ELECTRO CHEMISTRY Introduction: Electrochemistry is a branch of chemistry which deals with the inter relationship between electrical and chemical energy. It is the study of process involving the transformation of electrical energy into chemical energy and chemical energy into electrical energy. Electrical conductors: substances which allow electrical current to pass through them are known as electrical conductors. It is denoted by *C°. Insulators: substances which do not allow electrical current to pass through them are known as insulators. Current: © "Its the flow of charged particles like electrons, protons and ions. © The strength is denoted by the charge transferred in unit time. ime I =current. I= Qt where Q= charge, t Resistance: the tendency of a material to stop the flow of current is known as resistance. It is denoted by ‘R’. R=VA Conductance: it is the tendency of a material to allow the flow of current which is denoted bye. C=UR It depends on mobility of the ions and number of ions present in the electrolytic solution, Electrode: jt is a material or a metallic rod / bar / strip which conduct electrons. Electrolyte: it is a water soluble substance forming ions in solution and conduct an electric current. Electrode poten » When a metal rod is dipped in its salt solution (electrolyte), the metal atom tends to lose ¢lectrons (oxidation) or to accept electrons (reduction). the process of oxidation or reduction depends on the nature of metal, > Inthis process there develops a potential between the metal atom and its corresponding ion called the electrode potential.” Oxidation: M > M™ ne Reduction: M"'+ne——> The value of electrode potential depends upon Scanned with CamScanner© Nature of the metal © Temperature. © Concentration of the electrolyte led the oxidation potential and tendency I The tendency of an electrode to lose electrons is c: of an electrode to gain electrons is called the reduction po Standard electrode potential: The potential of electrode at 25°C with 1M concentration of electrolyte is called Standard electrode potential (E°), Or Itis the measure of tendency of a metallic electrode to loose or gain electrons, when itis in contact with a solution of its own salt solution of IM concentration at 25°C. Units: volts (V) Electro chemical cell: v It is a device used for converting chemical energy into electrical energy > The EMF of such a cell is directly proportional to the intensity of chemical reactions taking place in it, Eg: Daniel cell. > Daniel cell is the typical example of the electrochemical cell. v The electrode where oxidation occurs is called “anode” while the electrode where reduction occurs is called cathode. Voltmeter Ar Anode sal 1° catnose, (Onidation) i Dricios (Reduction) Ker ZnSO4 Cuso, Zm(a) + 26° —+ Zn? cut + 20+ Cuts Zn(s) | ZnSO4(aq)|| CuSO4(aq) | Cucs) > The galvanic cell is made up of 2 half cells: Scanned with CamScanner1. Oxidation or anodic cell. 2. Reduction or cathodic cell. It is having Zn and Cu electrodes. The first half cell consists of Zn electrode dipped in ZnSO4 solution and second half cell containing Cu electrode dipped in CuSO4 solution. Both half cells connected externally by metallic conductor and internally bent glass tube Having saturated solution of K2S04 called salt bridge. It acts as a bridge for two half cells. Cell notation: ‘Some rules to be taken care while representing an electrochemical cell. > > Cell reactic Cathode is on the right side and anode is on the left side. The cell is represented by the rule that metals are written first and then the metal ions that are present in the electrolyte. These two need to be separated by a verticalline ive. Zn/Zn", ‘The molar concentration is written within the brackets as Zr/Zn"? (M). Daniel cell is represented by Zn/Zn"(My/Cu*(M)/Cu The cell anode and cathode (half-cells) are separated by two bars (or) slashes which Representing a salt bridge. At anode oxidation reaction takes place. Zn » Zn'*+2e° (oxidation) At cathode reduction reaction takes place. Cu‘?