Engineering Chemistry

A hand book For B.Tech I year (all branches)

M.Shafiulla
Assistant professor ROYAL INSTITUTE OF TECHNOLOGY & SCIENCE Damergidda (V), Chevella ). R. R. Dist. A. P.

A hand book of engineering chemistry

Electrochemistry

UNIT

ELECTROCHEMISTRY

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A hand book of engineering chemistry

Electrochemistry

Electrochemistry: It is a branch of chemistry that studies chemical reactions which take place in a solution at the interface of an electron conductor (a metal or a semiconductor) and an ionic conductor (the electrolyte), and which involve electron transfer between the electrode and the electrolyte. Electrolyte: it is a substance which is an aqueous solution or molten state liberates ions and allows current to flow through it. Electrolysis: when electric current passes through the electrolyte which results in chemical decomposition and this phenomenon is called electrolysis. Electrolytic cells: The conversion of electrical energy to chemical energy takes place. Electrolysis takes place here. It contains aqueous solution of an electrolyte in which two metallic rods are dipped which is connected to a battery. Anode: The electrode through which current enters the cell is known as anode. It is denoted as the positive electrode. Cathode: The electrode through which current leaves the cell. It is denoted as the negative electrode. Ohms Law: The current I flowing through a conductor is given by relation E/R where E is the electromotive force and R is the resistance. I =E/R (OR) Ohm's law states that the current passing through a conductor between two points is directly proportional to the potential difference or voltage across the two points, and inversely proportional to the resistance between them. The mathematical equation that describes this relationship is

Where I is the current, Ampere in units Electromotive Force: The potential which is required to move a unit charge from one place to another place. It is also known as E.M.F It is measured in volts. M.Shafiulla Page 3

A hand book of engineering chemistry

Electrochemistry

Volt: The volt is defined as the value of the voltage across a conductor when a current of one ampere strength through a one ohm resistance. Amperes: The unit of strength of current is known as amperes. The current which deposits 0.001118 gms of silver per second. Ampere = volt/ohm Coloumb: The quantity of current is measured in Coloumb. Electrical resistance: The electrical resistance of an object is a measure of its opposition to the passage of an electric current. The unit of electrical resistance is the ohm (). Resistances ( reciprocal quantity is electric conductance is measured in siemens. The resistance of an object can be defined as the ratio of voltage to current:

Three types of conductance Specific Conductance Equivalent Conductance Molecular conductance Specific Conductance:

The resistance offered by a conductor to the passage of electricity through it is directly proportional to length and inversely proportional to the area of cross section. The resistance R is given by the relation:

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Electrochemistry

A certain weight of an electrolyte is dissolved in Vml of solvent and the conductance of one ml of the resulting electrolyte solution at a given dilution V is called the Specific Conductivity. Equivalent conductance: If one gram equivalent weight of an electrolyte is dissolved in Vml of the solvent, the conductivity of all ions produced from one gram equivalent of an electrolyte at the dilution V is known as Equivalent Conductance. It is denoted by v. Hence the equivalent conductance is equal to the product of specific conductance and volume.

v = Kv x v

Kv x 1000/ N

Molar Conductance: The conductance of all ions produced by dissolving one gram molecular weight of one mole of an electrolyte when dissolved in a certain volume Vml. Molar conductance is denoted by v.
v=

Kv x V =

Kv x 1000/ M

Units are ohm-1 cm2 mole-1 EFFECTS OF DILUTION ON CONDUCTANCE : Due to dilution ionisation increase and specific conductance decreases. This happens because specific conductance is the conductance of the ions present in one centimetre cube of the solution. On dilution the number of current carrying particles (or) ions present per one centimetre cube of the solution decreases. Equivalent conductance or molecular conductance of an electrolyte increases on dilution because The above conductance are the product of kv and the volume of the solution. When volume increases equivalent conductance also increases. The number of ions of the electrolyte solution increases on dilution contributing to the increase of conductance.Ionisation increases on dilution, till the whole electrolyte substance has ionised.the limiting value is known as equivalent conductance at infinite dilution and it is represented by the symbol .

