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What are the differences between carbon dioxide solubility (miscibility, reaction) in liquid water when in gaseous ($\pu{<38 bar}$) and liquid ($>\pu{38 bar}$) phase? The temperature in my experiments is usually between $0$ and $\pu{5\!^\circ C}$. Is there more phase - interface for the reaction between water and $\ce{CO2}$ 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? When observing a pressure drop in a closed stirred vessel with liquid water and $\ce{CO2}$ on top of it, the pressure drop is much larger for gaseous $\ce{CO2}$ than for the liquid $\ce{CO2}$, this does not however imply a larger solubility? In my understanding it just means, that the liquid $\ce{CO2}$ is not that compressible and will mix in a different manner than gas and liquid water, resulting in a lower pressure drop.

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  • $\begingroup$ The water doesn't care wether there is also some liquid CO2 in the same vessel. I'll doubt you find any significant change of CO2 solubility at 38 bars. $\endgroup$
    – Karl
    Sep 12, 2018 at 18:32
  • $\begingroup$ related, though I do not have access: link.springer.com/article/10.1023/A:1015294905132 $\endgroup$
    – A.K.
    Sep 12, 2018 at 20:56

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At a given temperature a mixture of gaseous $\ce{CO2}$ and liquid $\ce{CO2}$ will have a particular pressure. Thus more liquid $\ce{CO2}$ doesn't mean that more $\ce{CO2}$ will dissolve in the water.

Obviously liquid $\ce{CO2}$ has a lot more matter per unit volume than gaseous $\ce{CO2}$. So a little liquid $\ce{CO2}$ makes a lot of $\ce{CO2}$ gas.

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