Carbon dioxide in liquid and gaseous phases with liquid water

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Discussion Overview

The discussion focuses on the solubility and interaction of carbon dioxide in both gaseous and liquid phases when mixed with liquid water. It explores the effects of pressure and temperature on solubility, particularly in the context of experiments conducted at low temperatures (0 to 5°C) and specific stirring conditions (500 rpm).

Discussion Character

  • Exploratory
  • Technical explanation
  • Debate/contested

Main Points Raised

  • One participant questions the role of the Poynting correction, suggesting it may only apply to the fugacity of the liquid and asks about the non-ideality of the vapor phase mixture.
  • Another participant presents a formula related to the Poynting correction and Henry's constant, seeking clarification on the interaction between gaseous and liquid CO2 with water, particularly regarding solubility at different pressures.
  • There is a query about whether more CO2 dissolves at lower pressures due to the accessibility of gaseous CO2 compared to liquid CO2.
  • One participant notes that the non-ideal phase equilibrium behavior of mixtures at high pressures is complex and references a textbook for further details.

Areas of Agreement / Disagreement

Participants express differing views on the application of the Poynting correction and the implications for solubility in gaseous versus liquid phases. The discussion remains unresolved regarding the specific interactions and solubility behaviors of CO2 in these phases.

Contextual Notes

The discussion touches on complex interactions that may depend on various assumptions about phase behavior and the definitions of solubility in different states. The influence of pressure and temperature on these interactions is also highlighted but not fully resolved.

Zuzana Sediva
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What are the differences between carbon dioxide solubility (miscibility, reaction) in liquid water when in gaseous (<38 bar) and liquid (>38 bar) phase? The temperature in my experiments is usually between 0 and 5°C. The stirring speed is around 500 rpm.
Is the solubility given apart from pressure and temperature by the co2-water interface?
Is there more phase - interface for the reaction between water and CO2 in the gaseous phase? According to Henry's law for real gases (including a Poynting correction), the solubility should rise with the fugacity of the vapor. How is it however, when the carbon dioxide is liquid? More CO2 should dissolve at higher pressures (CO2 in liquid phase), however the liquid CO2 - liquid water interface should be harder to achieve than the gaseous CO2-liquid water interface. Thank you very much.
 
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Doesn’t the Poyntong correction apply only to the fugacity of the liquid? Are you considering non-ideality of the vapor phase mixture?
 
@ Chestermiller
Yes, the Poynting correction is at the Henry's constant for CO2 in the water solvent:
x_CO2=f_CO2/(H*exp^(V_co2 in water*(p-p_w))/(RT)), where H is the Henry constant for CO2 in water;

My question is more, how does CO2 and water interact when CO2 is gaseous and when liquid? Is there actually more dissolved at lower pressures because gas is more accessible to water than liquid CO2 or the other way around? The law above is clear until CO2 is gaseous. When CO2 is liquid, what happens?
 
Zuzana Sediva said:
@ Chestermiller
Yes, the Poynting correction is at the Henry's constant for CO2 in the water solvent:
x_CO2=f_CO2/(H*exp^(V_co2 in water*(p-p_w))/(RT)), where H is the Henry constant for CO2 in water;

My question is more, how does CO2 and water interact when CO2 is gaseous and when liquid? Is there actually more dissolved at lower pressures because gas is more accessible to water than liquid CO2 or the other way around? The law above is clear until CO2 is gaseous. When CO2 is liquid, what happens?
The non-ideal phase equilibrium behavior of mixtures at high pressures and with aqueous ionic solutions is too extensive to be covered in detail here. I refer you to Introduction to Chemical Engineering Thermodynamics by McCabe and Smith for a complete treatment.
 

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