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The conductance ratio is called the degree of ionisation: = v / Electrolytes can be divided into two types Strong Electrolytes Weak electrolytes Strong Electrolyte:

Electrochemistry

A strong electrolyte is a substance that gives a solution in which almost all the molecules are ionised, even at low concentration such solution have increasing value of equivalent conductance at low dilution. Strong Acids: HCl,H2SO4,HNO3 Strong Base: NaOH, KOH The Salts: Practically all salts are strong electrolytes Weak Electrolyte: The electrolyte which ionise to a small extent on dilution are called weak electrolyte. They have a low value of equivalent conductance even at a higher concentration and are not completely ionised even at very great dilution. Weak Acids: All organics acids like acetic acids, propionic acid and H2SO3 Weak Bases: Alkyl Amines, NH4OH Salts: A few salts such as mercuric chloride and lead acetate Measurement of conductance Conductance is the reciprocal of resistance and the resistance can be determined by a Wheatstone bridge circuit in which the conductivity cell forms one arm of the bridge. Wheatstone bridge circuit for is used for measuring conductivity, Conductivity cell with one arm of a resistance bridge for measurement of conductivity of an electrolyte. The arms AH and HB represented by resistance R1 and R2 are usually in the form of a single calibrated slide wire resistor with a sliding contact connected to the null detector. The solution whose conductance is to be determined is placed in conductivity cell. When the M.Shafiulla Page 6

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Electrochemistry

bridge is balanced, assuming that the conductivity cell behaves as a pure resistance, then the voltage between B and D is equal to zero. Conductance cell

If you put two electrodes into a solution that contains dissolved ions and apply a voltage to the electrodes, the ions will move through the solution: the negative ions (anions) will move toward the positive electrode (the anode); the positive ions (cations) will move toward the negative electrode (the cathode). This simple apparatus is called a conductance cell. The conductance is made of highly resistant glass such as Pyrex or quartz. The electrodes consists of platinum discs coated with finely divided platinum black. These are called Platinised platinum electrodes. Platinum black surface catalyse the union of hydrogen and oxygen which tend to be liberated by the successive pulse of the current and the polarization E.M.F is thus eliminated. The electrodes are welded to platinum wires fused in two glass tubes. The glass tube contains mercury and is firmly fixed in the ebonite cover of the cell, so that the distance between the electrodes may not alter during the experiment. The cell is connected to a Wheatstone bridge which consists of a wire of platinoid or manganin AB having a uniform thickness so that the ratio of lengths read on the scales gives the ratio of resistance. The wire of AB is stretched tightly over a meter scale graduated in millimetres. A sliding contact H moves along the wire. R is the resistance box and C is the conductance cell. Conductance cell containing electrolyte is placed in the thermostat for maintaining constant temperature during the measurement of conductance. The induction coil is used to pass M.Shafiulla Page 7

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Electrochemistry

alternate current in the circuit. The sliding contact H is moved until the sound in the head phones is minimum. This gives the null point where resistance of the resistance box R and resistance of the electrolyte in the cell C are equal. Determination of Cell Constant The electrodes in the cell are not exactly 1 cm apart and may not have surface area of 1 sq. cm (1cm2). Thus the value of observed conductivity is not equal to specific conductance but is proportional to it. Where, x = l/a = cell constant Cell constant, x = /G or Specific conductance, k = cell constant a X observed conductance G. IONIC MOBILITIES The electrolytic conductance is due to the mobility of ions .With the help of the theory of electrolytic dissociation, the higher value of osmotic pressure, depression of freezing point, elevation of boiling point, increase of ionisation and the abnormal behaviour of electrolytes in solution can be explained. The main points of this theory are: When dissolved in water, salts, bases and acids give two kinds of particles, one carrying the positive charge and the other carrying the negative charge. These charged particles are called ions. When dissolved in water the weak electrostatic forces of attraction of the charged ions in the molecules are weakened by the dielectric constant of water and ionization takes place. There is a state of dynamic equilibrium between the dissociated and undissociated molecules. A+B A' + B'

Thus applying law of mass action to the ionic equilibrium the ionization constant or dissociation constant K is given by

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Electrochemistry

When electric current is passed through the solution of the electrolyte, the positive ions move towards the cathode and the negative ions move towards the anode conducting electric current through the solution. Electric conductivity of solutions depends on the number of ions and the mobility of ions. The ions behave like molecules in elevating the boiling point, depressing the freezing point, lowering the vapour pressure and osmotic pressure. If a substance gives out two types of ions then twice the normal effect of the solute. The properties of electrolytes are the properties of the ions.

