N\ 4 3. ELECTROCHEMISTRY 5 \\ ELECTROCHEMISTRY > Electrochemistry is the 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. > Electrochemistry is the branch of chemistry which deals with the relationship between chemical energy and electrical energy IMPORTANCE OF ELECTROCHEMISTRY . > A large number of metals like Na, Mg. Ca and Al, sodium hydroxide, chlorine, fluorine ond many other ‘chemicals are produced by electrochemical methods. > Batteries and fuel cells convert chemical energy into electrical energy and aré used on @ large scale in various instruments and devices. > The reactions carried out electrachemically can be energy efficient and less polluting. > The transmission of sensory signals through cells to brain and vice versa and communication between the cells are known to have electrochemical or ELECTROCHEMICAL CELLS > An electrochemical cell is a device that consists of two metallic electrodes dipped in electrolytic: solutions which convert chemical energy into electrical energy > By suitable arrangement, the chemical energy produced in.a redox reaction can be-converted into electrical energy. The arrangement is called electrochemical cell or galvanic céll or voltaic cel €l. ELECTROLYSIS > Electrolysis is the production of a chemical reaction by passing an electric current through an electrolyte. > In electrolysis positive ions migrate to the cathode and negative ions to the anode. REDOX REACTIONS > A redox reaction is a reaction in which one substance loses electrons, i.e., undergoes oxidation ‘whereas another substance gain electrons, i.e. undergoes reduction. Example: Zn(s) + CuSO,(aq) ~—- > ZnSO, (aq) + Cu(s) > Zn has been oxidised to Zn” whereas Cu’* ions have been reduced to Cu. These reactions are accompanied by release of energy called chemical energy GALVANIC CELLS > A galvanic cell is an electrochemical cell that converts the chemical energy of a spontaneous redox reaction into electrical energy. > In this device the Gibbs energy of the spontaneous redox reaction is converted into electrical work which may be used for running a motor or other electrical gadget like heater, fan, geyser, etc. ‘SALT BRIDGE > The salt bridge allows the movement of ions from one solution to the other without mixing of the two solutions. > Ithelpsto maintain the electrical neutrality of the solutionsin the two half celts. > One type of salt bridge consists of a U-shaped glass tube filled with a relatively inert electrolyte. } tis usually 3 combination of potassium or ammonium ions and chloride or nitrate ions, which have similar mobility in solution. . Scanned with CamScannerea] cell converts the chemical energy liberated during the redox reaction f Zn(s) + Cu™(aq) > 2n®(aq) + Cu(s) to electrical energy and has an electrical potential equal to tay | when concentration ofZn® and Cu ions is unity ( 1 mol dm™). Such a device is called a galvanic ora cell, > panel cell havingelectrodes of zinc and copper dippingin the solutions of theirrespective salts, > Ifanexternal opposite potential is applied and increased slowly, the reaction continues to take place till the opposing voltage reaches the value 1.1 V when, the reaction stops altogether and no current flows through the cell. ection fw Eqs I1V > fae ae bsctie Current [eathode 2n. salt Cu “ve brid lave (a) When Exy <1.1V Y Electrons flow from zinc rod to Cu rod hence current flows from Cu to Zn Y Zndissolves at anode and copper deposits at cathode (6) When Exe =1.1V ¥ No flow of Electrons or current Y No chemical reactions. (c) When Eee > 1.1V Y. Electrons flow from Cu rod to zinc rod hence current flows from Zn to Cu Y Zincis deposited at the zinc electrode and copper dissolves at copper electrode > Any further increase in the external potential again starts the reaction but in the opposite direction. » It now functions as an electrolytic cell, a device for using electrical energy to carry non-spontaneous chemical reactions. > In Daniell cell in which the following redox reaction occurs. Za(s) + Cu(aq) > Zn” (aq) + Cus) > This reaction is a combination of two half reactions whose addition gives the overall cell reaction: Scanned with CamScanner{a) Cu’ +2e" > Cu(s) (reduction half reaction) {b) Zn{s) > Zn” + 2e" (oxidation half reaction) ‘These reactions occur in two different portions of the Daniell cell. The reduction half reaction occurs on the copper electrode while the oxidation half reaction occurs on the zine electrode. These two portions of the cell are also called half-cells or redox couples. > The copper electrode may be called the reduction half-cell and the zinc electrode, the oxidation half- cell, > innumerable number of galvaniccells can be constructed by taking combinations of different half-cells. Each half cell consists of a metallic electrode dipped into an