: HI HI Hil teroasyizal chemistry encompass & ep of quantitative analyteal methods that led pon the dei popes ofa "Sion ofthe ana WENT made put of eochemial al Tare pes of eleto> Soe eee, ‘xquatityof electricity, A second group em spsone ofthe foregoing electrical parameters ‘Netublsh the end point inatitration, A tied aepory includes methods in which the analyte Aouverted toa weighable form by means of lectial curren Regardless of 18%, the intelligent appica- Sen ofan electroanalytical method requires ‘understanding of the basic theory and ‘Ratal aspects ofthe operation of eecro- ‘encal eal Se se Cell Components Anelecrochemical ell consists of two metalic cenductors called decodes ach immeried 2 table cetroluesalinn. For eet to fw itis necessary (1) that the eecroves be ‘connected externally by means ofa mal con- ‘ductorand(2) that the two electolytsolutions bein contact to permit movement of ions from ‘one tothe other, Figure 18-1 shows an example fof e galvanic coll The fried pass disk is, porous, sothatZn"*, Cu? and SOP" fons as frell a8 H,0-molecles can move across the Junction bgtven the two elakolytesoltions; the dik simply prevents extensive mixing of the two solutions. 7 Conduction in an Electrochemical Cel. ety is condoned by ths dato: Fost b virion on ae Shown in Figure 18-1. In the copper and ‘lectrodes, as wel ad inthe externalIPLES OF INSTRUMENTAL ANALYSIS ‘of partial pressure data, 100 atm is imped) the indicated molar ser ion concetton 8 ofthe two inesfaee Thu, the el town = Figure 18-7 (p. S14) would be represent at MIME* AEH 240) Hale am FIGURE 18-3 Changes reiting fom ‘a current made up of sixdectons- 2|AN INTRODUCTION 70 ELECTROANALYTICAL ced = PRINCIPLES" OF INSTRUMENTAL ANALYSIS 2 eS ; tensinhscoanty wee : ech ef me ool. Tee yomeel oe FIGURE 18-4 Electric double layer formed at elestrode sur face as a est ofan applied poten ods. ‘Asin ll thermodynamic calculations agement wen aad pti sod txperimeta ndings requires te we of at‘PRINCIPLES OF INSTRUMENTAL ANALYSIS the fon strength pis defined by the Fr equationSecimee ny commas lewn ortiemechconvencnee Orson, Seca cea Tae eiapeace | bowre wi be debe or arma‘AN INTRODUCTION TO ELECTROANALYTICAL CHEMISTRY LF-CELL OR ELECTRODE POTENTIALS sivetcrmcon _quetion andthe andar yoga ehctode < Imus avae bebe find att te Ei tee rere! eke come ire raed Wie oe : © Searo. :| s4 PRINCIPLES OF INSTRUMENTAL ANALYSIS ‘ec employing a cel withoat quid junction ae of ie mcr with eps oe FIGURE 18-7 Schematic diagram ofan arrangement for the measure en fod poi eet te and hyopn era. whee Elo is called the standard elecrode otINCIPLES OF INSTRUMENTAL “$e ~ AN INTRODUCTION To ELECTROANALYTICAL CHEMISTRY ~ s47.-! shall not use the subscript the ten should ‘always be alert tothe fact however that the-—~" ‘quotients tha appea in this ype of equation srenocequilbrium constants despite hits > Hasty ia appearance 4 ‘Tosummarizethemeaningof the bracketed terms in Equgtion 18-15, when the substance © Raps, 3 [R= partial pressure in atmospheres s When Risse (lecomttonin mole pertte, 9 or ccationly 4 UR} actviy of oe 2 ‘When R isa pure solid or liuid in excesr oe, the solventPRINCIPLES OF INSTRUMENTAL ANALYSIS the cat : evnuon pen C8” concerto nto i constant and equal to F106 209s p pi LOY defen Ta Fr | ‘AN INTRODUCTION TO ELECTROANALYTICAL cr {5 aty, te potential i the sum of two con stants ius the standard eetwode poter- © Silo the hatereacion ' \etows ty the following example reagents +etAgO) +I ee —otsiy ‘atract with the participants of an lecrode aA ‘pat have a marked effet onthe potetal g oe B= 4079 +0081 og Ky eI)JUCTION TO ELECTROANALYTICAL CHEMISTRYAN INTRODUCTION TO ELECTAOANALYTICAL CHEMISTRY Re ce overvol tracted semble and should maintain an eseniiy cag, stant and reproducible potenilim the of small currents. Several eecrode rene meet these requirements. — "Kestometttctrden alow! hath may be reesei a eke La Ailes stars, KeKe) Hg ‘siere x represents the fonmal concentrton of potassium chore inthe soltion The eke, trode reaction is gen by the equation ~ HasCh() +2¢= 2H) + 201° The potemial of this cll wil vary withthe chlorite concentration x, aad ths quantity ‘ast be specified in describing te cosas “Table 18-4 lists the competion and the wise be expected to interfer. For example1UMENTAL ANALYSIS‘town it Feu 1811. STANDARD WESTON CELLS GitigC880, 3H, O(a}, Hg,SOsar) 4g cons as they ocarin the cel are ‘AN INTRODUCTION TO ELECTROANALYTICAL CHEMISTRY FIGURE 18-12 A Weston standard a (atorated) forthe owing ster > 10M), Co?" (1.00 x 10°21} (0.1008). BGs Pisow-0*- aon) H@00N)[Pe "Se iP. dx pinay Sai iy tthe car)