Chemistry for EEE stream BCHEE102/202 MODULE 5: SENSORS IN ANALYTICAL TECHNIQUES, Electrode System: Introduction, types of electrodes. Ion selective electrode — definition, construction, working and applications of glass electrode. Determination of pH using glasselectrode. Reference electrode- Introduction, calomel electrode— construction, working and applications of calomelel ectrode. Concentration cell— Definition, construction and Numerical problems Sensors:Introduction, working principle and applications of Conductometric sensors, Electrochemical sensors, Thermometric sensors, and Optical sensors. ‘Analytical Techniques: Introduction, principle and instrumentation of Colorimetric sensors; its application in the estimation of copper, principle and instrumentation of Potentiometric sensors; principle, instrumentation and its application in the estimation of iron, Conductometric sensors; its application in the estimation of weak acid. ELECTRODE SYSTEM ‘Types of electrodes: 1) Metal-metal ion exchange: In this electrode, a metal is immersed in the ionic solution of its own salts. Example: Cw/Cu”” 2) Redox electrode: In this electrode, ions of a chemical species in two different oxidation states are in contact with each other. Example: Pt 3) Gas Electrode: In this electrode, an inert metal like platinum is in contact with gas molecules Examples: Standard Hydrogen electrode 4) Metal-Insoluble salt electrode: In this electrode, metal is in contact with its insoluble salt Example: Calomel Electrode 5) Amalgum electrode: In this electrode, a known concentration of metal dissolved in liquid ‘mercury is in contact with ionic solution of the metal. Example: Pb(Hg) 6) Ion selective electrode: This electrode is more selective towards a particular type of ion in the mixture. Example: Glass electrode Ton-selective electrode The electrode, which are responds to a specific ion in a mixture by ignofing other ions are called as ion selective electrodes. They consist of a thin membrane in contact with ion solution. Example, glasselectrode Glass Electrode: This electrode works on the principle that when a thin, low resistivity glass membrane is in contact with a solution containing H'ions, a potential develops across the membrane and the solution, Potential developed depends on the concentration of hydrogen ions in thesolution, ‘Construction: > It consists of a long glass tube with a thin-walled glass bulb containing 0.1 M HCI [Ci]. Ag/AgCl electrode placed inside the solution to provide electrical contact. > The glass electrode is dipped in unknown solution of concentration C2, > Thepotential developed across the membraneby the exchange of ions with the composition of glass is known as the boundary potential B, (E> E)). > Even when C,=C> , E# 0 a small potential is developed across the membrane, it is calledas asymmetric potential (Eqs) Department of Chemistry, SVIT Page 1Chemistry for EEE stream BCHEE102/202 OAM HCICh, [— Glass bulb j}— XM HCI(c2) EE Cell representation: Ag / AgCl / HCI (0.1M) / unknown solution/ Glass Working: E,& Ep is the potential developed at outer and inner membrane respectively the boundary potential is, E, = Ey — Ey 0.0591 0.0591 a) {po By = £94 loglc2] fe — logical} z, Boos cz OOssI cL ip = log[c2] - —— — log{C1] 0.0591 0.0591 a By = bog] + log re Where p= 09 Therefore 0.0591 By = b+ togic2] Here n=1, [C2] = [H"] ions in outer membrane, Then Ey = L + 0.0591log[H*] Ey —0.0591p" (pH= -log{H"] ) The Glass electrode potential is given by Eq = Ey + Eagjagct + Easy Substitute the value of Ey, EG L—-0.0591p" + Eag/agct + Easy ConsiderL, = L + Eagyagct + Easy. Therefore Eg = L, — 0.0591p" Department of Chemistry, SVIT Page 2Chemistry for EEE stream BCHEE102/202 Determination of pH of a solution using Glass Electrode ‘The potential of a glass electrode depends on the concentration of H® ions. Hence, pH of a solution can be determined by using glass electrode and calomel electrode assembly. The cell assembly is represented as Hg/Hg:ClyCT / solution of unknown pH / glass/0.1 M HCI/ AgCl/ Ag * iene Glass electrode SCE }— Unknown solation The emf of a cell is determined by using voltmeter. [Link] is the difference b/w glass electrode potential Eg and the calomel electrode potential Esce Ecathoae — Eanode = Eg — Esce [K = Ly — Esce] Where K= Electrode assembly constant. Reference electrodes Reference electrodes are the electrodes whose potential is known and used for determination of potential of unknown electrodes Calomel Electrode: Construction: 1) Calomel electrode consists of long glass tube with two side tubes. 2) One at the top to fill saturated KCI solution and the other side tube is connected to the salt bridge. Mercury is placed at the bottom which is covered with a layer of Hg and HgxCh (calomel) paste. 