Factors Influencing Ionisation Ionisation of an electrolyte in solution is influenced by the following: Nature of the Solute: The nature of solute is a chief factor which influences the rate of ionization. Example: Strong electrolytes ionize completely whereas weak electrolyte is less ionized. Nature Of the Solvent: The solvent influences the rate of ionization to a greater extent. The solvent possess dielectric constant, which is its capacity to weaken the forces of attraction between the electrical charges of the ions present. Example: The dielectric constant of water is 80; alcohol is 25and ether is 4.1. The higher the value of dielectric consant the greater the ionisation. Concentration: The extent of ionization of an electrolyte is inversely proportional to the concentration of its solution. As the dilution increases the ionisation increases. Temperature: The ionisation of an electrolyte increase with increase in temperature. As the temperature increases the velocities of the molecules increase. M.Shafiulla Page 9

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Electrochemistry

KOHLARAUSH LAW : - The equivalent conductance at infinite dilution of different electrolytes is the sum of the ionic conductances of cations and anions. = a + c Ionic conductance is expressed in ohm-1 cm2 equiv-1 Ionic conductance is directly proportional to the transport numbers. a = K x v c = K x u = a + c =K(u +v)

Applications of Kohlrausch Law Calculation of molar conductivity of a weak electrolyte at infinite dilution It is not possible to determine the value of for weak electrolytes since we cannot obtain the limiting value of the molar conductivity for a weak electrolyte. This is done indirectly by the molar ionic conductance for the individual ions of the weak electrolyte and by using kohlraushs law. Determination of Solubility of Sparingly Soluble Salts Salts like AgCl, BaSO4, CaCO3, Ag2CrO4, PbSO4, PbS, Fe(OH)3 etc. are ordinarily regarded as sparingly soluble and have a very small but definite solubility in water. The solubility of such sparingly soluble salts is obtained by determining the specific conductivity () of a saturated salt solution. v = Kv x V = = a + c Calculation of Apparent Degree of ionisation or conductivity ratio The apparent degree of ionisation or conductivity ratio of an electrolyte is by v/

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Calculation of ionic product of water

Electrochemistry

The observed specific conductivity of the purest water at 25oc is 5.54x10-8 ohm cm-1 With the help of specific conductivity of water, the ionic product of water can be determined. The ionization of water may be represented as, H2O H+ + OH The product of the concentrations of H+ and OH- ions expressed in mol/L is called ionic product of water and is represented by Kw. Kw = [H+] [OH-] Half cell Electrode which is dipped in its salt solution is called half cell. The standard hydrogen half cell: 2H+(aq) + 2e- H2(g) The half cells of a Daniell cell: Original equation Zn + Cu2+ Zn2+ + Cu

Half cell (anode) of Zn Zn Zn2+ + 2e Half cell (cathode) of Cu Cu2+ + 2e Cu

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Electrochemistry

Galvanic cell DANIELL CELL It is designed to make use of the spontaneous redox reaction between zinc and cupric ions to produce an electric current it consists of two half-cells. The half-cells on the left contain a zinc metal electrode dipped in ZnSO4 solution. The half-cell on the right consists of copper metal electrode in a solution CuSO4. The half-cells are joined by a salt bridge that prevents the mechanical mixing of the solution. When the zinc and copper electrodes are joined by wire, the following observations are made: (i) There is a flow of electric current through the external circuit. (ii) The zinc rod loses its mass while the copper rod gains in mass. (iii) The concentration of ZnSO4 solution increases while the concentration of copper sulphate solution decreases. (iv) The solutions in both the compartments remain electrically neutral.

