LESSON PLAN

Sub Name & Name :CY 2161 ENGINEERING CHEMISTRY- II

LP- Engg.Chem II LP Rev.No:00 Date: Page 1of 6

Unit: 1

Branch: Common to all I Yr B.E / B.Tech (except Marine Engineering)

Unit syllabus:

ELECTROCHEMISTRY

9 hrs.

Electrochemical cells reversible and irreversible cells EMF measurement of emf Single electrode potential Nernst equation (problem) reference electrodes Standard Hydrogen electrode -Calomel electrode Ion selective electrode glass electrode and measurement of pH electrochemical series significance potentiometer titrations (redox - Fe+ vs dichromate and precipitation Ag+ vs CI- titrations) and conduct metric titrations (acid-base HCI vs, NaOH) titrations, Objective: To impart knowledge on Electro chemistry detailing electrodes, cells, conventional representation of cells and measurement of potentials. Session No 1 2 3 4 5 6 7 8 9. Topics to be covered Electrochemical cells Galvanic & Electrolytic cells reversible and irreversible cells, examples EMF Definition, measurement of emf (Poggendorffs method ) Single electrode potential Nernst equation Derivation from Thermodynamic considerations reference electrodes Standard Hydrogen electrode -Calomel electrode Ion selective electrode glass electrode and measurement of pH electrochemical series significance. potentiometer titrations (redox - Fe+ vs dichromate and precipitation Ag+ vs CI- titrations) conductometric titrations (acid-base HCI vs, NaOH) titrations, Problems on measurement of electrode and cell potentials using Nernst equation Revision Time min 50 -do-do-do-do-do-do-doRef 1,2 1,2 1,2 1,2 1,2 1,2 1,2 1,2 Teaching Aids BB & Chalk -do-do-do-do-do-do-do-

Lecturer Notes Electrochemistry

Lecturer Session No: 01 Topic: Electrochemical cells Galvanic & Electrolytic cells reversible and irreversible cells, examples

Electrochemical cells: The devices used for the inter-conversion between chemical and electrical forms of energy are called electrochemical cells. They are of two types namely galvanic cells and electrolytic cells. Electrolytic cell is one, which uses electric energy for the chemical reactions (decomposition) to take place. Redox processes are effected by electrolytic cells. Ex : Chlor-alkali generation by the passage of electric current through brine (NaCl) solution. At Cathode: Na+ + e Na (Primary process) Na + H2O NaOH+ 1/2 H2 (Secondary process) At anode: Cl - Cl + e- (Primary process) Cl + Cl Cl2 (Secondary process) Galvanic cell / Electrochemical cell is a device, which produces electric energy at the expense of chemical energy. Ex: Daniel cell made of copper and zinc electrodes possesses an emf of 1.1 V with the cell reaction mentioned below: Zn + Cu2+ Zn2+ + Cu At Anode: At Cathode: Net cell reaction Zn Zn2+ + 2 e ; Cu2+ + 2 e Cu Zn + CuSO4 ZnSO4 + Cu

Electrolytic cells consume electric energy to effect chemical reactions whereas electrochemical cells produce electric energy at the expense of chemical energy.

Reversible and Irreversible Cells:

Electrochemical cells are of two types namely reversible and irreversible cell. Reversible cell is an electrochemical with the reversibility of the electrode realizable i.e. if an infinitesimally small but excess applied emf (electro motive force) could change the direction of the electrode reaction, the cell is termed as reversible cell. E.g. Daniel cell is a reversible cell. Its cell potential is 1.1 V. Thus in Daniel cell (a galvanic cell), zinc undergoes dissolution and copper undergoes deposition to realize an emf of 1.1V, as per the following reaction sequence: Zn + Cu2+ === Zn2+ + Cu .. 1.1 V

