lon selective electrodes(ISE) *® -Also known as indicator electrodes: * -Respand directly to the analyte * -Used for direct potentiometric measurements * -Selectively binds and measures the activity of one ion {no redox chemistry) Examples © pHelectrode Calcium (Ca*") electrode tide (CI) electrode* An ion-selective electrode (ISE), also known as a specific ion electrode (SIE), is a transducer (or sensor) that converts the activity of a specific ion dissolved in a solution into an electrical potential, which can be measured by a voltmeter or pH meter. © Anideal L.S.E. consists of a thin membrane across which only the Intended ion can be transported. © The transport of ions from a high conc. toa low one through a selective ‘binding with some sites within the membrane creates a potential difference.‘elecvoue [ Uo fan | — rersteste onanlective reference —~ havi junc weer secre© When a charged species diffuses from a region of activity, Aa, toa region of activity, A2, there is a free energy change (decrease), © AG=-RTIn (e) © This decrease in free energy should equal the electrical work done to the surroundings. ® RT In @) =-nFE * Hence, © where zis the charge of the species, including the sign.* lon Selective Electrodes (including the mast common pH electrode) work on the basic principal of the galvanic cell .By measuring the electric potential generated across a membrane by "selected" ions, and comparing it to a reference electrode, a net charge is determined. The strengih of this charge is directly proportional to the concentration of the selected ion. The basic formula is given for the galvanic cell: Ecen = Eise - ETYPES OF ION SELECTIVE ELECTRODE (ISE) © Glass Membrane Electrode ® Solid State Electrode * Liquid Membrane Electrode © Gas Sensing Electrode XWGLASS MEMBRANE ELECTRODE * Glass electrode are responsive to univalent cations (HY Nat) * The selectivity for this cation by varying the composition of a thin ion sensitive glass membrane, ° Example: pH electrode - used for pH measurement - used as a transducer in various gas and biocatalytic sensor, involving proton generating or consuming reaction.Glass Internal eferment ° Glass membrane manufactured from SiO, with negatively charged oxygen atom. © Inside the glass bulb, a dilute HCI solution and silver wire coated with a layer of silver chloride. © The electrode is immersed in the solution and pH is measured.SOLID STATE ELECTRODE © Solid state electrode are selective primarily to anions. * \tmay be a homogenous membrane electrode or heterogeneous membrane electrode. © Homogenous membrane electrode: ion-selective electrodes in which ‘the membrane is a crystalline material (Agl/Ag.S). ~1s, qa Tal \ Crystalline \ membrane | \ \ Shield 4 t \ \ ‘Solid connection — © Solid state electrode are selective primarily to anions. ° ii may be a homagenous membrane electrode or heterogeneous membrane electrode, mogenous Membrane electrode: ion-selective electrodes in which embrane is a crystalline material (Agl/Ag.S).LIQUID MEMBRANE ELECTRODE ® Liquid membrane is a type of ISE based on water-immiscible liquid substances produced in a polymeric membrane used for direct potentiometric measurement. well as a certain anions. ® Used for direct measurement of several polyvalent cations (Ca ion) asLiquid Jon exchange Membrane. ——> * The polymeric membrane made of PVC to separate the test solution from ils inner compartment. © Contains standard solution of the target ion. ® The filing solution contains a chloride sall for establishing the potential f the internal Ag/AgCl wire electrode.GAS SENSING ELECTRODE * Available for the measurement of ammonia, carbon dioxide and nitrogen oxide, * This type of electrode consist of permeable membrane and an internal buffer solution. © The pH of the buffer changes as the gas react wilh il.Gas sensing Membrane Fill solution * The change is detecled by a combination pH sensor wilhin the housing. © This type of electrode does not require an external reference electrode.Advantages of lon Selective Electrode (\SE) Technique © When compared to many other analytical techniques, lon-Selective Electrodes are relatively inexpensive and simple to use and have an extremely wide range of applications and wide concentration range. © Under the most favorable conditions, when measuring ions in relatively dilute aqueous solutions and where interfering ions are not a problem, they can be used very rapidly and easily. © They are particularly useful in applications where only an order of Magnitude concentration is required, or itis only necessary to know al a particular jon is below a certain concentration level.© They are invaluable for the continuous moniloring of changes in concentration for example in potentiometric titrations or monitoring the uptake of nutrients, or the consumption of reagents. ° They are particularly useful in biological/medical applications because they measure the activity of the ion directly, rather than the concentration. ® ISEs are one of the few techniques which can measure both positive and negalive ions. © They are unaffected by sample colour or turbidity. * ISEs can be used in aqueous solutions over a wide temperature range. Crystal membranes can operate in the range 0 C to 80 C and plaslic membranes from 0 C to 50 C.F Non-destructive: no consumption of analyte. > Non-contaminating. © Short response time: in sec. or min, useful in industrial applications.LIMITATION Precision is rarely better than 1%. Electrodes can be fouled by proteins or other organic solutes. © Interference by other ions. Electrodes are fragile and have limited shelf life. Electrodes respond to the activity of uncomplexed ion. So ligands must be absent.Empirical Calibration Plot Slope = sgfz;mV z= charge-of ion Called Nemstian slope Potential (mV) = Used to determine the unknown concentration of analytes = Departure from linearity és observed at low concentrationsAPPLICATION © ton-selective electrodes are used in a wide variety of applications for determining the concentrations of various ions in aqueaus solutions. The following is a list of some of the main areas in which ISEs have been used. * Pollution Monitoring: CN, F, 5, Cl, NO3 etc, in effluents, and natural waters. *® Agriculture: NO3, Cl, NH4, K, Ca, I, CN in soils, plant material, fertilisers and feedstuffs. © Food Processing: NO3, NO2 in meat preservatives. © Salt content of meat, fish, dairy products, fruit juices, brewing solutions. © Fin drinking water and other drinks.* Kin fruit juices and wine making. ® Corrosive effect of NO3 in canned foods. © Detergent Manufacture: Ca, Ba, F for studying effects on water quality. ® Paper Manufacture: S and Clin pulping and recovery-cycle liquors. ° Explosives: F, Cl, NO3 in explosive materials and combustion products. ® Biomedical Laboratories: Ca, K, Clin body fluids (blood, plasma, serum, sweat). ® Fin skeletal and dental studies. © Education and Research: Wide range of applications. © Cain dairy products and beer,Determination of Fluoride lon * Inthe lanthanum fluoride electrode, the sensing element is a crystal of lanthanum fluoride LaF, doped with europium fluoride EuF, to create lattice vacancies. Such a crystal is an ionic conductor by virtue of the mobility of fluoride ions which jump between lattice vacancies. * An electrochemical cell may be constructed using such a crystal as a membrane separating two fluoride solutions. This cell acts as a concentration cell with transference where the fluoride transport number isa. As transference of charge through the crystal is almost exclusively due to fluoride, the electrode is highly specific to fluoride© The only ion which significantly interferes is hydroxide (OH’). Generally such “alkaline error" can be avoided by buffering the sample toa pH below7 * The cell diagram of a typical experimental arrangement is: * Cu' [Ag AgCl| KCI || solution | LaF, | KF,KCI | AgCl,Ag |Cu * where: © Cu'fAg, AgCl| KClis an external reference electrode © KF KCHAGCI,AgiCuis an internal reference inside the fluoride selective electrode