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Temperature effects on the activity coefficient of the bicarbonate ion


Cadena-Cepeda, Fernando (1977) Temperature effects on the activity coefficient of the bicarbonate ion. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/DX7Y-8N64.


Natural waters may be chemically studied as mixed electrolyte solutions. Some important equilibrium properties of natural waters are intimately related to the activity-concentration ratios (i.e., activity coefficients) of the ions in solution. An Ion Interaction Model, which is based on Pitzer's (1973) thermodynamic model, is proposed in this dissertation. The proposed model is capable of describing the activity coefficient of ions in mixed electrolyte solutions. The effects of temperature on the equilibrium conditions of natural waters and on the activity coefficients of the ions in solution, may be predicted by means of the Ion Interaction Model presented in this work.

The bicarbonate ion, HCO3-, is commonly found in natural waters. This anion plays an important role in the chemical and thermodynamic properties of water bodies. Such properties are usually directly related to the activity coefficient of HCO3- in solution. The Ion Interaction Model, as proposed in this dissertation, is used to describe indirectly measured activity coefficients of HCO3- in mixed electrolyte solutions.

Experimental pH measurements of MCl-MHCO3 and MCl-H2CO3 solutions at 25°C (where M = K+, Na+, NH4+, Ca2+ or Mg2+) are used in this dissertation to evaluate indirectly the MHCO3 virial coefficients. Such coefficients permit the prediction of the activity coefficient of HCO3- in mixed electrolyte solutions. The Ion Interaction Model is found to be an accurate method for predicting the activity coefficient of HCO3- within the experimental ionic strengths (0.2 to 3.0 m). The virial coefficients of KHCO3 and NaHCO3 and their respective temperature variations are obtained from similar experimental measurements at 10° and 40°C. The temperature effects on the NH4HCO3, Ca(HCO3)2, and Mg(HCO3)2 virial coefficients are estimated based on these results and the temperature variations of the virial coefficients of 40 other electrolytes.

Finally, the Ion Interaction Model is utilized to solve various problems of water chemistry where bicarbonate is present in solution.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Environmental Engineering
Degree Grantor:California Institute of Technology
Division:Engineering and Applied Science
Major Option:Environmental Science and Engineering
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Morgan, James J.
Thesis Committee:
  • Unknown, Unknown
Defense Date:20 December 1976
Record Number:CaltechTHESIS:04292014-085219405
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:8203
Deposited By: Benjamin Perez
Deposited On:29 Apr 2014 17:18
Last Modified:09 Nov 2022 19:20

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