If an emf of 1.101 V is impressed on Daniel cell (by interchanging the polarity / terminals Remember that voltage is a vector quantity, characterized by direction), copper undergoes dissolution and zinc undergoes deposition. These changes can be visually observed by the fading / deepening of the blue colour of the cupric (sulphate) solution on interchanging the terminals. Also, the solid deposit becomes brown if copper and grey / black if zinc. Irreversible is a cell where the cell reaction cannot be reversed even on applying infinitesimally small but excess applied emf i.e. the products produced during the cell reaction are not available for recombination on reversal of voltage. Example of an irreversible cell is the cell used for the electrolysis of brine or the dry cell used in pentorches. In the electrolysis of brine (aqueous NaCl solution) for example, on applying voltage, Na+ ions move towards cathode, gain one electrode and become elemental sodium atoms. But the sodium atoms immediately react with water to form sodium hydroxide. Similarly, chloride ions move towards anode, loose one electron to form chlorine atoms. These chlorine atoms recombine forming molecular chlorine, which is evolved as a gas. The reaction sequence is given below: Na+ + e Na ; 2 Na + 2 H2O 2 NaOH + H2 Cl- Cl + e ; Cl + Cl Cl2 Thus the products are not available for recombination, even on reversal of the voltage. A similar type of reactions takes place with dry cell also. Thus these cells are irreversible cells. 3

Another standard example of a reversible cell is a cell made of zinc and silver electrodes immersed in dil. H2SO4. When these electrodes are connected externally, zinc dissolves with the liberation of hydrogen gas. Zn + H2SO4 ZnSO4 + H2 The reaction at the silver electrode, on the other hand, is 2 Ag+ + 2 e 2 Ag The thermodynamic concept of reversibility applied to reversible cells involves the following conditions: 1. The driving force is infinitesimally greater than the opposing force. 2. The process can be reversed if the external force, infinitesimally greater than the opposing force is applied to the system in opposite direction. Thus on applying slight excess emf in the opposite direction, the reaction cannot be reversed as hydrogen gas has already evolved. Such a cell, which does not obey the conditions of thermodynamic reversibility, is termed as irreversible cell.

Lecturer Notes Electrochemistry

Lecturer Session No: 02 Topic: EMF Definition, measurement of emf

(Poggendorffs method ) Single electrode potential

Electromotive Force The emf (electro motive force) of a cell is the algebraic sum of the potentials of the two constituent single electrode systems. It is obvious that cell is made of two halfcells / single electrode systems. A cell is generally represented with the negative electrode / anode written first at the left and then the cathode / positive electrode at the right. Thus the emf of a galvanic cell is calculated from the half-cell potentials using the relation Ecell = Eright - Eleft = Ecathode - Eanode Here it is to be noted the values of std potentials (reduction potentials) of cathodes are more positive and those of anodes are more negative, so that the cell potential is positive. e.g. for Daniel cell, Ecell = Eright - Eleft = Ecathode - Eanode = ECu2+/ Cu EZn2+/ Zn = 0.34 (-0.76) = 1.10 Volt Measurement of EMF The potential difference, which causes current flow from the electrode of higher potential to the electrode of lower potential, is called electromotive force (emf) of the cell. The emf of a cell cannot be directly determined by connecting across a voltmeter, as some part of the cell current is drawn by the voltmeter during its measurement. This results in the formation of reaction products at the electrodes and hence a change in the electrolyte concentration around the electrodes. This difficulty can be overcome by the measurement of excess applied opposite emf that just nullifies the cell emf (Pogendorffs external compensation method). Care is to be taken during the measurement such that the current taken from the cell is negligibly small and the ionic concentrations are not appreciably altered. The emf of the cell thus remains constant and its value can be determined with high degree of accuracy / precision. The emf of acell can be determined by Pogendorffs external compensation method. In this potentiometric measurement of cell emf, a standard cell is used whose emf is known and does not vary with time. Weston cadmium cell is the conventionally used standard cell. Fig. below is the schematic of a simple potentiometer. C R

