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    Conductivity Zafran

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    Dany Panda

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    © All Rights Reserved
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    Comprehensive Laboratory Experie! Microscale Inorganic Chemist nce Zvi Szafran Ronald M. Pike Mono M. Singh Department of Chemistry ‘Merrimack College ® JOHN WILEY & SONS, INC. Chichester Brisbane Toronto Copyright © 1991 J by John Wiley & Sons, Ine All gts reserved, Published simultaneously in Canada, Reproduetion of tansaton of any part of the work beyond that permitted by Sections 107 and 108 ofthe 1976 United States Copyght Act sethout the permission ofthe copyright owner. Regus fr perio ‘oF Further information should be addressed to the Permissions Department, John Wiley & Sons Library of Congress Cataloging in Publication Data: 102 Chapter 5 / tnorganie Microscale Laboratory Techniques fa} Kennedy, J. H., Analvtical Chemisiny: Principles, Harcourt Brace J vanovieh: New York, 1984 {b) Christian, G. D., Analytical Chemistry, 4th ed., Wiley: New York, 1 3 These pipet pumps may be obtained from Bel-Art Products, Pequar NJ 07440-1992, 44 Adams, R.; Johnson, J. R; Wilcox, C. F., Laboratory Experiments in Or Chemistry, 6th ed., Macmillon: New York. 1970. 5.3 CONDUCTIVITY In ionic compounds ofthe rain group elements, iis usually @ trivial mat MEASUREMENTS | (0 deduce the number of ions per mole present in infinitely dilute solution. onic compounds are viewed as dissociating completely in the dilute solutl (although as the concentration of solute rises, the degree of ionization cha rasticaly), and thus Ca(NOs)2 would be expected to consist of three ions: Ca?” ion and two nitrate (NOs } ions. Ih transition metal complexes, the situation is not nearly as simple. A gi anion may be a part of the complex (in which case it generally does not sociate} or it may be present as a counterion (in which case it does). We in 1912, investigeted the octahedral complex Colen)sCly (en = ethylen amine) which could have three difierent potential ligand amangements i ‘aqueous solution: [Colenio(HzO}2ICs ions [ColeniotHO1CICl, 3 tons (Colen}Cle|ct Zions There is no way of knowing in advance which of the above formulas is co (The situation is complicated further in that optical activity is also possible in above case.| The number of ions constituting the complex is best determin by measuring the conductivity of the solution of that compound. This cont Lvity measurement allows one to tell how many ions (cations and anions) present in solution when an ionie product is dissolved in water. ‘Those ionic compounds that ate soluble in water and conduct electric cu in aqueous solution ate called electrolytes. The dissolution process co of complete dissociation of sonie compounds into mobile cations and ani There are many compounds which, though soluble in weter, do not exhibit. conductivity. These are termed monelectrolytes. There i still another ‘of compounds that exhibit conductance in solutons only when that solution quite dilute. Such compounds are known as weak electrolytes. Solutk that contain large numbers of mobile ions (cations and anions frm the solu ‘onic compounds} conduct current well, and solutions that contain only a f tons (acete acid) or relatvely immobile ions show poor conductivity ~The conductivity of a solution veries with the number, sie, and charge the ions consituting the solution ! The viscosity of a solution also aifects conductuiy, by affecting the mobility of the ions. Ions of different species i Solution wil therefore show different conductivities. I, by means of a chemi reaction, we replace one ionic species by another having a different size andi charge, we would observe a comesponding change in conductivity of the sulting solution, The conductivity, L, of a solution is represented by the equation 1 = Bead, 5.4 Conductivity Measurements 103 \where B is a consiant that depends on the size and the geometry of the con- ductance cell, c, 18 the concentration of individual ions in solution, a, is the ‘equivalent ionic conductance of individual ions, and Z, isthe charge of the ions. In practice, although the conductance of a solution is more useful in dealing with electiclyte solutions, it's the resistance of a solution that is experimentally measured. The conductance fs calculated from the resistance. The resistance of a solution 1s determined by inserting two electrodes into a solution. The resis- tence, Rs proportional to the cistance, d, between the two electrodes and inversely proportional to the cross-sectional area, A, of the solution enclosod between the electrodes. 5 2 R= pdia < The term p is called the apecific resistance or more simply, the resistivity. The rato dA is usually referred to as the cell constant, K. Thus, the above relation becomes R= Kp The conduetance, L, of a solution is defined as the reciprocal of the re- sistance, and the speeific conduetivity, kis defined as the reciprocal ofthe specitic resistance. : ke = Lip = (aay) = KL In practice, the cell constant, K, Is determined for any cell by measuring the conductivity of a 0.0200M KCI soluon at 25°C, for which the specific con- ductivity, k, is 0.002768 2-". The total conductivity of a solution arises from several sources, the largest of which is the ions. The self-ionization of a solvent contributes as well, but in practice is small enough to be neglected in all but the most careful measurements. A very useful quantity is the equivalent conductivity, A. It's defined as the value of the specific conductivity, k, contributed by one equivalent of tons ‘of either charge. More specifically, it is defined as the conductance of a solution containing one gram-equivalent of an electrolyte placed between electrodes separated by a distance of 1 cm, If cls the concentration of the solution n gram- ‘equivalents per liter, the volume of the solution in cubic centimeters per equiv- alent (cmequiv) is equal to 1000/c. The equivalent conductance, A, is then siven by ‘Substituting for k, Another frequently used quantity in conductance measurements fs the molar conductance, Am, defined as the conductance of a one cubic centimeter volume of solution that contains one mole (or formula weight) of the electrolyte. ICM is the concentration of the solution in moles per liter, then the volume in cubic centimeters per mole is 1000/M. The molar conductance is then given by _ 100k fe = WM ind 104 chapter 5 / Inorganic Microscale Laboratory Techniques By comparing the molar conductance measured for a perticular compout with that of e known ionic compound, we can estimate the number of i produced in a solution, A range of velues of molar conductances for 2-5 10 at 25°C in water is given below.?* ‘Molar Conductances Number of Ions (cm—* mol"? 0") 2 118-131 3 235-273 4 408-435 5 ~560 As an example, some experimental values of molar conductance obtained a series of platinum(IV) complexes are given below. Molar Conductance (cm"" mol" 0-1) Number of {PH(NH5)6]Cl, 523, 5 [PH(NH3),CIICh 404 4 IPH(NH3)

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