During the passage if electric current through external circuit, electrons flow from the zinc electrode to the copper electrode. At the zinc electrode, the zinc metal is oxidized to zinc ions which go into the solution. The electrons released at the electrode travel through the external circuit to the copper electrode where they

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Electrochemistry

are used in the reduction of Cu2+ ions to metallic copper which is deposited on the electrode. Thus, the overall redox reaction is: Zn(s) + Cu2+ Cu(s) + Zn2+(aq)

Thus, indirect redox reaction leads to the production of electrical energy. At the zinc rod, oxidation occurs. It is the anode of the cell and is negatively charged while at copper electrode. (i) Voltaic or Galvanic cell consists of two half-cells. The reactions occurring in half-cells are called half-cell reactions. The half-cell in which oxidation taking place in it is called oxidation half-cell and the reaction taking place in it is called oxidation half-cell reaction. Similarly, the half-cell occurs is called reduction half-cell and the reaction taking place in it is called reduction half-cell reaction. (ii) The electrode where oxidation occurs is called anode and the electrode where reduction occurs is termed cathode. (iii) Electrons flow from anode to cathode in the external circuit.

Single Electrode potential The potential difference developed between metal electrode and the solution of its ions of unit molarity (1M) at 25C (298 K) is called standard electrode potential. Depending on the nature of the metal electrode to lose or gain electrons, the electrode potential may be of two types:

(i) Oxidation potential: When electrode is negatively charged with respect to solution, i.e., it acts as anode. Oxidation occurs. M --> Mn+ + ne(ii) Reduction potential: When electrode is positively charged with respect to solution, i.e., it acts as cathode. Reduction occurs. Mn+ + ne- --> M Emf of the cell = EAnode + ECathode = Oxidation potential of anode + Reduction potential of cathode M.Shafiulla Page 13

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Electrochemistry

Knowing the value of reference electrode, the value of other electrode can be determined. Measurement of single electrode potential ECell = EoAnode + EoCathode NERNST EQUATION The electrode potential and the emf of the cell depend upon the nature of the electrode, temperature and the activities (concentrations) of the ions in solution. The variation of electrode and cell potentials with concentration of ions in solution can be obtained from thermodynamic considerations. For a general reaction such as M1A + m2B n1X + n2Y + .... .......(i) Occurring in the cell, the Gibbs free energy change is given by the equation G = Go + 2.303RT log10....... (ii) Where 'a' represents the activities of reactants and products under a given set of conditions and Go refers to free energy change for the reaction when the various reactants and products are present at standard conditions. The free energy change of a cell reaction is related to the electrical work that can be obtained from the cell, i.e., Go = -nFEcell and Go = -nFEo. On substituting these values in Eq. (ii) we get -nFEcell = -nFEo + 2.30eRT log10....... (iii) or Ecell = Ecello - 2.303RT/nF log10....... (iv).This equation is known as Nernst equation. Putting the values of R=8.314 JK-1 mol-1, T = 298 K and F=96500 C, Eq. (iv) reduces to E = Eo - 0.0591/n log10....... (v) = Eo - 0.0591/n log10 ([Products])/([Reactants]) ....... (vi) Potential of single electrode (Anode): Consider the general oxidation reaction, M --> Mn+ + neApplying Nernst equation, Eox = Eoxo - 0.0591/n log10 [Mn+]/[M] Where Eox is the oxidation potential of the electrode (anode), is the standard oxidation potential of the electrode. [Note: The concentration of pure solids and liquids are taken as unity.] M.Shafiulla Page 14

A hand book of engineering chemistry

Eox = Eoxo - 0.0591/n log10 [Mn+]

Electrochemistry

Let us consider a Daniell cell to explain the above equations. The concentrations of the electrolytes are not 1 M. Zn(s) +Cu2+ (aq) <=> Zn2+(aq) + Cu(s) Zn(s) |Zn2+ (aq) ||Cu2+ (aq) |Cu Potential at zinc electrode (Anode) Eox = Eoxo - 0.0591/n log10 [Zn3+] Potential at copper electrode (Cathode) Ered = Eredo - 0.0591/n log10 [Cu2+] Emf of the cell Ecell = Eox + Ered = (Eoxo + Eredo )- 0.0591/n [Zn2+/Cu2+] REVERSIBLE AND IRREVERSIBLE CELLS Daniell cell has the emf value 1.09 volt. If an opposing emf exactly equal to 1.09 volt is applied to the cell, the cell reaction, Zn + Cu2+ --> Cu + Zn2+ stops but if it is increased infinitesimally beyond 1.09 volt, the cell reaction is reversed. Cu + Zn2+ --> Zn + Cu2+ Such a cell is termed a reversible cell. Thus, the following are the two main conditions of reversibility: (i) The chemical reaction of the cell stops when an exactly equal opposing emf is applied. (ii) The chemical reaction of the cell is reversed and the current flows in opposite direction when the opposing emf is slightly greater than that of the cell. Any other cell which does not obey the above two conditions is termed as irreversible. A cell consisting of zinc and copper electrodes dipped into the solution of sulphuric acid is irreversible. Similarly, the cell M.Shafiulla Page 15