E A Std. Cell S K Cell X

E B

It consists of a uniform wire AB of high resistance. A storage battery C of constant but large emf is connected to the ends A and B of the wire through a variable resistance (rheostat) R. The cell X whose emf is to be determined is included in the circuit through a galvanometer G and a sliding contact E. The circuit is closed using a plug key K. The position of the sliding contact D is slowly changed along the wire AB till a point is reached at which there is no net current flowing through the galvanometer (its deflector points to zero). This null point position Dx is noted. The standard cell S (whose emf is known) is then introduced into the circuit and the circuit closed using the plug key K. The position of the sliding contact D is again slowly changed along the wire AB till a point is reached at which there is no net current flowing through the galvanometer (its deflector points to zero). This null point position Ds is noted. The emf of the cell X (unknown) is determined using the relation mentioned below: Emf of cell E Emf of cell X Ex balancing length AD balancing length ADs balancing length ADx Emf of standard cell S Es

Thus Es / Ex = (length ADs) / (length ADx), from which Ex can be determined, as the value of Es is known. Nowadays the digital potentiometers are used which have the inbuilt circuitry of potentiometer set up and standard cell with switching arrangement for standard cell so that the unknown cell is connected externally to directly read the cell emf as digital display. Single Electrode Potential When a zinc metal strip is immersed in copper sulphate solution for a short while and taken out, a brown deposit (of copper) can be observed on the bright colored strip,

which turns black (due to the formation of cupric oxide) with time. On the other hand, zinc strip when immersed in dilute hydrochloric acid, produces copious gas (hydrogen) evolution. These phenomena indicate that metals are in equilibrium with their cations in solution and the equilibrium is shifted towards either metal dissolution or metal deposition, depending on the nature of metal. Metal dissolution (M Mn+ + n e) process can be viewed as oxidation and metal deposition process (Mn+ + n e M) as reduction. The metal dissolution (oxidation) process is spontaneous for metals such as zinc whereas the metal deposition (reduction) process is spontaneous for metals such as copper. The former types of metals are called anodes and the latter type as cathodes. Thus the anodic or cathodic behaviour of metal explains the phenomena such as the spontaneous immersion deposit of copper and gas evolution by zinc with HCl. Similarly non-metallic elements will be in equilibrium with their anions (ex. Cl with Cl-). The tendency and the extent of the equilibrium between the element and its ion varies with element and this tendency termed as electrode potential. Electrode potential of any system can be defined as the tendency of any element to be in equilibrium with its either cation or anion in solution (aqueous). The system possessing this tendency is termed as electrode system. Generally metals will be in equilibrium with their cations in solutions whereas non-metallic elements will be in equilibrium with their anions in solutions. Thus the condition for an electrode system is the establishment of equilibrium between the element and its ion and not the electronic conduction. Ex : Copper electrode system consists of a copper strip immersed in any copper salt
2+

solution as electrolyte. Electrode reaction for this system is Cu

+ 2 e Cu. The

electrode system is represented as Cu | Cu2+. Since some electrode systems lack electronic conductivity, platinum electrode (which does not take part in electrode reaction) is provided and the electrode system set up. Ex. Hydrogen electrode is set up with Pt and represented as H2 | H+ | Pt. Electrode reaction: H2 2 H+ + 2 e-

Platinum does not involve in electrode reaction. Thus, hydrogen electrode consists of platinum metal immersed in hydrochloric acid (of concentration 1 molar) into which hydrogen gas is bubbled at a particular pressure (1 atmosphere), called standard hydrogen electrode (SHE).Thus an electrode system consists of an element, its cation or anion in solution with or without platinum support for electronic conductivity. The equilibrium exists between the element and the ion but the extent varies from system to system. The associated reversible reaction is termed as electrode reaction. 1. 2. 2H+ + 2e H2 is the electrode reaction in hydrogen electrode. Cu2+ + 2e Cu is the electrode reaction in copper electrode.