+2e° —————> Cu (reduction) ‘Net reaction: Zn ——» Zn? 420 Cu?+2e° ———» Cu “ZntCu? 5 Zn? +Cu Scanned with CamScanner+h has a stable and well known I, to determine the potential of the of other electrode. Reference electrode: A reference electrode is an electrode whic! potential. I is used as half cell to construct an electrochemical cel ther electrode. It ean act both as an anode or cathode depending upon the nature ‘The Reference electrodes can be classified into two typ: 1) Primary reference electrodes Ex: Standard Hydrogen Electrode Il) Secondary reference electrodes Ex: Standard Calomel Electrode ‘Types of electrodes: Standard Calomel Electrode: (SCE): Itis secondary standard electrode and consists of a glass tube having a side tube on each side. The mercury of high purity is placed at the bottom of the glass tube. The surface of mercury is covered with a paste of Hg2Cl; and mercury in KCI solution. The platinum wire sealed in a glass tube which connected to the circuit. ‘The electrolyte is a solution of KCI vvvyvvy The electrode is connected with the help of a left side tube through a salt bridge with the other electrode. v The potential of calomel electrode depends upon the concentration of the KCI solution. > The cell is represented as: Hg.HgsCh/KCI (ai snc PL. wire To salt bridge Saturated 7 KCI solution Hg,Cl, and Hg paste Mercury Fig. 12.15 Calomel electrode Scanned with CamScanner‘The calomel clectrode can act as anode or cathode depending on the nature of other electrode of the cell. ‘When it acts as anode, the electrode reaction is 2 Hg(l) > Hen + 2e° He:"* + 2Cl > HgsClo 2Hg + 2Cl > Hg2Ch + 2¢° (Oxidation reaction) When it acts as cathode, the electrode reaction is, Hey" + 2e— 2 Hg HgxCh, > He: + 2cr HgxCls + 2c’ 2Hg (1) + 2CI’ (Reduction reaction) tee ee eee ees The net reversible electrode reaction is, Hg2Cla(s) + 2e"<===> 2 He (I) + 2Cl° Electrode potential is given by E=E®- 2.303 RT/2F log [Cl]* ‘The reduction potential for the various KCI concentrations at 25°C are: © For saturated KCI solution electrode potential is “0.2415V". © For IN KCI standard reduction potential is “0.28V™. @ For 0.1 KCI standard reduction potential is “0.3338V". Scanned with CamScannerQuinhydrone electrode: ° OH a y e2ne2e = (B= + 0.699 s o OH Quinhydrone hydroquinone Q+2H'42e <—— & ‘The potential E developed when a platinum electrode is immersed in this system is given by the Nernst equation. E=E°- 2.303RT_log [QH2] ——> () nF (HT {Q)= [QH:] From equation (1) E=E?- 2303RT_ log _{Q] nF (ony 2) n=2e", R=8.303J, T=298K at25°C, F=96500C Substitute above values in equation (2) «cape y y2:303 x 8.303 x 298 SuESE?42 * 2x96500 el] E=E°40.0591 log [1] [E=E°-0.0591P" Since the electrode potential of the quinhydrone electrode depends upon the concentration of hydrogen ions, it can be used for the determination of P* value. ‘The standard oxidation potential of quinhydrone electrode at 25°C is 0.6994V. Scanned with CamScannery Construction of electrode: Add a pinch of quinhydrone to the solution under examination and immersed a c jean platinum a 7 7 no i +t examination and i Jean plati Advantages of quinhydrone electrode with limitations. © The electrode is very easy to setup. © The ph value obtained is very accurate. © Very small quantity of the solutions is sufficient for the measurement. Standard electrode potential of quinhydrone electrode is E°g 0.6994V Eg = 0.6994V - 0.00591 VP" (from above equation) Determination of P" of a solution: To determine P" of a solution, quinhydrone electrode is connected to reference electrode like calomel electrode whose electrode potential is known.Quinhydrone electrode is known as indicator (or) working electrode. These two electrodes are connected through