electrolyte. The two half-cells are connected by a metallicwire through a voltmeter and a switch externally. The electrolytes of the two half-cells are connected internally through a salt bridge. > Sometimes, both the electrodes dip in the same electrolyte solution andin such cases salt bridges are not required. > Ateach electrode-electrolyteinterface there is a tendency of metal ions from the solution to deposit ‘on the metal electrode trying to make it positively charged. > At the same time, metal atoms of the electrode have a tendency to go into the solution as ions and leave behind the electrons at the electrode trying to make it negatively charged. vy At equilibrium, there isa separation of charges and depending on the tendencies of the two opposing reactions, the electrode may be positively or negatively charged with respect to the solution. FEATURES OF AN ELECTROCHEMICAL CELL {a) The zinc rod at which oxidation occurs is called anode while the copper rod at which the reduction takes place is called the cathode {b) The overall reaction taking place in an electrochemical cell is due to two half reaction one occuring in each beaker. Each beaker constitutes a half cell also called the electrode. Thus a half cell or an electrode consists of a metal rod dipped in the solution of its own ions. (©) The reaction taking place in a half cel is called a half cell reaction. (d) The half-cell reaction occurring at anode is called oxidation half-cell reaction while that occurringat the cathode is called reduction half-cell reaction. {e) The two half reaction always take place simultaneously, Le. half-cell reactions cannot take place independently. (f) Ina galvaniccell anode has a negative potential with respectto the solution and cathode has positive potential with respective to the solution. (@) Electrons flow from negative electrodeto positive electrode. The direction of current flow is opposite to that of electron flow. ELECTRODE POTENTIAL > The tendency of an electrode to lose or gain electrons is called electrode potential. Since each electrode represents a half cell, therefore, electrode potential is called potential for half-cell. STANDARD 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. > According to IUPAC convention, standard reduction potentials are now called standard electrode potentials. CELL POTENTIAL > The potential difference between the two electrodes of a galvanic cell is called the cell potential and is ‘measured in volts. [OR] The cell potential is the difference between the electrode potential of cathode ‘and anode. Scanned with CamScannerREPRESENTATION OF GALVANIC CELL > A galvanic cel is an electrochemical cell that converts the chemical energy of a spontaneous redox reaction into electrical energy. \n this device the Gibbs energy of the spontaneous redox reaction is converted into electrical work which may be used for running motor or other electrical gadgets like heater, fan, geyser, etc. > 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 other half-cell in which reduction takes place is called cathode and it has a positive potential with respect to the solution. > Thus, there exists potential difference between the two electrodes and as soon as the switch is in the ‘on position the electrons flow from negative electrode to positive electrode. > The direction of current flow is opposite to that of electron flow. > The potential difference between the two electrodes of a galvanic cell is called the cell potential and is measured in volts. > Agalvanic cell is generally represented by, putting a vertical line between metal and electrolyte solution and putting a double vertical line between the two electrolytes connected by a salt bridge. Under this convention the emf of the cell is positive and is given by the potential of the half-cell on the right hand side minus the potential Of the half-cell on the left hand side i.e., Econ = Eright— Eee « EME OF A GALVANIC CELL > Whenever current flow through two points, a potential difference is said exist between the electrodes, The potential difference generated by a cell when the circuit draws no current under conditions of zero electron flow is called the cell electromotive force (emf) CELL REACTION Cu(s) + 2Ag"(aq) ---- > Cu(aq) + 2 Ag(s) Half-cell reactions ¥ Cathode (reduction): 2Ag'(aq) + 2e"-> 2Ag(s) ¥. Anode (oxidation): Cu(s) > Cu” (aq) + 2e" ¥ The sum of the above reaction leads to overall reaction. Silver electrode acts as a cathode and = copper electrode acts as an anode. Y The cell can be represented as: ‘Cu(s)| Cu**(aq)| | Ag"(aq) | Ag(s) and agilng— Ecuzsleu Y The potential of individual half-cell cannot be measured. MEASUREMENT OF ELECTRODE POTENTIAI > The potential of individual half-cell cannot be measured. Only the difference between the two half-cell