3) The remaining portion is filled with saturated KCI solution, 4) A platinum wire is dipped into the mercury and is used to provide external electrical contact. Department of Chemistry, SVIT Page 3Chemistry for EEE stream BCHEE102/202 é Hg + Calomel paste =_ — Hg ‘The calomel electrode is represented as, CI/Hg2CL/Hg Working: Calomel electrode behaves as anode or cathode depending upon the nature of another electrode. The half-cell reaction when it acts as an anode is 2Hg + 2Cl- + HgaCly + 2e~ ‘The half-cell reaction when it acts as a cathode is HgzCl; + 2e~ > 2Hg + 2CI~ The electrode reaction is, Hg2Cl, + 2e~ © 2Hg + 2Cl- Applying Nernst equation, 0.0591, [Reactants] ah °9 Products] 0.0591, [Hg2Cla] [Hg ICl- E=Eo+ E=Eo+ Since [HgxCh] = [Hg] °= 1, the above equation becomes 0.0591, 1 0 2 ice] ‘The calomel electrode potential is depending on the concentration of chloride ions in KCl. If the Concentration of chloride ions increases, the potential decreases and vice versa, (The potential of calomel is inversely proportional to the concentration of chloride ions) ‘The potential of calomel electrode is measured with respect to SHE and it depends on concentration of KCI solution used, Conc. KCI | [Link] IN Saturated KCI Potential (V) | 0.334V 0.281V 0.242V E=E°+ Oooo Department of Chemistry, SVIT Page 4Chemistry for EEE stream BCHEE102/202 Applications: 1) Used to determine the potential of the otherelectrodes. 2) Itiscommonly used as reference electrode in all potentiometricdeterminations. Electrolytic Concentration Cel It is galvanic cell, which consists of two identical electrodes, which are in contact with the same solution of electrolyte in different concentrations. Example: Consider two silver electrodes that in contact with the AgNO; solution of different concentrations (M; and Mz) connected through voltmeter. The electrolytes are connected through salt bridge. The cell representation Ag/ AgNO; (M,)// AgNOs (Mo/Ag Where Mj and M2 are the molar concentration of the Ag” ions in the two half-cells. At Anode: Ag > Ag*(M1) + e~ At Cathode: Ag*(M2) + e~ > Ag Net Cell Reaction: Ag*(M2) Ag*(M1) Apply Nernst equation for the cell reaction, 0.0591 [Reactants] 70 de 109 Products] E° = E°catnoae — E° anode Since both anode & cathode is made up of same metal, E° = 0 0.0591, [M2] _ 0.0591, [M2] E=04 ogi or E = log Department of Chemistry, SVIT Page 5Chemistry for EEE stream BCHEE102/202 SENSORS A sensor isa device that detects and responds to some type of input from the physical environment. Anal Product Transducer Receptor Schematic diagram of components of sensors ‘Components of Sensors: 1, Receptor: it is a chemical element which is capable of interacting with analyte specifically and selectively. It produces signal corresponding to interaction in the form of change in potential, conductivity heat, pH etc. 2. Transducers: Transducers is used to convert the signal created by the receptor-analyte interaction into a readable value. 3. Electrical signals and Display. 4, The electronic system analyses the signal given by the transducer, converts the signal into digital form, These signals are then displayed. Electrochemical Sensors: These sensors use electrode as transducer component. The main components of electrochemical sensors are working or sensing electrode, electrolyte, counter and reference electrode. Electrolyte is a part of the electrochemical Sensors and role is to transport charge within the sensors, contact all electrode effectively, it is stable under all conditions. Following steps are involved in working of an electrochemical sensor 1. Diffusion of the analyte to the electrode/electrolyte interface (in the liquid form) 2. Adsorption onto the electrode surface 3. Electrochemical reaction with electron transfer 4. Desorption of the product 5. Diffusion of the products away from the reaction zone to the bulk of electrolyte or gas phase. Applieatior 1. The oxygen sensors are used to determine dissolved oxygen in boiler water and to monitor dissolved oxygen concentrations in hydrogen fuel cell. 2. Used in security and defence applications like detection of toxic gases. 3. Used in water analysis and environmental monitoring. 4, Used in diagnostic and health care applications. 5. Used in soil parameter analysis and in agricultural applications. Department of Chemistry, SVIT Page 6Chemistry for EEE stream BCHEE102/202 Note: Types of electrochemical sensors 1. Potentiometric Sensors In this sensors change in potential during chemical interaction between receptor and analyte is measured using indicator electrode and reference electrode. Indicator electrode is used to measure the change in the potential due to redox reaction occurring on the surface of the electrode. 2. Amperometric Sensor Conductometrie Sensors It involves the determination of the concentration of analyte based on the ee measurement of changes occur in electrolyte solution. Conductance is depending on Fie ¥ No. of ions u : Y¥ Mobility of ions fee Electrode used is conductivity cell. It is made up of two platinum foils oe with unit cross sectional area and unit distance between them. Conductance of unit volume of the solution is called specific conductance and it is given by ae ayt i Roa Here Va is known as cell cot ant, R is resistance, Applications: Used to estimate acid, base and mixture in the sample Used to check ionic impurities in water sample Used to measure acidity or alkalinity of sea water and fresh water 4, Conductometric biosensors are used in biomedicine, environment monitoring, biotechnology and agricultural related applications. Optical Sensors: 1. These sensors based on the interaction of electromagnetic radiation with the chemical species. Commonly UV-Visible-Infrared electromagnetic radiations are used. In an optical sensor, the optical signal arises from the interaction of the analyte with an incident radiation. This interaction could results in absorption, emission, scattering and reflection of light. The intensity of the radiation gives the information on the concentration of the analyte. 