potential of Quinhydrone electrode, which is reversible to H* ions, depends on pH of a solution; therefore it is used to determine pH of a solution. To determine pH of a solution, quinhydrone electrode is combined with a reference electrode like calomel electrode. The cell consists of Quinhydrone and Calomel electrode is represented as, Pt, He/ Hg2Cl2,Cl(Sat ,aq) // H* (sq),Q, QHz/Pt. Feat = Fque — Esce E, 0.699V— 0.0591 pH —.2420 Econ = 0.457 — 0.0591pH 1p 9887 = Boon pus G05oT Problems Based on Applications of Nernst Equation: 1. Consider the cell , 2n/2n*?(aq) //Cu’*{aq) /Cu .The standard electrode potentials are; Cur? +2e° ~ 2° = 0.35V Zn*42e" >in, £9 = -0.763V (i) Write down the cell reaction (ii) Calculate the EMF of the cell.B.E II Sem (AICTE Model Curriculum) Chemistry notes (Group -A: ECE, IT, Mech, AE) (2019-20) Solution: (i) Reduction potential of Zn is less than Cu, hence Zn acts anode and Cu acts as cathode. At anode Zn~ AtCathode Cu"? +2e “>Zn'242e (Oxidation) >cu (Reduction) Zn #Cu"? > Cu + Zn"? (i) Eben = Eut2jcu~ Eant2/an = 0.350 ~ (-0.763V) 1113 2. Calculate the electrode potential at a copper electrode dipped in a 0.1M solution of copper sulphate at 25°C.The standard electrode potential of Cu*?/Cu system is 0.34V at 298K. Ans: 0.31045 Volts 3. Ege of a given cell, Zn(s) /Zn" 1M(aq) //Cu"? 1M (aq) /Cu(s) , is 1.10 V at 25°C Calculate equilibrium constant for the cell reaction, Zn(s) +Cu%aq)=> Cu(s) + Zn*(aq). Ans : 1.67 x10 4. Azinc rod is placed in a 0.1M solution of ZnSO, at 25°C.Calculate the potential of the is temperature, assuming 96% dissociation of ZnSOs and E9,,+2 len Ans: Ezqt2), = —0.79V. lan 5. The emf of a cell corresponding to the reaction, Zn + 2H’ > Zn’? +He (g) 1 atm is 0.28V at 25°C. Write the half cell reactions and calculate the pH of the solution at hydrogen electrode. (Eons =-0.76V Egy =0V) len na Ans : pH= 8.6218 Batteries Battery: Battery is a device con: ing of one or more electrochemical cells connected parallelly or in series that converts stored chemical energy into electrical energy.B.E II Sem (AICTE Model Curriculum) Chemistry notes (Group -A: ECE, IT, Mech, AE) (2019-20) What are primary and secondary batteries? Primary batteries Secondary batteries (Rechargeable batteries) Batteries which are not rechargeable | The batteries which can be recharged are after their use are called primary | called Secondary batteries. batteries The chemical reactions that take place |The chemical reaction that take place are are not reversible reversible Eg: Zinc - Carbon battery Eg: Lead-Acid battery, Lithium ion battery. Explain construction, working, advantages and disadvantages of Zinc-Carbon battery. Zinc = Carbon Battery (Dry Cell) It is primary battery. Anode (Negative electrode): Zn Container Cathode (Positive Electrode): Carbon rod/MnO2 i Electrolyte: A moist mixture of NH.Cl, ZnCl2 Moist mixture of NHsCI & ZaCk} | Cardb card case fine -Carbon battery is a battery packaged in a (om ides cai zinc container that also serves as a negative ‘ikmossy ire" electrode. The positive electrode is carbon rod surrounded by a mixture of manganese dioxide and carbon powder. The electrolyte used is a moist paste of ammonium chloride and zinc chloride. Working ‘At Negative Electrode (Anode): Zn(s) At Positive Electrode (Cathode) : 2MnO,(s) + 2H0 (I) + 2e > Zn®*(aq) + 2e (Oxidation) -> 2MnO(OH) (s) + 20H (aq) (Reduction) In addition to main reactions, some secondary reactions also take place within the cell. 2NHs* (aq) + 20H (aq) —————-—-> 2NHs(g) + 2H20 (I) Zn? + 2NHa(g) + 2 Cl: -------------> [Zn(NHs)2] Ch(aq) Overall cell reaction: Zn(s) + 2MnO2(s) +2NH«CI (aq) --> 2MnO(OH) (s) + [Zn(NHs)2]Cl2 (aq)B.E II Sem (AICTE Model Curriculum) Chemistry notes (Group -A: ECE, IT, Mech, AE) (2019-20) Voltage of the cell : 1.6 Volt. ‘Applications Dry cells are used in flashlights, transistor radios, calculators etc. ‘Advantages Cost of this battery is quite low, Portable. dvantages Batteries are not rechargeable, short shelf life. Explain the construction, Working, advantages and disadvantages of Lead-Acid battery. Lead -Acid battery The lead-acid battery was invented in 1859 by French physicist Gaston Planté. tt is the oldest rechargeable battery. Construction Negative electrode: Spongy Lead (Pb) Positive electrode: Lead plate coated with PbO2 Electrolyte: 30 % H:S0, solution. It consists of a group of Lead plates coated with spongy Lead, which acts as anode and alternating with a group of lead plates coated with PbO: acts as cathode. These two are separated by insulating material like thin wooden or It is a secondary battery. fibre glass sheets. These plates are immersed in a solution of about 30% H,S0x, Eectoite ‘The cell is represented as, Pb(s) , PbSOs(s) / H:50s (aq) (30%) / PbSO«{s) ,PbO2(s) , Pb(s) Working During Discharging During Charging During discharging, Lead-Acid battery acts as| During charging, Lead-Acid battery acts as electrochemical cell (Voltaic cell). electrolytic cell. ‘At Negative Electrode (Anode): ‘At Negative Electrode (Cathode): Pb(s) -> Pb®* + 2e PbSO4(s)----—----> Pb + SO. Pb? + S02 —-> PbSOs (Precipitate) Pb? + 2e > Pb(s) Pb(s) + SO," —------> PbSOx(s) + 2€ PbSO.