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In search of the elusive hydration number. S.H. Shakman
1.Average ratio of hydration Fig.1: Na+ Li+ Ratio numbers for Na+:Li+ for 14 sets [FLINT** 11 19 .579] of data in Amis* (.608)are MacInnes* 2.0 4.7 .426 generally compatible with ratio " 8.4 14 .600 maximally prescribed by Flint** " 14.9 23 .648 (11/19=.579) based on atomic no. " 9.8 14.3 .685 [Z] & valence[C] per equation Washburn* 8.4 14 .600 H=23-(Z+C) [see fig.1] Baborovsky*8-9 13-14 .630 " 9 14 .643 2.Degree of persistence of hy- " 44.5 62 .718 drates at elevated temperatures, Collet* 5 7 .714 in general agreement w/relative Haase* 13 22 .591 hydration nos. per Flint**, is Ulich* 2-4 6-7 .462 evidenced by comparing ratios, Devyatykh* 10 21 .476 relative to Na+=1.00, Robinson* 5 7 .714 of observed (CRC'67) to Gapon* 3 5 .600 calculated conductivi- fig.2: (h/a)0øC 18øC 25øC 50øC 75øC ties, calculated as in- Na+BASE (h)1.00 1.00 1.00 1.00 1.00 verse-sq.-root of anhy- K+ (h)1.01 .97 .95 .91 .89 drous(a) [Wa=2(Z+C)] or C2H3O2- (h) .98 1.00 1.00 1.02 1.04 hydrated(h) [Wh=Wa+18H] Ba++ (a) .92 .91 .92 .92 .93 weights (for 8 ions with La+3 (a) .99 1.03 1.04 1.07 1.10 ratios w/in 10% of BASE SO4-- (a)1.02 1.01 1.00 .98 .98 at 0&C) after Graham C2O4-- (a) .92 .89 .88 .86 .84 per Flint [see fig.2]. OH- (a)1.08 1.06 1.01 .93 .83
*AMIS,E.& J.HINTON,Solvent Effects...(1973) Tables 3-1,4,15. **FLINT,LH,J.Wash.Acad.Sci.22(1932)97+;-Behavior...(1964)21.
Fig.2. example: calculation for K+=.97 at 18&C: Observed
conductivities for K+ and Na+ are 64.6 & 43.5 resp.; anhydrous
weights[(Wa)=2(Z+C)] 40 & 24, hydrated weights [(Wh)= Wa+18H]
94 & 222, and calculated conductivities 1//94=.1031 & 1//222=
.0671 resp.; (64.6/.1031)/(43.4/.06712)=.97.
(c)1985 Txu219626 SHShakman/ (c)1988
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