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Zn|H2S04(aq)|Ag

Electrochemistry

is also irreversible because when the external emf is greater than the emf of the cell, the cell reaction, Zn + 2H+ --> Zn2+ + H2 is not reversed but the cell reaction becomes 2Ag + 2H+ --> 2Ag+ + H2

Calomel electrode: It consists of mercury at the bottom over which a paste of mercurymercurous chloride is placed. A solution of potassium chloride is then placed over the paste. A platinum wire sealed in a glass tube helps in making the electrical contact. The electrode is connected with the help of the side tube on the left through a salt bridge with the other electrode to make a complete cell. The potential of the calomel electrode depends upon the concentration of the potassium

chloride solution. If potassium chloride solution is saturated, the electrode is known as saturated calomel electrode (SCE) and if the potassium chloride solution is 1 N, the electrode is known as normal calomel electrode (NCE) while for 0.1 N potassium chloride solution, the electrode is referred to as decinormal calomel electrode (DNCE). The electrode reaction when the electrode acts as cathode is: 1/2 Hg2Cl2 + e- <---> Hg + ClM.Shafiulla Page 16

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Electrochemistry

The reduction potentials of the calomel electrodes on hydrogen scale at 298K are as follows: Saturated KC1 0.2415 V 1.0NKC1 0.1NKC1 0.2800 V 0.3338 V

QUINHYDRONE ELECTRODE: The quinhydrone electrode is essentially an oxidation reduction electrodeand is based on the oxidation-reduction equilibrium set up in aqueous solution between quinoneand quinol, namely,

Quinone and hydroquinine form a reversible redox system in the presence of hydrogen ions. Hydroquinone Quinone + 2H+ +2eHydroquinone Quinone + 2H+ +2eThe potential E developed when an innert electrode example platinum is immersed in this system is given by the NERNST equation E=E+ E=E+ E= E E= E E= E E= E 0.0591V.pH M.Shafiulla {- ln[H]= pH} Page 17 ln ln ln

{ [QH2]/[Q] = 1}

A hand book of engineering chemistry

Electrochemistry

Please note that log is the logrithm function based 10, and ln, the natural logrithm function. Advantages and limitations of quinhydrone electrode The electrode is very easy to set up. The pH value obtained is very accurate. ION selective electrode Ion selective electrodes use a membrane which is sensitive to a particular chemical species. ISE respond to certain specific ions present in a mixture of ions while ignoring others. The potential develop is a measure of the concentration of the species of interest. Different types of membranes are used in io selective electrodes, they are 1.) 2.) 3.) 4.) Glass membrane Solid membrane Heterogeneous membrane Liquid membrane. internal electrolyte

Glassmembrane--Reference electrode---------

Applications of ion selective electrodes. 1.) 2.) 3.) 4.)

To determine the concentrations of CO2 level in blood samples. To determine the concentrations of a number of cat ions like H+ ,LI+, Na +,Ag+ ,NH+4 . To find the concentratiuons of an ions like F-,NO-,CN- . To determine the pH of solution.

