Jain, Ajay K.

Malik, Wahid U.

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.................. "" _ ........... --.-- -----_ _-- -- .INDIAN J. CHEM., VOL. 14A, JANUARY 1976TABLE 2-CORRESPONDING CONDUCTANCESOF CsClO., AgClO., KH.ClO., AgNOs IN DIMETHYLFORMAMlDEAT25°C(ohm'+ cm-2 mole-l)Concentration (M)0·0001 0·0002 0·0003LiClO. (exp) 75·76 74·98 74'61RbClO. 82·71 82·08 81'80CsClO.* 84·67 84·13 83·90(84-6698) (84'0509) (83'5532)AgCIO. (expl] 85-83 85·02 84'548(85'8298) (85'2174) (84'97772)NH.ClO. 89·00 86·69(expH (88'9997) (88·4053) (88'2055)KJ (exp)KBrAgNOs (exp)§0·000479·6980'7477-06(77-0601)0·0006 0·0008 0·001073-69 72'6180'76 79·59(82'7226) (81'5276)83065(83'8842) (82-6744)(87'0586) (85'8084)78'4879·5970·67(75·7349)0·0015 0·001977·19 76·4377·1664·02(74-16)Calc. values in parentheses assuming *1'=1'2776; tr=1·4419; tr=1'8909; §1'=2·5047.TABLE 3 - CORRESPONDINGCONDUCTANCEOF KClO. IN AQUEOUSMEDIA AT 25°C (ohm:" cm-2 mole'<)Concentration (M)0·0005 0·001 0·002 0·005 0·010 0·020 0·050 0·070 0·100LiClO. (exp) 104'18 103·44 102·46 100·57 98·61 96·18 92·20 90·50 88'56NaClO. 115'64 114'87 113'80 111·75 109'59 106'96 102·40 100'52 98·43KClO. (exp)* 138·76 137·87 136·62 134-16 131-46 127·92 121-62 118·79 115'20(138'75) (137'92) (136'67) (134'30) (131,74) (128'64) (122-97) (120-73) 118·3417*Calculated values in parentheses assuming 1'=3·0174.ductance study of AgN03 in dimethylformamidehas been done in the concentration range of 0·0004 to0'0019M by choosing KI and KBr as the subscripts1 and 2. Finally theoretical values of conductancehave been calculated in the case of KCl04 (Table 3)in the cone. range of 0·0005 to 0·100M. The resultsare in good agreement with the experimental values.Theoretical values of 1\0 and Walden product 1\01)obtained for these salts are shown in Table 1.References1. GUGGENHEIM,E. A., Trans. Faraday Soc., 65 (1969), 2474.2. PITTS, E., Proc. R. Soc. Sec., A, 217 (1953), 43.3. PITTS, E., TABOR, B. E. & DALY, J., Trans. Faraday Soc .,65 (1970), 693.4. PITTS, E., TABOR, B. E. & DALY, J., Tmns. Faraday Soc.,66 (1969), 849.5. PRUE, J. E. & SHERRINGTON,P. J., Trans. Faraday Soc.,57 (1961), 1795.6. JONES, J. H., J. Am. chem , Soa., 67 (1945), 855.Studies on the Cell NiINi-Soap(s), K-Soap,Cu-Soap(s)\CuVVAHlDU. MALIK & AJAY K. JAINDepartment of Chemistry, University of Roorkee, RoorkeeReceived 9~Dece1nbey 1974; accepted 22 February 1975The e.m.f., temperature coefficient of e.m.f. and thethermodynamic parameters of the cell reaction havebeen computed for the cells of the type NiJNi-soap(s),K-soap, Cu-soap(s)!Cu. The soaps have been derivedfrom lauric, myristic, palmitic and stearic acids. Thecell's reactlon'[Is accompanied by decrease in enthalpyas well as entropy. The cell e.m.f. is also found to beindependent of concentration ofpotassium soap solution.fiOIN continuation of our earlier workl-5 on metal-metal soap electrode system, the e.m.f. of thecell of the type (A) has been evaluated.Ni'Ni-soapjs), K-soap, Cu-soap(sjC» (A)Potassium salts of lauric (C11), myristic (C13), pal-mitic (CIS) and stearic (C17) acids were preparedfrom reagent grade (BDH) acids and crystallizedfrom ethanol.Nickel and copper soaps were prepared by adirect metathesis reaction at 50-55° from the corres-ponding potassium soaps and aqueous solution ofnickel or coppe~ sulp?ate. The precipitated soapswere washed WIth distilled water and then withethanol to remove free precipitant. The soapsgave satisfactory elemental analysis.Nickel electrodes were prepared by depositingnickel on platinum wires by the electrolysis of asolution containing nickel sulphate (15%), boricacid (1%) and sodium chloride (0,6%). The elec-trodes were connected to a 4 V battery and a currentof 20 mamp was passed for about 2 hr. Copperelectrodes were prepared by depositing copper onplatinum wires by the electrolysis of a solutioncontaining CuS04 (8%) and H2S04 (4,6%). Theelectrodes were connected to a 2 V battery and acurrent of 15 mamp was passed for 4 hr.A Cambridge portable potentiometer was usedfor ~.m.f. measurements of the cell of the type (A)at different temperatures. The cell vessel employedwas of H type. The two limbs of the ceil wereprovided with nickel and copper electrodes. Thecell contained aqueous solution of potassium soapsaturated with nickel and copper soaps. Somesolid metal soaps were always added to the cell [tomake certain that potassium soap solution wassaturated with respect to metal soaps.IJNOTESTABLE 1 - TEMPERATURECOEFFICIENTOF E.M.F. AND IlG, IlH AND IlS FOR THE CELL REACTIONSCell reaction e.m.f. dE/dT IlG303°K .IlH303°K IlS303°Kat 303°K (V deg-1) (cal.) (cal.) (cal. deg-1)(V)Ni+ (CllH2SCOO)2CU?