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Electrochemistry

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Electrochemistry ELECTROCHEMISTRY Electrochemistry mostly deals with two things. How electricity can be used to bring about a chemical reaction. This is one and the second is how can we get electricity by means of a chemical reaction. The processes are reverse of each other. In the first, electricity is used and in the second electricity is produced. These two processes are carried out in a special kind of vessel called cells. The first process, i.e use of electricity to carry out a chemical change is done in electrolytic cell and the second process, i.e use of chemical reaction to generate electricity is is done in electrochemical cell or Galvanic cell or Voltaic cell. The chemical process which is carried out in electrolytic cell is called electrolysis and electrochemical cells are commonly called batteries. A non-spontaneous reaction, which is otherwise not possible, is forcefully carried out in electrochemical cell. For example, when electric current is passed through a molten NaCl solution in an electrolytic cell, metallic sodium is obtained at cathode and Cl2 gas is obtained at anode. Without the use of electricity, this reaction could not have been possible. + - electrolysis 2 Na Cl 2 Na + Cl2 Similarly when electric current is passed through an aqueous solution of any electrolyte, say Na2SO4, we get hydrgen gas at cathode and oxygen gas at anode by the decomposition of water. electrical energy 2 H2O 2 H2 + O2 H2O cannot decompose of its own. It has become possible by supplying electrical energy. Hence during electrolysis, the electrical energy is converted to chemical energy. On the other hand, when we allow a lump of sodium metal to react with Cl2 gas, spontaneous reaction occurs to form NaCl. Na atom loses one electron to become Na+ while Cl atom accepts that electron to become Cl–. This the two ions are held together by ionic bond. This is a spontaneous reaction. Na → Na+ + e Cl + e → Cl– The transference of electron from Na atom to Cl atom takes place in the same vessel without giving any extra benefit to us. Only it produces some heat due to friction. In stead of carrying out this reaction in one container, if we keep the two reactants separate from each other and connect them by a conducting wire, the electron will spontaneously flow from Na to Cl2 through the conducting wire and thus electric current is now generated. We can harness this electricity in whichever way we like by putting any load in its path, like lighting a bulb, blowing a fan or putting any electric gadget. This is the principle of galvanic cell or a battery. A spontaneous reaction is used to generate electricity. To conclude, an electrochemical cell i.e a battery is used to bring about electrolysis in an electrolytic cell. We shall take up first the electrolysis and electrolytic cells. 1 ELECTROLYTIC CELLS AND THE PROCESS OF ELECTROLYSIS: . An electrolytic cell is used to carry out a chemical process by the help of electric current. A chemical compound is decomposed to neutral elements in this process which is called electrolysis. If you take a small battery in your house and connect two electric wires to the two terminals of the battery and put other ends of these wires in pure water (say distilled water), you will not find anything occurring. But when you add a pinch of common salt(NaCl) in that water, you will find that gas bubbles are coming out from the ends of the two electric wires dipped in the solution. On analysis you will find that one gas is H2 and the other gas is O2. In this process H2O is decomposed to its elements H2 and O2 by passing electric current through it. NaCl acts as an electrolyte which increases the conductivity of water. Water in its pure form is a bad conductor of electricity but when some electrolyte like NaCl, H2SO4 etc. is added, water not only conducts electricity but also decomposed to give H2 and O2 at the two ends of the wire dipped in solution, called electrodes. An electrolytic cell consists of the following components. (i) Electrolysis bath or tank: This is vessel in which electrolysis is carried out. Two electrodes called anode and cathode are dipped or suspended inside the bath. Electrodes are the good conductors of electricity usually made of metals. Sometimes a nonmetallic conductor such as graphite is used as electrode. (ii) Cathode: The electrode which is connected to the negative (-ve) end of the battery is called the cathode. This carries negative potential and is called the negative plate. (iii) Anode: The electrode which is connected to the positive (+ve) end of the battery is called the anode. This carries positive potential and is called the positive plate. (iv) Electrolyte: An electrolyte is taken inside the electrolytic bath either in the form of aqueous (water) solution or molten state (liquid state). For example, you can take NaCl solution in water or you can use molten NaCl. In the above diagram, molten NaCl has been shown as electrolyte. You know that electrolyte contains free positive and negative ions which conduct 2 electricity. Na+ migrates to cathode(the negative electrode) and Cl– migrates to anode(the positve electrolde) and get themselves discharged their as show before to form neutral sodium metal at cathode and chlorine gas at anode. The reactions have been given before. (v) Battery and electrical conducting wires: A d.c battery is used to supply electric current through conducting wires to the electrolytic cell and carry out the chemical decomposition of the substance present in the bath. ELECTROLYTES: There are two types of electrolytes which are used in electrolysis experiments. (i)Strong electrolytes: These are substances which are dissociated to a large extent to produce a large number of ions(+ve and -ve ions). Ionic salts like NaCl, KBr, CaCl2 etc. and strong bases like NaOH, KOH etc, strong acids like HCl, H2SO4, HNO3 etc. are included in this category. Na+Cl -(s) + aq. ----------> Na+(aq) + Cl -(aq) The term aq. stands for aqueous (H2O). The ionic solid dissolves in water giving freely moving hydrated ions. Please refer the chapter, " chemical bond" to revise the process of hydration of ions. These free ions are responsible to conduct electricity. The ionic compounds can also be used in the molten (liquid) form in stead of aqueous solution. Free ions are present in the liquid state in case of ionic substances which conduct electricity. Strong acids like H2SO4, HNO3, HCl, HBr etc. although are covalent in their pure form, undergo dissociation to produce freely moving hydrated ions as follows. These free ions conduct electricity. + 2- H2SO4(l) + aq. -----------> 2H (aq) + SO4 (aq) HCl(g) + aq. ---------> H+(aq) + Cl -(g) When a strong electrolyte is used in the form of aqueous solution or in molten state, large amount of ions are produced and large current passes through the circuit and if a bulb is connected in the path of the circuit, we shall find that the bulb produces bright light. (ii)Weak Electrolyte: The substances which undergo weak dissociation and produce a small number of +ve and -ve ions are called weak electrolytes. All weak acids and weak bases fall into this category. Refer the chapter, 'acids and bases' for getting more details. HCN(g) + aq ---------> H+(aq) + CN-(aq). - + CH3COOH(l) + aq --------> CH3COO (aq) + H (aq) These substances remain predominantly in the non-ionised form(LHS) and produce small number of ions(RHS). Therefore such weak electrolytes conduct electricity to a small extent. The electric bulb connected in the path of the circuit glows with a dim light when a weak electrolyte is used as electrolyte. MECHANISM OF ELECTROLYSIS: Before the current is allowed to pass through the electrolyte, the ions move in a random manner in all possible directions. But when current is passed through the electrolytic cell, the positive ions present in the electrolyte are attracted by the negative electrode called cathode and the negative ions are attracted by the positive electrode called anode. They get themselves discharged and become neutral at the respective electrodes and are liberated as free elements. Note that the positive ions are called cations and negative ions are called anions because they migrate and are discharged at the cathode and anode respectively. Let us see how they are discharged at the respective electrodes. 3 CATHODE REACTION: A cation contains less number of electrons than protons and thus carries positive charge, while the cathode (negative electrode) carries excess of electrons. While the cation reaches the cathode, it takes electron from the cathode and gets itself neutralised to free element. There is no more attraction with the electrode as soon it becomes neutral and is liberated at the cathode as neutral element. Na+ + e -------> Na Na+ was having one electron less (deficit of one electron) and so it picks up one electron from the cathode and becomes neutral (Na). Neutral sodium is deposited at the cathode. Can you say, what kind of reaction is this? Oxidation or reduction? Gain of electron is called reduction. So it is a reduction process. Remember that reduction occurs at cathode. ANODE REACTION: The anion contains excess number of electrons than protons and thus carries -ve charge, while anode(positive electrode) is deficient in electron and carries +ve charge. When anion reaches the anode, it gives out the excess electrons present in it to the anode which is deficient in electrons. Thus the negative charge vanishes from the anion which is converted to free and neutral element. There is no more attraction with the electrode as soon it get itself discharged and is liberated at the anode as free element.
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