Concentration cells A concentration cell is a Galvanic cell in which electrical energy is produced by the transfer of material from a system of hight concentration to one low concentration.. If two plates of the same metal are dipped separately into two solutions of the same electrolyte and are connected with a salt bridge, the whole arrangement is found to act as a galvanic cell. In general, there are two types of concentration cells: (i Electrode concentration cells: In these cells, the potential difference is developed between two like electrodes at different concentrations dipped in the same solution of the electrolyte. For example, two hydrogen M.Shafiulla Page 18

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Electrochemistry

electrodes at different has pressure in the same solution of hydrogen ions constitute a cell of this type. (Pt,H2 (Pressure p1))/Anode |H+ | (H2 (Pressure p2)Pt)/Cathode If p1, p2 oxidation occurs at L.H.S. electrode and reduction occurs at R.H.S. electrode. Ecell = 0.0591/2 log(p1/p2) at 25o C In the amalgam cells, two amalgams of the same metal at two different concentrations are interested in the same electrolyte solution. (ii) Electrolyte concentration cells:

In these cells, electrodes are identical but these are immersed in solutions of the same electrolyte of different concentrations. The source of electrical energy in the cell is the tendency of the electrolyte to diffuse from a solution of higher concentration to that of lower concentration. With the expiry of time, the two concentrations tend to become equal. Thus, at the start the emf of the cell is maximum and it gradually falls to zero. Such a cell is represented in the following manner: (C2 is greater than C1). M|Mn+(C1)||Mn+(C2)|M or (Zn|Zn2+ (C1))/Anode || (Zn2+ (C2 )|Zn)/Cathode

The emf of the cell is given by the following expression: Ecell = 0.0591/n log C(2(R.H.S.))/C(1(L.H.S.)) at 25o C The concentration cells are used to determine the solubility of sparingly soluble salts, valency of the cation of the electrolyte and transition point of the two allotropic forms of a metal used as electrodes, etc.

ELECTROCHEMICAL SERIES By measuring the potentials of various electrodes versus standard hydrogen electrode (SHE), a series of standard electrode potentials has been established. When the electrodes (metals and M.Shafiulla Page 19

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Electrochemistry

non-metals) in contact with their ions are arranged oh the basis of the values of their standard reduction potentials or standard oxidation potentials, the resulting series is called the electrochemicalor electromotive or activity series of the elements. By international convention, the standard potentials of electrodes are tabulated for reduction half reactions, indicating the tendencies of the electrodes to behave as cathodes towards SHE. Those with positive E values for reduction half reactions do in fact act as cathodes versus SHE, while those with negative E values of reduction half reactions behave instead as anodes versus SHE. The electrochemical series is shown in the following table. Standard Aqueous Electrode Potentials at 25C 'The Electrochemical Series' Element Electrode Reaction (Reduction) Eo, volt Li K Ca Na Mg Al Zn Cr Fe Cd Ni Sn Li+ + e- = Li K + + e- = K Ca2+ + 2e- = Ca Na+ + e- = Na Mg2+ + 2e- = Mg Al3+ + 3e- = Al Zn2+ + 2e- = Zn Cr3+ + 3e- = Cr Fe2+ + 2e- = Fe Cd2+ + 2e- = Cd Ni2+ + 2e- = Ni Sn2+ + 2e- = Sn -3.05 -2.925 -2.87 -2.714 -2.37 -1.66 -0.7628 -0.74 -0.44 -0.403 -0.25 -0.14 Standard Electrode Reduction potential

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H2 Cu I2 Ag Hg Br2 Cl2 Au F2 2H+ + 2e- = H2 Cu2+ + 2e- = Cu I2 + 2e- = 2IAg+ + e- = Ag Hg2+ + 2e- = Hg Br2 + 2e- = 2BrCl2 + 2e- = 2ClAu3+ + 3e- = Au F2 + 2e- = 2F0.00 +0.337 +0.535 +0.799 +0.885 +1.08 +1.36 +1.50 +2.87

Electrochemistry

Difference in electrolytic cell and galvanic cell Electrolytic cell Galvanic cell

1. Electrical energy is converted into Chemical energy is converted into chemical energy. electrical energy. 2. Anode positive electrode. Cathode Anode negative electrode. Cathode positive electrode. negative electrode. 3. Ions are discharged on both the Ions are discharged only on the cathode. electrodes. 4. If the electrodes are inert, concentration of the electrolyte decreases when the electric current is circulated. Concentration of the anodic half-cell increases while that of cathodic half-cell decreases when the two electrodes are joined by a wire.