(CllH23COO)2N i-j-Cu 0·1242 -0·000826 -5728 -17268 -38'11Ni+ (C13H27COO)2CU?(C13H27COO)2Ni +Cu 0·1287 -0·00075 -5936 -16416 -34'59Ni + (C15H31COO).CU?(C15H31COO) 2Ni+Cu 0·1315 -0'0007 -6064 -15845 -32-28Ni + (Cl~H3'COO) 2CU?(C17H3,COO) 2Ni+ Cu 0'1343 -0'00066 -6194 -15415 -30·44TABLE 2-E.M.F. OF THE CELL OF THE TYPE (A)Pot. Temp. e.m.f. dE/dT Meansoap (0C) (V) (V/deg) dE/dT(Cx103) (Vjdeg)MSOAP DERIVED FROMLAURICACID5 25 0·12858 25 0·128510 25 0·128510 30 0'1242 -0'0008610 40 0·1162 -0,00080 -0·00082610 45 0·1120 -0,00082SOAP DERIVED FROMMYRISTICACID1 25 0·13252'5 25 0·13255 25 0·13255 30 0·1287 -0'000765 35 0·1250 -0'000745 40 0'1212 -0'00076 -0'000755 45 0'1175 -0,00074SOAP DERIVED FROMPALMITICACID1'0 25 0·13501'5 25 0·13502'5 25 0·13502·5 30 0·1315 -0'000702'5 35 0·1280 -0'000702'5 40 0·1246 -0'00068 -0·00072'5 45 0·1210 -0·00072SOAP DERIVED FROM STEARICACID0·5 25 0'13750·7 25 0·13750'8 25 0'13750'8 30 0·1343 -0·000640'8 35 0·1310 -0,000660'8 40 0·1276 -0'00068 -0,000660'8 45 0·1243 -0,00066The e.m.f. values recorded at different temperaturesare given in Table 2.The reaction taking place in the cell isNi +CUD2~NiD2 +Cuwhere D stands for laurate, myristate, palmitateor stearate ion.Both the electrodes involved in the cell underconsideration are reversible with respect to thedetergent anion. The e.m.f. of t.he cell'S should. beindependent of the concentration of potassiumsoap and should be equal to algebraic difference ofstandard reduction or oxidation potential of elec-trodes. The concentration ranges of potassiumsoaps investigated were from 1X 10-2 to 5 X 10-3,5 X 10-3 to 1X 10-3 2·5 X 10-3 to 1X 10-3 and 8 X 10-4to 5X 10-4M for potassium laurate, myristate, palmi-tate and stearate respectively. These concentrationsof potassium soaps are just below the critical micelleconcentration (cmc) values", It is evident fromTable 2 that the e.m.f. of the cells are independentof the concentration of potassium soap solution.The following equations have been used for cal-culating t:...G, t:...H and t:...S at 303°K:t:...G=-nEFt:...S= nF (dE/dT)pb.H = -nEF +nFT (dE/dT)pThe values of the e.m.f. of the cells at 303°K, thetemperature coefficient of e.m.f. and the values of t:...G,t:...Hand t:...Sfor the cell reactions are given in Table 1.References1. MALIK, WAHID U. & JAIN, A. K., ]. electroanal . Chem.,14 (1967), 37.2. MALIK, WARID U., AHMAD, S. 1. & JAIN, A. K.,Kolloid-Z., 218 (1967), 155.3. MALIK, WARlD U. & JAIN, A. K., Aust. ]. Chem., 22(1969). 465.4. MALIK, WAHID U. & JAIN, AJAY K.,]. electroanal, Chem •.16 (196R), 271. .5. MALIK, WARID U. & JAIN, A. K., Indian J. Chem., 6(1968), 140.Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II),Pd(II), Cd(II) & U02(II) Chelates of SchiffBases Derived from o-AminobenzenesulphonicAcid & 2-Aminoethanesulphonic Acid &2-Hydroxy-l-naphthaldehydeD. D. OZHA, K. N. KAUL & R. K. MEHTADepartment of Chemistry, University of Jodhpur, JodhpurReceived 10 September 1974; accepted 3 March 1975N - (2 - Hydroxy - 1 - naphthalidene)orthanilic acid(H2NO) and N-(2-hydroxy-l-naphthalidene)taurine(H2NT), the two structurally similar Schiff bases, formsolid chelates with Mn(II), Fe(II), Co(II), Ni(II), Cu(II),Zn(II), Pd(II), Cd(II) and U02(II). Elemental analyses,molecular weight, magnetic moment values and elec-tronic spectral data indicate nearly octahedral stereo-chemistry for Mn(II), Fe(II), Co(II), Ni(II) and U02(II)chelates, whereas Cu(II) chelates display a tetra-gonal configuration. Zn(lI) and Cd(lI) chelates aretetrahedral in structure and the Pd(lI) chelate possessessquare-planar geometry.A PERUS~L of t~e literature- reveals that nosystematic studies have been carried out onSchiff bases derived from o-aminobenzenesulphonic61

Studies on the Cell Ni|Ni-Soap(s), K-Soap, Cu-Soap(s)|Cu

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Studies on the Cell Ni|Ni-Soap(s), K-Soap, Cu-Soap(s)|Cu

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