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Thermodynamic Quantities for the Ionization Reactions of Buffers

Thermodynamic Quantities for the Ionization Reactions of Buffers

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262 GOLDBERG, KISHORE, AND LENNEN<br />

Values adjusted to TÄ298.15 K and IÄ0<br />

pK rH°/(kJ mol 1 ) rC p /(J K 1 mol 1 ) Reference<br />

Reaction „1…: H2L ¿ ÄH ¿ ¿HL<br />

1.78 3.51 76LEW/HAN<br />

Reaction „2…: HLÄH ¿ ¿LÀ 6.3 04JOH<br />

6.3 10HOL<br />

6.31 28MOR<br />

6.18 29BRO/WYN<br />

6.273 49KIL<br />

6.14 3.3 76LEW/HAN<br />

6.288 76WAU<br />

6.45 82TAK/YAG<br />

6.25 83CAP<br />

6.27 87KIT/ITO<br />

6.4 97KOB/SUG<br />

6.35 2.6 86 98FUK/TAK<br />

Comments: The selected pK value <strong>for</strong> reaction 2 encompasses <strong>the</strong> results <strong>of</strong> what we believe to be <strong>the</strong> most reliable <strong>of</strong> <strong>the</strong> studies 49KIL, 76WAU. There<br />

is a reasonable agreement <strong>of</strong> this selected pK value with <strong>the</strong> o<strong>the</strong>r results. We adopt rH°/(kJmol1 )3.0, <strong>the</strong> rounded average <strong>of</strong> <strong>the</strong> calorimetric results<br />

<strong>for</strong> reaction 2.<br />

TABLE 7.18. CAPS<br />

O<strong>the</strong>r names 3-cyclohexylamino-1-propanesulfonic acid; CAS No. 1135-40-6<br />

Empirical <strong>for</strong>mula C 9H 19NO 3S<br />

Molecular weight 221.32<br />

<strong>Ionization</strong> reaction<br />

Evaluation: AAC<br />

Structure:<br />

HL H L , where HLC 9H 19NO 3S<br />

Selected values at TÄ298.15 K and IÄ0:<br />

pK10.499, rG°/(kJ mol 1 )59.929, rH°/(kJ mol 1 )48.1, and rC p /(J K 1 mol 1 )57<br />

Values from literature<br />

pK rH°/(kJ mol 1 ) T/K I Methods and comments Reference<br />

10.35 48.5 298.15 0.01 M Potentiometric titration—glass electrode; and calorimetry. Dilute<br />

solutions 0.005–0.01 M were titrated with 0.1 M NaOH or 0.1 M<br />

HCl.<br />

76MCG/JOR<br />

10.60 298.15 ? Potentiometric titration <strong>of</strong> sample 0.01–0.014 M with 0.1 M HCl<br />

or 0.1 M NaOH.<br />

87KIT/ITO<br />

10.39 298.15 0.10 M Potentiometric titration—glass electrode. 97ORA/AZA<br />

11.094 278.15 0 Electrochemical cell—no liquid junction. The pK value at T 97ROY/MOO<br />

10.940 283.15 0<br />

10.790 288.15 0<br />

10.643 293.15 0<br />

10.499 48.22 298.15 0<br />

10.359 303.15 0<br />

10.223 308.15 0<br />

10.168 310.15 0<br />

10.087 313.15 0<br />

9.958 318.15 0<br />

9.831 323.15 0<br />

J. Phys. Chem. Ref. Data, Vol. 31, No. 2, 2002<br />

278.15 K in <strong>the</strong> published paper 97ROY/MOO contains a<br />

typographical error. The value given here is correct 2001ROY. The<br />

value <strong>of</strong> rH° given here was calculated from pKs measured at<br />

several temperatures. The value rC p /(J K 1 mol 1 )93 was also<br />

calculated from <strong>the</strong> temperature dependency <strong>of</strong> Roy et al.’s<br />

97ROY/MOO reported pKs.

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