5. Both the electrodes can be fitted in The electrodes are fitted in different compartments. the same compartment.

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PRIMARY VOLTAIC CELL (THE DRY CELL)

In this cell, once the chemicals have been consumed, further reaction is not possible. It cannot be regenerated by reversing the current flow through the cell using an external direct current source of electrical energy. The most common example of this type is dry cell. The container of the dry cell is made of zinc which also serves as one of the electrodes. The other electrode is a carbon rod in the centre of the cell. The zinc container is lined with a porous paper. A moist mixture of ammonium chloride, manganese dioxide, zinc chloride and a porous inert filler occupy the space between the paper lined zinc container and the carbon rod. The cell is sealed with a material like wax. As the cell operates, the zinc is oxidised to Zn2+ Zn ---> Zn2+ + 2e(Anode reaction)

The electrons are utilized at carbon rod (cathode) as the ammonium ions are reduced. 2NH4++2e- --> 2NH3 + H2 The cell reaction is Zn+ 2 NH4+ ---> Zn2+ + 2NH3 + H2 Hydrogen is oxidized by MnO2 in the cell. 2MnO2 + H2 ---> 2MnO(OH) Ammonia produced at cathode combines with zinc ions to form complex ion. M.Shafiulla Page 22 (Cathode reaction)

A hand book of engineering chemistry

Zn2+ + 4NH3 ---> [Zn(NH3)4]2+ Ecell is 1.6 volt

Electrochemistry

Alkaline dry cell is similar to ordinary dry cell. It contains potassium hydroxide. The reaction in alkaline dry cell are: Zn + 2OH- ---> Zn(OH)2 + 2e(Anode reaction) (Cathode reaction) (Overall)

2MnO2 + 2H2O + 2e- ---> 2MnO(OH) + 2OHZn + 2MnO2 + 2H2O ---> Zn(OH)2 + 2MnO(OH) Ecell is 1.5 volt.

SECODARY VOLTAIC CELL (LEAD STORAGE BATTERY)

The cell in which original reactants are regenerated by passing direct current from external source, i.e., it is re-charged, is called secondary cell. Lead storage battery is the example of this type. It consists of a group of lead plates bearing compressed spongy lead, alternating with a group of lead plates bearing leaf dioxide, PbO2. These plates are immersed in a solution of about 30% H2SO4. When the cell discharge; it operates as a voltaic cell. The spongy lead is oxidized to Pb2+ ions and lead plates acquire a negative charge. Pb --> Pb2+ + 2e(Anode reaction)

Pb2+ ions combine with sulphate ions to form insoluble lead sulphate, PbSO4, which begins to coat lead electrode. Pb2+ + SO42- ---> PbSO4 M.Shafiulla (Precipitation) Page 23

A hand book of engineering chemistry

The electrons are utilized at PbO2 electrode. PbO2 + 4H+ + 2e- ---> Pb2+ 2H2O Pb2+ + SO42- ---> PbSO4 Overall cell reaction is: Pb + PbO2 + 4H+ + 2 SO42- ---> 2PbSO4 + 2H2O Ecell is 2.041 volt.

Electrochemistry

(Cathode reaction)

(Precipitation)

When a potential slightly greater than the potential of battery is applied, the battery can be recharged. 2PbSO4 + 2H2O ---> Pb + PbO2 + 2H2SO4 After many repeated charge-discharge cycles, some of the lead sulphate falls to the bottom of the container, the sulphuric acid concentration remains low and the battery cannot be recharged fully. FUEL CELL

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Fuel cells are another means by which chemical energy may be converted into electrical energy. The main disadvantage of a primary cell is that it can deliver current for a short period only. This is due to the fact that the quantity of oxidising agent and reducing agent is limited. But the energy can be obtained indefinitely from a fuel cell as long as the outside supply of fuel is maintained. One of the examples is the hydrogen-oxygen fuel cell. The cell consists of three compartments separated by a porous electrode. Hydrogen gas is introduced into one compartment and oxygen gas is fed into another compartment. These gases then diffuse slowly through the electrodes and react with an electrolyte that is in the central compartment. The electrodes are made of porous carbon and the electrolyte is a resin containing concentrated aqueous sodium hydroxide solution. Hydrogen is oxidised at anode and oxygen is reduced at cathode. The overall cell reaction produces water. The reactions which occur are:

Anode [H2(g) + 2OH-(aq) Cathode

--->

2H2O(l) + 2e-] 2 4OH-(aq)

O2(g) + 2H2O(l) + 4e- --->

------------------------------------------------------------Overall 2H2(g) + O2(g) ---> 2H20(l) This type of cells are used in space-crafts. Fuel cells are efficient and pollution free.

