Solutions: Equilibrium of Salts in Solution

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Discussion Overview

The discussion revolves around the equilibria of sulfur compounds in solution, specifically focusing on the behavior of SO2, HSO3-, and SO32- in aqueous environments. Participants explore mass and charge balances, the implications of different initial concentrations of sulfur species, and the effects of adding various salts to the system. The scope includes theoretical considerations and mathematical reasoning related to chemical equilibria.

Discussion Character

  • Exploratory
  • Technical explanation
  • Mathematical reasoning
  • Debate/contested

Main Points Raised

  • One participant presents equilibria involving SO2, HSO3-, and SO32- and proposes that the initial concentration of sulfur determines the equilibrium concentrations of all species.
  • Another participant questions the need for mass balances for hydrogen and oxygen, suggesting that these balances are essential for a complete understanding of the system.
  • Concerns are raised about the number of variables and equations, with one participant asserting that there are six variables rather than five due to the inclusion of water's concentration.
  • Participants discuss the implications of adding different sulfur species (SO2, HSO3-, SO32-) and how they affect the total amounts of hydrogen and oxygen in the system.
  • There is a debate about the charge balance when adding salts like NaHSO3 or Na2SO3, with one participant emphasizing the importance of including sodium ions in the charge balance equations.
  • Some participants express a desire to simplify the discussion by assuming dilute solutions where activity equals concentration for solutes, while others challenge this assumption.
  • There is a discussion about the differences in equations when adding salts versus sulfur dioxide, particularly regarding the treatment of sodium ions and their impact on charge balance.

Areas of Agreement / Disagreement

Participants do not reach consensus on several key points, including the treatment of water's concentration, the necessity of mass balances for hydrogen and oxygen, and the implications of adding different sulfur species. Multiple competing views remain regarding the effects of various initial conditions on the equilibria.

Contextual Notes

Participants acknowledge the complexity of the relationships between activities and concentrations in non-dilute solutions, as well as the potential need for advanced models like Debye-Hückel theory for ionic substances.

  • #31
Come on, try to work out something yourself!
Big-Daddy said:
What do you mean? Can you just write the one equation?

The problem with Na+ conservation is that Na+ is also contributed to by another salt.

Of course, but ##c_0(NaHSO3)## is known as it is completely dissolved, at least, that's what you were assuming.
 
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  • #32
I'm sorry, I've tried and I don't know the answer.
 
  • #33
Set up the conservation equation for Na and use it to eliminate c0(Na2SO3)=n0(Na2SO3)/V, where n0(Na2SO3) is the total amount of dissolved Na2SO3) (i.e. c0(Na2SO3) is an additional variable in your system).
 
  • #34
Ok, what if I then added K2SO3 up to saturation? Is it

Mass Balance for S: (1/2) * [K+] + (1/2) * ([Na+] - c0[NaHSO3]) + c0[NaHSO3] = [SO2] + [HSO3-] + [SO32-]
 

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