Chemical Oceanography: Volume 8 by J. P. Riley

By J. P. Riley

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7 2 5 MOLAL N a C l AND SEA-WATER We will now examine the use of the methods discussed in the last section to estimate partial molai properties of electrolytes in NaCl and sea-water. 725 molai NaCl. For example, a number of workers (Wirth, 1937,1940; Owen and Brinkley, 1941; Lee, 1966; Millero et ai, 1977b, 1980a) have measured the partial molai volumes of electrolytes in this medium. 725 molai NaCl at 25 °C. These measured values have been 28 F. J. 00 Mg \ \? 50 RTvQ FIG. 3. Correlation of the heat of mixing (RTho) and volume of mixing (RTVQ) of NaCl with common cation (NaX) and anion (MCI) electrolytes at 25 °C.

00 400 800 1200 1600 2000 P (bars) FIG. 8. Values of y+/y+ at 25 °C for NaCl solutions at various concentrations as a function of pressure. 40 F. J. 05 \jé . 5 FIG. 9. Values of yp+lyQ+ at 25 °C for NaCl solutions at various pressures as a function of the square root of the ionic sfrength. 21 along with the calculated values of yp+/y°+ at 1000 bars. For Na salts the values of ypJy\ are in the order CO 2 - > SO 2 - > O H " > HCO3- > F - > NO3- > C\- > Br- > I", and for Cl salts the values are in the order Ba2+ > Sr 2+ > Ca 2+ > Mg 2+ > Rb + > Cs+ > Na+ > K + > Li + > NH+ > H + .

68) Unfortunately, there is no a priori method of determining whether an ion will form a contact or outer sphere ion pair. At present the average value of AK(excess) calculated by using equations (66) and (67) must be used. 19 (Millero, 1977). 4. ERRORS IN ESTIMATING yp±/y°± AND KP/K° FROM PARTIAL MOLAL VOLUME AND COMPRESSIBILITY DATA Before proceeding to calculate yp+/y°+ and Kp/K° for sea-water solutions, an examination will be made of the errors involved in the pressure coefficients due to errors in the values of V and k.

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