potentials that gives the emf of the cell can be measured. > If we at ‘arily choose the potential of one electrode (half- cell) then, that of the other can be determined with respect to this. > According to convention, a half-cell called standard hydrogen electrode represented by Pt(s) ell H+(aq), is assigned a zero potential at all temperatures corresponding to the reaction W(aq)+e —>2HAle) Scanned with CamScannersvar ARI IN ELECTRODE Itis used as reference electrode. Its electrode potential is taken as 0,000 volt The standard hydrogen electrode consists of a platinum electrode coated with platinum black. The electrode is dipped in an acidic solution and pure hydrogen gas is bubbled through it. The concentration of both the reduced and oxidised forms of hydrogen is maintained at unity. This implies that the pressure of hydrogen gas is one bar and the concentration of hydrogen ion in the solution is one molar. ‘At 298 K the emf of the cell, standard hydrogen electrode | | second half-cell constructed by taking standard hydrogen electrode as anode (reference half-cell] and the other half-cell as cathode, gives the reduction potential of the other half-cell. If the concentrations of the oxidised and the reduced forms of the species in the right hand half-celll are unity, then the cell potential is equal to standard electrode potential, E°, of the given half-cell. Eom Em - EY ‘As E° for standard hydrogen electrode is zero P= E%-0 = Ee The measured emf of the cell: Pt(s) | H2(g, 2 bar) | H* (aq, 1M) || Cu* (aq, 1M) | Cu is0.34 Vani electrode potential of the half-cell corresponding to the reaction: Cu” (aq, 1M) + 2e” —> Cu(s) Similarly, the measured emf of the cell: Pt(s) | Hz (g 1 bar) | H* (aq, 1M) |] Zn* (aq, 1M) | Zn is -0.76 V correspon electrode potential of the half-cell reaction: Zn® (aq, 1 M) + 2e° — > Zn(s) The positive value of the standard electrode potential in the first case indicates that Cu" ions get reduced more easily than H’ ions. The reverse process cannot occur, thatis, hydrogenions cannot oxidise Cu (or alternatively, hydrogen gas can reduce copper ion) under the standard conditions. Thus, Cu does not dissolve in HCl. In nitricacid it is oxidised by nitrate ion and not by hydrogen ion. The negative value of the standard electrode potential in the second case indicates that hydrogen ions can oxidise zinc (or zinc can reduce. hydrogen ions). | 99220%00%s0 1g to the standard In view of this convention, the half reaction for the Daniell cell can be written Left electrode: Zn(s) —~- > Zn”* (aq, 1M) + 2e™ Right electrode: Cu”*(aq, 1M) +2” ~--> Culs) The overall reaction of the cell is the sum of the above two reactions and obtain the equation as: Zn(s) + Cu’* (aq) — > Zn** (aq) + Culs) Emf of the cell = E°en= E%y— E%, = 0.34V - (- 0.76) V= 1.10 Sometimes metals like platinum or gold are used as inert electrodes. They do not participate in the reaction but provide their surface for oxidation or reduction reactions and for the conduction of electrons. Example: Pt is used in the following half-cells: Hydrogen electrode: Pt(s) | H(e)|H'(aq) With half-cell reaction: H’ (aq) +e” —- > % Ho (g) Bromine electrode: Pt(s)| Br, (aq)|Br'(aq) With half-cell reaction: % Bra(aq) + &* > Braq) Scanned with CamScannerof ‘SOME IMPORTANT POINTS ON STANDARD ELECTRODE POTENTIALS, > If thestandard electrode potential of an electrode is greater than zero then its reduced form is more stable compared to hydrogen gas, > Mf thestandard electrode potential is negative then hydrogen gasis more stable than the reduced form of the species. > ‘Standard electrode potential for fluorine is the highest indicating that fluorine gas (F;) 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. > 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. > The standard electrode potential decreases with this, decreases the oxidising power of the species on the left and increases the reducing power of the species on the right hand side of the reaction. (Ref Table} > Electrochemical cells are extensively used for determining the pH of solutions, solubility product, ‘equilibrium constant and other thermodynamic properties and Tor potentiometric titrations.