2. Optical sensors are used to determine the concentration of coloured solution, It is based on the measurement of absorbance of the coloured solution at particular wavelength, It is governed by Beer-Lambertz law. 3. The optical sensors components are light source, filters, photocell and display system. 4. Schematic diagram is as follows yuu WAY 8 ~ 5 Ay) y — ae y ——: —_ — Depa Usht source Filter car Photocell Recorder Page 7Chemistry for EEE stream BCHEE102/202 Applications: ‘© Used in the determination of any chemical species which can interact with electromagnetic radiations * Can be used in environmental, pharmaceuticals, food related applications ‘Thermometric Sensors: It is based on the measurement of thermal changes during the interaction between analyte and receptor. Working: Main component is a small tubular catalytic reactor fitted with a temperature transducer. Analyte is fed into the reactor. The wall of the reactor is coated with a catalyst which is capable of catalyzing the reaction, liberating the heat energy. Heat liberated is quantified by transducer and convert into voltage and fed to the data storage and processing unit. ‘The two main transducers which convert change in temperature into an electric signal are Resistive transducers: Most commonly used resistive transducer is the thermistor. It is a semiconductor device made up of oxides of transition metals. 2. Thermocouple: It is a device which converts the temperature difference into an electrical voltage, Applications: Used in determination of metabolites, bioprocess monitoring and environmental control and determination of combustible gases. ANALYTICAL TECHNIQUES COLORIMETRIC METHOD Introduction: this method is useful to determine the concentration of unknown solution, ‘The concentration of the unknown solution is determined by measuring the absorbance of the light radiations w.r. known concentration, The instrument name is Photoelectric Colorimeter Principle: The colorimeter is explained by Beer ~ Lambertz Law. When a monochromatic light is passed through a solution, a part of light is absorbed by the solution, The absorbance depends on the concentration of the solution and the path length of the light through the solution. Beer-Lambert’s law: Absorbance is directly proportional to concentration and thickness. A=€ct € = molar absorption co-efficient A = Absorbance of light, T = Path length, C = ‘Concentration of the solution Instrumentation: The instruments is used to measure the absorbance of a solution is called photoelectric colorimeter. It consists of Source: tungsten bulb or lamp is used as a light source Filter: It is a device to provide desired wavelength range Sample cell: Sample is hold in glass cell Photocell: Converts the emitted light into electrical signal. When light is allowed to fall on the sample cell at particular wavelength. The blank solution is taken in the sample cell and placed in the path of light beam. Its absorbance is adjusted to zero. Then the analyte solution I placed in the path of light and its Department of Chemistry, SVIT Page 8Chemistry for EEE stream BCHEE102/202 absorbance is measured. A plot of absorbance against standard concentrations of analyte is used to find the unknown concentration of analyte in the samples. uu SAY YN f Z((p }= Y im | fe —F — Light source Iter ‘Sample cell Photocell, tecorder * (cuvette) na Applications: > Inquantitative analysis: large number of metal ions, anions and cations compounds can be determined by in this method. > Photometric Titration i.e. equivalence point can also be determined, > Determination of the composition colored complex, blood analysis, urine analysis. For example: Procedure: Pipette out 2, 4, 6, 8, 10 ml of standard copper sulphate solution into 25 ml standard flask. Add 2.5 ml of ammonia solution into each of them and make up to the mark with distilled water and shake well. Set the filter to 620 nm, Adjust the initial reading to zero by ‘Volume of copper sulpate sing blank solution in the sample tube, Measure the absorbance for each standard flask solution and plot graph of absorbance v/s concentration of copper sulphate. Advantages: > Can be determine the concentration of the colored solution > Itis very simple method > Colorimeter gives most accurate value » Used for lower concentration Volume of unknown copper sulphate solution aourquosqy Potentiometric Titration Aim: Determination of the weight of ferrous ammonium sulphate and ferrous iron in the given solution by