Thus the tendency of element to be in equilibrium with its cation or anion or the extent of reversibility of the associated electrode reaction is spoken of as electrode potential. It takes the unit of volt and is a vector quantity. If the reaction is spontaneous, potential is positive and vice-versa. For a given electrode system, either oxidation (loss of electrons) or reduction (gain of electrons) is spontaneous and accordingly the potential will be of positive or negative sign. For ease of convention, reduction potential is taken as positive i.e. a system having positive potential has the reduction reaction spontaneous. Ex: electrode potential is + 0.34 V means that the reaction Cu 2+ + 2e Cu is spontaneous for copper electrode. Zinc electrode potential is - 0.76 V meaning that Zn Zn2+ + 2 e is spontaneous reaction for zinc electrode. Anodes are represented with the element symbol first, followed by a vertical line (which shows electrode-electrolyte interface), which is turn is followed by the ionic form of the electrolyte. Ex. Zinc electrode is represented as Zn | Zn2+; cathodes are represented in similar manner but in the reverse order. Ex: Copper electrode is represented as Cu2+ | Cu.

The potential of an electrode system depends on (i) the nature of the metal / element (electron transfer number), (ii) temperature of the electrolyte and (iii) concentration of the electrolyte or pressure of the gas for gaseous systems. As the potential of the same electrode system varies with these conditions, potential under a set of standard conditions is considered as standard electrode potential. Thus standard electrode potential is defined as the (reduction) potential of the electrode system when all the components are at their unit active levels i.e. tendency of element to be in equilibrium with its cation or anion or the extent of reversibility of the associated electrode reaction when the electrolyte concentration is unity (1 molar) and the gas pressure is 1 atmosphere.

Lecturer Notes Electrochemistry

Lecturer

Session

No:

03

Topic:

Nernst

equation

Derivation

from

Thermodynamic considerations reference electrodes Standard Hydrogen electrode -Calomel electrode

Nernst Equation: The potential of any electrode system (E) depends on (i) nature of the metal / element (ii) temperature and concentration of the electrolyte. The functional dependence of potential of any electrode system (E) on these factors is given by Nernst equation E = E 0 + (RT / nF) ( log Mn+) where Eo , n, T, R and F denote respectively. The standard electrode potential, charge transfer number, absolute / Kelvin temperature, Universal Gas Constant and Faradays constant. The derivation / explanation of the terms are as follows: It is obvious that the concept of electrode potential evolves from the inter-conversion between chemical and electrical forms of energy. The equation pertaining to these two forms of energy is G = G0 + RT ln K ----- (1) where G, G0, K and R are respectively the free energy change for a process under given conditions of Kelvin Temperature, standard free energy change for the process, equilibrium constant for the process and universal gas constant. The free energy change for any chemical to electrical energy conversion process is given by the equation G = - nFE ----- (2) where E is the potential of the electrode system, F Faradays constant = 96496 or 96500 coulombs and n is the number of electrons transferred between the element and the ion which are in equilibrium. Combining equations (1) and (2), we get - nFE = - nFE0 + RT ln K ----- (1) where E0 is the standard electrode potential of the electrode system.

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Consider the reduction reaction Mn+ + n e M Equation (3) becomes E = E0 - (RT / nF) ln (aproducts / areactants ) ----- (4) where a is the activity of the species. The activity of a (homogenous / uniform) solid is taken as unity, that of the electrolyte expressed in terms of the concentration and that of a gas (or gaseous mixture) expressed in terms of pressure (or partial pressure) of the gas. Equation (4) can be written as E = E0 - (RT / nF) ln (aM / aMn+ ) (or) E = E0 + (RT / nF) ln [Mn+] ----- (4) where [Mn+] is the concentration of the electrolyte / metal ion in solution. i.e. E = E0 + (RT / nF) ln [Mn+] ----- (5) substituting the values of R= 8.314 Joules, F = 96500 Coulombs and introducing the factor 2.303 to convert natural logarithms to common logarithms, equation (5) becomes E = E0 + (0.059 / n) log [Mn+] ----- (6) Eequations (5) and (6) are the two forms of Nernst equation which gives the dependence of electrode potential on the factors mentioned.

Problems:Calculate the std emf of the cell

Zn | ZnSO 4 || CuSO4 | Cu, if the std

electrode potentials of copper and zinc are respectively 0.337 V and 0.763 V.