SOLVED PROBLEMS.
Example : The equivalent conductances of sodium chloride, hydrochloric acid and sodium acetate at infinite dilution are 126.45, 426.16 and 91.0 ohm-1cm2 equiv-1, respectively, at 250C. Calculate the equivalent conductance of acetic acid at infinite dilution.

Solution: According to Kohlrausch's law,_(CH_3 COONa)=_(CH_3 COO^)+_(Na^+ )=91.0 ......(i)

HCl = H+ + Cl-=426.16 ...(ii) NaCl = Na+ + Cl-=126.45 ...(iii)

Adding Eqs. (i) and (ii) and subtracting (iii), M.Shafiulla Page 25

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CH3 COO- + Na+ + H+ + Cl- - Na+ + Cl= 91.0 + 426.16 - 126.45 CH3 COO- + H+ =CH3 COOH = 390.7 ohm-1 cm-2 equiv-1

Electrochemistry

Example : The equivalent conductivity of N/10 solution of acetic acid at 250C is 14.3 ohm-1 cm2 equiv-1. Calculate the degree of dissociation of CH3COOH if is 390.71. Solution:

CH3 COOH =390.7 ohm-1 cm(-2) equiv(-1)

(CH3 COOH)=143.3 ohm(-1) cm(-2) equiv(-1)

Degree of dissociation, = v/ =14.3/390.71

= 0.0366 i.e., 3.66% dissociated Example : A decinormal solution of NaCI has specific conductivity equal to 0.0092. If ionic conductances of Na+ and Cl- ions at the same temperature are 43.0 and 65.0 ohm-1 respectively, calculate the degree of dissociation of NaCl solution. Solution: Equivalent conductance of N/10 NaCl solution

v = Sp. conductivity dilution

= 0.0092 10,000 = 92 ohm-1

= (Na+ )+ Cl= 43.0 + 65.0 = 108 ohm-1 Degree of dissociation,

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A hand book of engineering chemistry

Electrochemistry

Example : 1.0 N solution of a salt surrounding two platinum electrodes 2.1 cm apart and 4.2 sq.cm in area was found to offer a resistance of 50 ohm. Calculate the equivalent conductivity of the solution. Solution: Given, l = 2.1 cm, a = 4.2 sq xm, R = 5- ohm Specific conductance, k = l/a.1/R or k= 2.1/4.21/50=0.01 ohm-1 cm-1 Equivalent conductivity = k = V V = the volume containing 1 g equivalent = 1000 mL So Equivalent conductivity = 0.01 1000

= 10 ohm-1 cm-2 equiv-1 Example : Specific conductance of a decinormal solution of KCl is 0.0112 ohm-1 cm-1. The resistance of a cell containing the solution was found to be 56. What is the cell constant? Solution: We know that Sp. conductance = Cell constant conductance or Cell constant = (Sp.conductance)/Conductance = Sp. conductance Resistance = 0.0112 56 = 0.06272 cm-1

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A hand book of engineering chemistry

1

Electrochemistry

Example : The specific conductivity of 0.02 M KCl solution at 250C is 2.768 10-3 ohm-1. The resistance of this solution at 250C when measured with a particular cell was 250.2 cm ohms. The resistance of 0.01 M CuSO4 solution at 250C measured with the same cell was 8331 ohms. Calculate the molar conductivity of the copper sulphate solution. Solution: Cell constant = (Sp.cond.of KCl)/(Conductane of KCl)

= (2.76810-3)/(I/250.2) = 2.768 10-3 250.2 For 0.01 M CuSO3 solution Sp. conductivity = Cell constant conductance = 2.768 10-3 250.2 1/8331 Molar conductance = Sp. cond. 1000/c = (2.76810-325.2)/83311000/(1/100)

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