potentiomettic titration method. ‘Theory: In this titration the amount of substance in the solution is determined by measuring the emf between two electrodes that are dipped into the solution. When the metal M is immersed in the solution containing its own ions M"" ions, the electrode potential is given by Nernst equation, B= £9 +21 logia"*] From this equation the potential of the electrode is directly proportional to the concentration of ecies present in the solution. Department of Chemistry, SVIT Page 9Chemistry for EEE stream BCHEE102/202 Instrumentation; A potentiometer consists of a indicator electrode (e.g.: Platinum) and an saturated reference electrode (E.g.: Calomel electrode), stirrer & potentiometer to measure the potential values. Emf of the solution can be measured by combining reference electrode with indicator electrode. The electrode which responds to the change in the concentration of the ion in the solution is called indicator electrode & reference electrode is one whose potential is constant. A known volume of the analyte is taken in beaker and its potential is measured. The titrant is added in increments of 0.5mi and potential is measured each time. Near the equivalence point there is a arp increase in the potential. The end point is determined by plotting change in potential against volume of the titrant. Applications Estimation of concentration of the ionic species present in the givensolution. Coloured solution can also betitrated . Acid-base titration can also be done in thismethod. In this method Oxidation-reduction titrations can also be carriedout. . Precipitation reactions can also be carried outpotentiometrically. were For example: Procedure: Pipette out 25cm’ of FAS solution into a 50 em* beaker. Add one test tube full of dil H)SOy. Immerse Pu. & Ag calomel electrodes into the solution, & connect the electrodes to7R a potentiometer. Fill the burette with KxCr,0) solution. Add K,Cr,0; solution from the burette with increment of 0.5cm’, stir well and measure the potential after each addition. Continue the titration till the potential indicates a rapid jump with a drop Equivalence point oftitrant. Plot the graph of AE/ AV vis vol. of KxCr20z. Volume of pot. dichromate Conductometric Titration Conductance is ease with which current flows through the solution. It is reciprocal of resistance. C=1/R = 9" or mho or siemen Theory: ‘The Conductance of the solution is explained by considering ohm’s law. According to ohm’s law the current flowing through the conductor is directly proportional to voltageand inversely proportional to the resistance. I=g0r E=IR ‘The resistance of the any conductor is directly proportional to the length, inverselyproportional to the area of cross section of the conductor Therefore R = S (V/a) where S is specific resistance Oe eo Department of Chemistry, SVIT Page 10Chemistry for EEE stream BCHEE102/202 Therefore C = 1/R =1/S(all), K(wl), _ K = specificconductance Itis defined as the conductance of the solution present between two parallel electrodes of lem? area of cross section and lem apart. ‘The conductance of the solution is depending on mobility of the ion and number of the ion, Instrumentation: It consists of two platinum electrodes each of unit area of cross section placed at unit distance apart. The electrodes are dipped in the electrolytic solution taken in a beaker. It is connected to a conductometer to measure the conductance. The conductance is measured after the addition of the titrant at interval of 0.5 ml. ‘Types of conductance: There are three type’s namely specific conductance, equivalence conductance, and molar conductance. Specific conductance (K) is the conductance of the solution present between two parallel electrodes of 1cm? area of cross section and lem apart. K = I/R (Va) K = Siemen m" Equivalence conductance () is the conductance of the solution when 1g equivalent weight of solution is placed between two electrodes of area lem? at Iem apart. Molar conductance (1) is the conductance of the solution when 1g molecular weight of solute is placed between two electrodes of area 1em? at lem apart Application of Conductometric titration It is used in the estimation of acids and bases present in the sample solutions. The possible combinations and conductance responses are explained below, Weak acid v/s Strong base (CH;COOH v/s NaOH) Consider the titration of acetic acid against NaOH. The conductance of the acid will be initially low since acetic acid is a weak electrolyte. When NaOH is added to the acid, the salt formed is highly ionized and the conductance increases. On complete neutralization of the acid, further addition of base leads to an increase in the number of mobile OH’ ions. Hence the conductance increases sharply. CH, COOH + NaOH — CH3COONa + H,0 A plot of conductance against the volume of base added is shown in the figure. The point of intersection of two curves gives the neutralization point. Equivalence point oa eouenunpuo9, Volume of NaOH ehbirioitierisrineeineenonenersinisisitincriisebnsnck tsar ioe eienirse ren sae ase Department of Chemistry, SVIT Page 11