Reference Electrodes: 11

The potential of an electrode system (electrode of interest or working electrode) can be measured by coupling with other electrode with a voltmeter introduced between them. The coupled electrode should not possess any charge transfer reaction (electrode reaction) in the electrolyte used or it should not be polarized. Such ideally nonpolarizable electrodes used for the measurement of working electrodes are called reference electrodes. Reference electrodes are two types namely primary and secondary reference electrodes. Primary reference electrode is one that is universally used such as standard hydrogen electrode (SHE) and its potential is arbitrarily taken as zero. But SHE involves tedious and cumbersome construction. This difficulty is overcome by the use of secondary reference electrodes, which can be constructed easily and their potentials can be determined with SHE as reference.

H2 (1 atm.)

Pt. foil 1 N HCl

Saturated KCl

Examples of secondary reference electrodes are calomel electrode, silver-silver electrode, glass electrode, quinhydrone electrode etc. Calomel electrode is set up with mercurous Hg + Hg2Cl2 Pt wire 12 Hg

chloride, mercury and potassium chloride electrolyte and represented as Hg | Hg 2Cl2 | KCl. Depending on the concentration of KCl, calomel electrode is of three types namely saturated normal and decinormal calomel electrodes.

The electrode reaction for calomel electrode is Hg2Cl2 (s) + e Hg(s) + ClThe potentials of the different calomel electrodes against SHE reference is given below:

[ KCl ]

Saturated

1.0 N

0.1 N

Potential , V

0.2422

0.2810

0.3335

Merits and Demerits of Calomel electrode: 1. Gives relative pH values compared to hydrogen electrode, which gives absolute values of pH.

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Ag/AgCl electrode is prepared by depositing a thin layer of AgCl electrolytically on a Ag or Pt wire and immersing in a solution containing the chloride ions. It is represented as Ag | AgCl | Cl-( M) The electrode reaction of Ag/AgCl electrode is : AgCl + e Ag + Cl-

Lecturer Notes Electrochemistry

Lecturer Session No: 04 Topic: Ion selective electrode glass electrode and

measurement of pH

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Glass electrode is made of special glass of relatively low melting point and electrical conductivity with composition Na2O (22%), CaO (6%) and SiO2 (72%). The glass elctrode assembly consists of a thin glass bulb filled with 0.1 N HCl and a silver wire coated with silver chloride immersed in it. The Ag/AgCl electrode here acts as the internal reference electrode. The glass electrode is represented as Ag | AgCl(s) | 0.1 M HCl | glass. Working: when glass electrode is immersed in the solution whose pHis to be determined, a potential difference is set up between the two surfaces of the glass membrane. The potential value developed is proportional to the pH of the test solution (sample). Actually, the glass membrane of the glass electrode undergoes an ion-exchange reaction in which the sodium ions of the glass membrane are exchanged with protons of the sample solution. The electrode reaction of the glass electrode immersed in the test solution can be represented as glass ---- Na+ + H+ = glass ---- H+ + Na+

Ion selective electrodes (ISEs): ISEs are the electrodes useful in the qualitative and quantitative analysis of sample ion only, in a mixture of variety of species. As the potential of an electrode system varies with the ionic concentration of the electrolyte, the electrode system can be used as an ISE by coupling with a suitable reference electrode. ISEs are normally used with saturated calomel electrode (SCE) reference and the developed potentials are measured using potentiometers or pH meters. The use of metals directly as ISE has the following disadvantages: (i) slow electrode response (ii) Nernst equation not followed (iii) chage of electrode potential due to the availability of electrons on theelectrode surface (iv) no well defined electron change. Hence various membranes are used in ISEs and such electrodes are called Ion selective membrane electrodes (ISMEs). ISMEs show some degree of specificity and selectivity, These electrodes utilize some membrane to confine an inner solution and the reference electrode. Membranes in the ISE and reference electrode (RE) sides function by ion exchange (IE) mechanism. Various types of ISEs are as follows: 1. Glass membrane electrodes 2. Liquid membrane electrodes 3. Double membrane electrodes 4. Solid-state membrane electrodes 5. Precipitate membrane electrodes.