- DIFFERENCE BETWEEN DANIEL CELL AND GALVANIC C1 cn electrochemical cell that derives electrical energy from the spontaneous redox reaction Zn(s) + Cu’(aq) > Zn**(aq) + Cu(s) taking place within the cell that consists of two specific metal electrodes, copper and zinc, immersed in a solution of copper(l) sulfate and zinc sulfate, ‘respectively, and connected by a salt bridge. > A galvanic cell is an electrochemical cell that derives electrical energy from spontaneous redox reactions toking place within the cell. it generally consists of two different metals immersed in electrolytes or of individual half-cells with different metals and their ions in solution connected by a salt bridge. > Daniel cell is primarily a Galvanic cell but all the galvanic cells are not Daniel cell ELECTROLYTIC CELL An electrolytic cell can be defined as an electrochemical device that uses electrical energy to facilitate a non- spontaneous redox reaction, > Electrolyticcells are electrochemical cells that can be used for the electrolysis of certain compounds. Example: Water can be subjected to electrolysis (with the help of an electrolytic cell) to form gaseous oxygen and gaseous hydrogen. This is done by using the flow of electrons (into the reaction environment) to overcome the activation energy barrier of the non-spontaneous redox reaction. > The three primary components of electrolytic cells are ¥, Cathode (which is negatively charged for electrolytic cells) Y Anode (which is positively charged for electrolytic cells) Y Electrolyte » The electrolyte provides the medium for the exchange of electrons between the cathode and the anode. Commonly used electrolytesin electrolytic cells include water (containing dissolved ions) and molten sodium chloride. > Molten sodium chloride (NaCl) can be subjected to electrolysis with the help of an electrolytic cell. > Two inert electrodes are dipped into molten sodium chloride (which contains dissociated Na° cations and CI" anions). Scanned with CamScanner> When an electric current is passed into the circuit, the cathode becomes rich in electrons and develops 2 negative charge. The positively charged sodium cations are now attracted towards the negatively ‘charged cathode. This results in the formation of metallic sodium at the cathode. > Simultaneously, the chlorine atoms are attracted to the positively charged cathode. This results in the formation of chlorine gas (Cl,) at the anode {which is accompanied by the liberation of 2 electrons, finishing the circuit), The associated chemical equations and the overall cell reaction are provided below. Reaction at Cathode: Na’ + €" — > Na Reaction at Anode: 2CI”—> Cl, +2e Cell Reaction: 2NaCl — > 2Na + cr > Thus, molten sodium chloride can be subjected to electrolysis in an electrolytic cell to generate metallic sodium and chlorine gas as the products. APPLICATIONS OF ELECTROLYTIC CELLS > The primary application of electrolytic cells is for the production of oxygen gas and hydrogen gas from water. > They are also used for the extraction of aluminium from bauxite. > Another notable application of electrolytic cells is in electroplating which is the process of forming a thin protective layer of a specific metal on the surface of another metal. > The electro-refining of many non-ferrous metals is done with the help of electrolytic cells. Such electrochemical cells are also used in electro-winning processes. ~ > The industrial production of high-purity copper, high-purity zinc, and high-purity aluminium is almost always done through electrolytic cells. DIFFERENCE OF ELECTROCHEMICAL CELL AND ELECTROLYTIC CELL ‘S.No | ELECTROCHEMICAL CELL (GALVANIC OR ELECTROLYTIC CELL VOLTAIC CELL) 7. [An electrochemical cell converts chemical energy | An electrolytic cellis 0 cell in which electrical energy is into electrical energy ‘converted into chemical energy Electrical energy brings out chemical reaction with the help of an external force B._| A cathode is negative and an anode is positive Chemical energy generates electrical energy with the help of redox reaction ‘A cathode is positive ond an anode is negative “4. | Oxidation takes place at cathode and reduction at the anode. i.e,, based on redox reactions, which is spontaneous. AG =-ve Oxidation takes place at anode and reduction at the cathode. ie., Redox reaction is non-spontoneous and takes place only when electrical energy is supplied. AG= +e %s, | Both the anode and cathode are in different containers known os a half cell which are connected by a salt bridge ‘Both the anode and cathode are in the same container with an electrolytic solution. Salt bridge not used 6._| Used in purifying copper and electroplating Used in batteries for example, batteries in TV remotes > The galvanic cell does not continue working indefinitely and stops working after sometime. > Indeed as the cell reaction progresses, there isa fall inthe concentration of cations around cathode due to reduction and at the same time there is an increase in the concentration of metal cations around anode due to oxidation. As a result electrode potential of cathode decreases and that of anode increases with the passage of time and in the end stage reaches when the potential difference becomes zero and the flow of electrons stops. > Standard electrode potential is measured under standard conditions i.e., electrolyte concentration is 1 Mand temperature is 298 K Scanned with CamScanner