potentiometer and emfis determined, Cell notation: PUH gq Hg2Clays), KCl say//H" Q.QH2/Pt Cell reaction: 2 Hew t2Cl#Q* 2H") —————® HCl QH> + VEcat= Er- Et =Eg-Esce = (0.6994-0.0591P") - 0.2422 Nernst equatio1 Consider the following redox reaction Mine ———= M For such a redox reversible reaction, the free energy change (AG) and its equilibrium constant (K) are related as; AG =-RT Ink + RT In [product] [Reactant] = AG’ + RTln [product] —— Eq- (1) “(Reactant] Where, AG? = standard free energy change The above equation is known as Van’t Hoff Isotherm. Scanned with CamScannerThe decrease in free energy in the reversibl - AG = nEF and AG"=-nE°F Eq-2) Where, E = Electrode potential E? = Standard electrode potential F = Faraday (96,300 coulombs) Comparing equation 1 & 2 -nEF = -nE°F + RT In [M]_ [M"] °F +RTIn1_ IM") Where, concentration of the metal is unity i.e. [M] = 1 -nEF = -nE°F - RT In [M™] Dividing the equation by ‘~nF” E=E°+RT In[M™] nF E=E® +2.303RT log [M"’] oF E=E? +0.0591log [M"]_ —__—— Eq-(3) n This equation is known as “Nernst Equation” for electrode potential. Applications of Nernst Equation: One of the major applications of Nernst equation is in determining ion concentration. It is used in oxygen and the aquatic environment. Itis also used in solubility products and potentio-metric titrations. It is also used in pH measurements, Scanned with CamScannerBatteries: © A battery is an arrangement of 5 ? everal elec P asa source of direct electric eure et ochemical cells connected in series that ean be used @ Acell contains only one anode and one cathode, © A battery contains several anode and cathodes, © Battery is an electrochemical cell, which conv ‘mical energy into electrical energ) : 7 al s mverts chemic: y y Batteries are classified into two categories depending on their recharging capabilities. 1. Primary batteries Il. Secondary Batteries I. Primary batteries: In which the cell reaction is irreversible. Once the reactants are converted into products no_ more electricity is produced and the battery becomes dead so it must be discarded after use and it can’t be recharged and it cannot be used as storage device. Ex: Lithium cells Lithium cells: Lithium cells belong to primary cells. The cells having lithium anodes are called lithium cells, Lithium cells are two types a) Lithium cells with solid cathodes b) Lithium cells with liquid cathodes a) Lithium cells with solid cathode: ‘Anode: lithium Cathode: MnO2 Electrolyte: mixture of propylene carbonate and 1,2-dimethoxyethane. Cathode MnO; should be heated to >3000 C to remove water before incorporating it in cathode. Anodic reaction: Li ——___» Li*te’ (oxidation) Cathodic reaction: Li‘+e+MnO, ————-» LiMnO; (reduction) Net reaction: Li+Mn0, ———-—» LiMn0) Applications: Cylindrical cells are used in fully automatic cameras. Coin cells are widely used in electronic devices such as calculators and watches. Scanned with CamScanner») Lithium cells with liquid eathoa a le: In this first type cell ig Anode: li ithium: Cathode: $0.81 * SOpElectrolyte: Ei “olyte: Either acrylonitrile or Propylene carbonate or mixture of these {wo Net reaction: Li+ 280, > LiS:0, Second type cell is Anode: lithium Cathode: SOC], (thionyl chloride) Thionyl chloride acts as an electrolyte and an active cathode Net reaction: 4 Li +2 SOCh-—->_ 4 LiC1 +802 +8 Applications: ‘These cells are used for military and space applications ‘These cells are used in medical devices such as neuro-stimulators and drug delivery systems. Il. Secondary battery: The cells in which the cell reaction is reversed by passing direct current in opposite direction, These batteries have very large capacitance and long periods of low current rate discharge. They can be used as energy storage devices and can be recharged. Ex: Lead-acid cell, lithium ion cell Lead-acid battery: Construction: © The lead acid storage cell