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Lecturer Notes Electrochemistry

Lecturer Session No: 05 Topic: Electrochemical series significance.

Electrochemical series:

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Electrochemical series is the arrangement of elements in the ascending (or descending) order of their electrode (reduction) potential values with hydrogen at the centre. Electrode systems appearing earlier in the series have the oxidation reaction spontaneous and are termed as anodes and those appearing later in the series have the reduction reaction spontaneous and are termed as cathodes. Electrode system Li | Li+ Mg | Mg2+ Zn | Zn2+ Sn | Sn2+ H2 | 2 H+ Cu2+ | Cu Ag+ | Ag F2 | 2 FStandard Potential (E0), volt -3.05 -2.40 -0.76 -0.44 0.00 +0.34 +0.80 +2.87

The potential of a redox electrode system is given merely as a number (modulus value, irrespective sign). Thus if the reduction potential is positive, the oxidation potential is negative for the same system and vice-versa. Std. electrode potential conventionally represents the reduction potential or potential of the reduction reaction.

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Importance / Significance / Applications of electrochemical series: Electrochemical series is useful / significant in the prediction of 1. Spontaneity of reactions: The feasibility / spontaneity of reactions of the reactions be predicted from the knowledge of the electrode potential values. Such processes are spontaneous whose standard potential is positive. 2. Corrosion behaviour of metals and alloys: Metals / alloys with negative values of

std. electrode potentials are prone / susceptible to corrosion and those with positive values of std. electrode potentials are resistant to corrosion (an undesirable phenomenon). e.g. zinc is more easily corroded than copper (or) copper is more resistant to corrosion than zinc. 3. Redox behaviour of materials: Materials with more negative values of std. electrode potentials are used in reduction reactions addition of electrons (as they can donate electrons) and Materials with more posittive values of std. electrode potentials are used in oxidation reactions removal of electrons (as they can accept electrons). E.g. zinc, tin etc. are used as reducing agents whereas oxides of copper etc are used as oxidizing agents. 4. Displacement characteristics of metals: Metals with more negative std. electrode potentials will displace metals with more positive std. electrode potential values. E.g. zinc will displace copper from its salt solution and not vice-versa. 5. Determination of equilibrium constant of the reaction from the knowledge of electrode potential values, using the relation G = - nFE = - RT ln K. Galvanic series is the arrangement of industrial metals or alloys in the ascending or descending order of their electrode potential values in the seawater electrolyte medium. It predicts the corrosion tendencies of metals and alloys in common corroding media. It differs from the electrochemical series in that it is more practical than electrochemical series and the potentials are expressed with reference to Saturated Calomel Electrode (SCE) whereas in electrochemical series, the potentials are expressed with reference to Standard Hydrogen Electrode (SHE). It is to be noted that the potential of pure metal is

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different from that of the alloy. Galvanic series is more useful as it predicts the corrosion behaviour of different metals and alloys in various corroding media.

Lecturer Notes Electrochemistry

Lecturer Session No: 06 Topic: Potentiometer titrations (redox - Fe+ vs dichromate

and precipitation Ag+ vs CI- titrations) 19

Potentiometric Titration: Potentiometric titration is used for following the course of reactions involving electrolytes, where there is no proper indicator available. The potential of the electrode system is determined using the platinum and calomel electrodes immersed in the reaction mixture after regular additions of the titrant. The potential observed is plotted against the volume of titrant added. The endpoint is determined graphically from the change in trends before and after the completion of the reaction. E.g. the redox reaction between ferrous (ammonium) sulphate (FAS) and potassium permanganate or dichromate is followed by determining the potential using the platinum and calomel electrodes immersed in the reaction mixture after adding regular volumes of permanganate or dichromate. The potential observed is plotted against the volume of titrant added (E Vs V plot). The endpoint is determined graphically from the change in trends before and after the completion of the reaction. A derivative plot can also de made between change in potential to change in volume (E/V) and the average volume of the titrant [(V1+V2)/2]. The volume corresponding to the peak in the derivative plot directly gives the end point condition whereas the involved electrode systems and their potentials can be got from the E Vs V plot. The model graphs for the potentiometric titrations are given below:

Emf (V)

E / V mV/ml

Volume of titrant (ml)

V1 + V2 2

The S-shaped curve for the E Vs V plot is due to the fact that the electrode system itself is changed after the completion of reaction i.e. initially when a small amount of

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permanganate (MnO4- with manganese in its Mn7+ state) is added to the reaction mixture containing FAS and dilute sulphuric acid in a beaker, corresponding amount of ferrous ions (Fe2+) is oxidized to ferric state (Fe3+) and permanganate is reduced to Mn2+ state. Thus the beaker contents are two ionic (redox) species of iron (i.e.Fe2+ and Fe3+) with platinum electrode (inert electrode, contributing only electronic conductivity) immersed. This constitutes the iron electrode system, whose potential varies gradually (as given by Nernst equation) with regular additions of titrant. The After the end point (reaction completion), all the ferrous ions are completely oxidized to ferric ions and the excess added permanganate ions (Mn7+) exist as redox couple with manganous ions (Mn2+), leaving only one type of species for iron (Fe3+) in the beaker. Now the electrode system is manganese electrode system, whose potential varies gradually (as given by Nernst equation) with regular addition. As the electrode system itself is changed during the reaction, there is a shoot up in potential in the E Vs V plot and hence it is S-shaped. pH determination: A cell is constructed with saturated calomel electrode (SCE) or and a glass electrode or quinhydrone electrode immersed in the solution, whose pH is to be determined and its potential measured. By applying Nernst equation for the cell constructed, the pH of the sample can be determined. where the potentials are in
Potentiometer volts. The glass electrode potential can be determined by previously dipping in

solutions of known pH (buffers) and noting the potential observed with the similar cells construted. The actual cell representation is Glass | solution of unknown pH || SCE pH of the buffer = pHb = (ESCE- EG0- Ecell) / 0.0591 ------- (i) Pt. wire Saturated KCl where Ebcell is the cell potential observed with the buffer. pH of the sample = pHs = (ESCE- EG0- Ecell) / 0.0591 ------ (ii) where Escell is the cell potential observed with the sample. From Equations (i) and (ii) pH of the sample can be calculated from the observed cell 0.1M HCl potentials. Similarly, pH determination can be made with other electrodes such as Hg + Hg2Cl2 Pt wire quinhydrone electrode. Thin walled glass bulb

Hg

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Lecturer Notes Electrochemistry

22

Lecturer Session No: 07 Topic: Conductometric titrations (acid-base HCI vs,

NaOH) titration). Conductometric titration of strong acid against a strong base: The course of neutralization of a strong acid by a strong base can be determined by condutometric method (without the use of indicator). The principle of conductometric titration is that the conductance of a reaction follows a specific trend before the completion of the reaction and it follows a different trend after the completion of the reaction. From the change in trends, the end point of the reaction can be determined graphically. The model graph for this titration is shown in fig.

Conductance (mho)

Conductance (mho)

Vol. of titrant (ml) Neutralisation titration

Vol. of titrant (ml) Precipitation titration

In the case of neutralization of strong acid (say HCl) by a strong base (say NaOH), the conductance of HCl (taken in a beaker) is determined at regular additions of NaOH, from the burette. H+Cl- + Na+OH- Na+Cl- + H2O