+2e Pb(s) + SOB.E Il Sem (AICTE Model Curriculum) Chemistry notes (Group -A: ECE, IT, Mech, AE) (2019-20) ‘At Positive Electrode (Cathode): ‘At Positive Electrode (Anode): PbO;(s) + 4H" + 2e° ---—---> Pb?" + 2H,0(I) PbSO,(s) ------> Pb?* + SO,” Pb? + SO,?-——---> PbSOs (Precipitate) Pb? + 24,0 —--—-> PbO2(s) + 4H" + 2e PbOs(s)* 4H" + 250. + 2e———> PbSO«(5) +2H:0(I) | PLSO«(s) +2H:0{I) ——> PbOs(s) + 4H’ + 2500 + 2e Net cell reaction: Pb + PbO, + 2H,S0, é 2PbSO, + 2H,0 Charging During discharging H2SOs is consumed and its concentration decreases. During charging HySOs is regenerated and its original concentration is restored. The variation of concentration of the acid and hence the extent of discharge or charge of the cell can be easily monitored by changes in specific gravity of the acid. During charging, Specific gravity of HSOs increases whereas during discharge specific gravity decreases. Voltage of each cell is 2V. In general, lead-Acid battery consists of such 6 cells which are connected in series to get higher voltage(12V) ‘Applications: Lead acid -batteries are used in telecommunication, power systems, radio, and television systems, solar, UPS, electric vehicles, automobile, emergency lights. ‘Advantages Low maintenance, Low Cost, Disadvantages Heavy in weight, Lead is not environmentally friendly. Explain the construction and working of lithium ion battery. Lithium — ton Battery (LIB) Lithium ion battery is a secondary battery. Lithium ion batteries are rechargeable batteries. Construction The primary functional components of a Li-ion battery are, 7 @ + Anode (-ve): Porous Graphite ischarge Cathode (+ve): Lithium metal oxide (Lir.CoO2) lecupivte xCg+ LiCo0, The electrode reactions that take place during discharging and charging can be summarised as, Discharge ~ x! jan CoO2 ETE LICe +t «CoO EE xCo+ LICOO? The cobalt electrode reaction is only reversible for x < 0.5 Voltage: 3.7 V Depending on the material choices the voltage, capacity, life and safety of a Li-ion battery can changes. ‘Advantages: Light weight, no self-discharge, compact Disadvantages: Over charging may lead to overheating and battery may explode. Over charge and discharge makes this battery irreversible. ‘Applications: 1. As mobile phone batteries, laptop batteries. 2. Asa battery in electric cars. What are fuel cells or Flow batteries? Fuel cells (Flow batteries): Fuel cell is an Electrochemical cell consisting of two electrodes and an electrolyte which converts chemical energy (Free energy) of a fuel and oxidant directly into electrical energy. Fuel cells can supply current if the reactants are supplied.B.E II Sem (AICTE Model Curriculum) Chemistry notes (Group -A: ECE, IT, Mech, AE) (2019-20) Methanol -Oxygen fuel cell Construction; boa cathodic compartments and electrolyte compartment. Usually the electrodes are made up of platinum since they are inert. Methanol and water is fed into anodic compartment where CH;OH undergoes oxidation. Oxygen is fed into cathodic compartment where it undergoes reduction. These two are separated by a proton exchange membrane. The protons generated during oxidation pass through the proton exchange The methanol oxygen fuel membrane and reaches to cathodic compartment and cell consists of anodic, combines with 2 to form = 20 Working: The electrode reactions that take place are, At anode: CH3OH (I) + H20(1) > CO2 «+ 6H* + 6e At cathode: 3/2 O2 «) + 6H’ + 6e' > 3 H20 (I) The overalll reaction: CH3OH (I) +3/2 O2@> 2 H20(I) + COr) What are the advantages and applications of fuel cells? Advantages: 1. Fuel cells have a higher efficiency than diesel or gas engines. 2. Most fuel cells operate silently, compared to internal combustion engines. They are therefore ideally suited for use within buildings such as hospitals. 3. Fuel cells can eliminate pollution caused by burning fossil fuels; for hydrogen fuelled fuel cells, the only by-product at point of use is water. 4, Noise and thermal pollution is low. Applications: 1. Portable electronic applications such as batteries in laptops, smart phones 2. Stationary fuel cells are used for commercial, industrial and residential primary and backup power generation. 3. Transportation: Fuel cells are used in Automobiles, in military applications, Space vehicles applications