contains of lead anode and lead dioxide cathode. © A number of lead plates (- ve plates) are connected in parallel and a number of lead dioxide plates (+ve plates) are also connected in parallel. © The lead plates are fit in between the lead dioxide plates. © The plates are separated from adjacent plates by insulators like wood strips, rubber or glass fiber. © = The entire combination is immersed in 20 — 21 % dil.H2SOx, Scanned with CamScannerGlass vessel Working: Discharging: Discharging At anode: pb+SO% 9 POU HE Charging Discharging At Cathode: PbO2 + 4H"+SO3+20° ————_ PbSO,+ 2H:0 Charging pb+PbO)+4H'#2803, —————— 2PbSO. + 2H: O+E Scanned with CamScannerCharging: Charging Atanode: PbSO4+2e" Pb + SO? Discharging Charging AtCathode: — PbSO,+2H0 __ PbO; + 4H"+SC Discharging Net reaction: 2 PbSO, + 2H,0+F Pb + PbO: + 4H" 2S Applications of Lead-acid battery: > Lad acid battery is used for starting motors > Automobile and construction equipment > Used mainly for engine batteries > Standby / backup system. Lithium ion battery: > Alithium ion battery is a rechargeable portable battery in which lithium ions move from negative electrode to positive electrode {> The primary components of lithium ion battery are the negative electrode made from carbon (graphite), positive electrode made from a metal oxide like lithium cobalt oxide or lithium manganese oxide and the electrolyte is either non aqueous lithium hexa fluro phosphate (LiPF.) or lithium perchlorate (LiC1O.) Scanned with CamScannerCharging Atanode: — PbSOy#2e" — Pb+So? Discharging Charging AtCathode: PbSO,+2H,O = ——— — PbO + 4H*+SO7+2e° Discharging Net reaction: 2 PbSO;+2H,O+E = —— = Pb+ PbO, + 4H"+ 2807 Applications of Lead-acid battery: Lad acid battery is used for starting motors. Automobile and construction equipment. Used mainly for engine batteries. vvvyv Standby / backup system. Lithium ion battery: > A lithium ion battery is a rechargeable portable battery in which lithium ions move from. negative electrode to positive electrode. > The primary components of lithium ion battery are the negative electrode made from carbon (graphite), positive electrode made from a metal oxide like lithium cobalt oxide or lithium manganese oxide and the electrolyte is either non aqueous lithium hexa fluro phosphate (Li or lithium perchlorate (LiCIO,). phosphate (LiPF,) Scanned with CamScannerLithium-ion Battery: Powering a dev ice Working: Discharging: At anode: At cathode: Net reaction: Charging: Atanode: At cathode: ‘Net reaction: Electrolyte x Lic ——»5 xLity xe+ xc Limno, + cLie 1s nme, “LIC + Limno, ——_s xc + Lh pmet ez x Llity t+ XC —— 2 Lic ui sng @ 4 4 ~ Limno, + xu x x i . aul Leng t+ F—_» Linino, + XLic Scanned with CamScannerapplications: Lithium-ion batteries are used j c sed in Laptops, Table > Lithium metal batteries h plops, Tablets problem, Some safety disadvant, Fuel cell: Ina fuel cell electrical energy is obtai . al energy is obtained fro fuel that can be oxidized The essential process in a fuel cell ic rom oxygen and a fuel that can be oxidized Fuel + Oxygen ——___, Oxidation product +Electricity Methanol- oxygen fuel cell: y Itconsists of two electrodes made up of platinum in between the electrodes HSOs is placed as a electrolyte. > Methanol and H0 is supplied at the anode and pure oxygen gas is supplied at the cathode. In this H’ ions moved from anode to cathode. > The Methanol is oxidized to CO2& HO with the liberation of electrical energy. > The cell delivers an emf of 1.20v. ‘The cell reactions are as follows. At anode: CH;OH + HAO ———> COn + 6H" + 6 At cathode: 3/2 02 + 6H'+ 6° =§ ————> 3H,0 Net reaction: CH;OH +3/202 » CO: 42H,0 Scanned with CamScanner7 ‘Uses: Used in Military applications. Used for large scale power production station Electrical current —_3 — Carbon Water dioxide CO. CH,OH Methanol Air Water Cathode Anode Electrolyte Scanned with CamScanner