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The conductance of the reaction mixture (HCl) decreases till the end point because lighter protons (H+) are replaced by heavier Na+ ions, whose mobility is lower than that of protons. The conductance of the reaction mixture increases after the end point because heavier chloride ions (Cl- whose atomic mass is 35.5) are replaced by lighter hydroxyl (OH-) ions (with mass 17), whose mobility is higher than that of chloride ions. A plot of the conductance of the reaction mixture against the volume of the titrant gives two straight lines of opposite slopes. The point of intersection of the straight lines is the end point. Conductometric titration of weak acid against a strong base: The course of neutralization of a weak acid by a strong base can be determined by condutometric method (without the use of indicator). The principle of conductometric titration is that the conductance of a reaction follows a specific trend before the completion of the reaction and it follows a different trend after the completion of the reaction. From the change in trends, the end point of the reaction can be determined graphically. In the case of neutralization of weak acid (say CH 3COOH) by a strong base (say NaOH), the conductance of CH3COOH (taken in a beaker) is determined at regular additions of NaOH, from a burette. CH3COOH + Na+OH- CH3COO-Na+ + H2O (weak) (feebly ionized) The conductance of the reaction mixture (CH3COOH) is initially low because of the poor dissociation of the weak electrolyte. On the addition of strong alkali, the strong electrolyte, sodium acetate is formed. It tends to suppress the ionoization of acetic acid, due to common ion effect. Further there is increase in conductance of the reaction mixture, because of the larger proportion of the strong electrolyte, CH3COONa. Immediately after the end point, the conductance increases sharply because of the fast moving hydroxyl ions compared to the acetate ions. A plot of the conductance of the reaction mixture against the volume of the titrant gives two straight lines of positive, but varying slopes. The point of intersection of the straight lines is the end point. Conductometric titration of strong acid against a weak base:

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The course of neutralization of a strong acid by a weak base can be determined by condutometric method (without the use of indicator). The principle of conductometric titration is that the conductance of a reaction follows a specific trend before the completion of the reaction and it follows a different trend after the completion of the reaction. From the change in trends, the end point of the reaction can be determined graphically. In the case of neutralization of strong acid (say HCl) by a weak base (say NH4OH), the conductance of HCl (taken in a beaker) is determined at regular additions of NH4OH, from a burette. H+Cl- + NH4OH NH4+Cl- + H2O (weak) The conductance of the reaction mixture (HCl) decreases sharply, with the addition of the weak base, ammonium hydroxide, because of the formation of the salt ammonim chloride, which is a weaker electrolyte than HCl. Immediately after the end point, the conductance decreases further but slowly because ammonium hydroxide is a still weaker electrolyte than ammonium chloride.A plot of the conductance of the reaction mixture against the volume of the titrant gives two straight lines of negative, but varying slopes. The point of intersection of the straight lines is the end point. Conductometric titration of weak acid against a weak base: The course of neutralization of a weak acid by a weak base can be determined by condutometric method (without the use of indicator). The principle of conductometric titration is that the conductance of a reaction follows a specific trend before the completion of the reaction and it follows a different trend after the completion of the reaction. From the change in trends, the end point of the reaction can be determined graphically. In the case of neutralization of weak acid (say CH3COOH) by a weak base (say NH4OH), the conductance of CH3COOH (taken in a beaker) is determined at regular additions of NH4OH, from a burette. CH3COOH + NH4OH CH3COONH4 + H2O (weak) The conductance of the reaction mixture (CH3COOH) increases gradually with the addition of the weak base, ammonium hydroxide, because of the formation of the salt

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ammonium acetate. Immediately after the end point, the conductance remains almost constant, because the titrant, ammonium hydroxide is a weake electrolyte. A plot of the conductance of the reaction mixture against the volume of the titrant gives first a sloping line and a line parallel to one of the co-ordinate axes. The point of intersection of the straight lines is the end point. This method is quite suitable when there is no proper indicator available, particularly this case.

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Lecturer Notes Electrochemistry

Lecturer Session No: 08 Topic: Problems on measurement of electrode and cell

potentials using Nernst equation

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Lecturer Notes Electrochemistry

Lecturer Session No: 09 Topic: Revision

TEXT BOOKS FOR THIS UNIT. 1. P.C.Jain and Monica Jain, Engineering Chemistry Dhanpat Rai Pub, Co., New Delhi (2002). 2. S.S.Dara A text book of Engineering Chemistry S.Chand & Co.Ltd., New Delhi (2006). REFERENCES BOOKS FOR THIS UNIT. : 1. B.Sivasankar Engineering Chemistry Tata McGraw-Hill Pub.Co.Ltd, New Delhi (2008). 2. B.K.Sharma Engineering Chemistry Krishna Prakasan Media (P) Ltd., Meerut (2001).

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