Obtaining Chlorosulphonic Acid (HSO3Cl)

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Discussion Overview

The discussion centers around the theoretical methods for obtaining chlorosulphonic acid (HSO3Cl) and the relative strengths of hydrochloric acid (HCl) and sulfuric acid (H2SO4). Participants explore various chemical reactions and the implications of acid strength in these processes.

Discussion Character

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

Main Points Raised

  • One participant proposes that chlorosulphonic acid can be obtained by dissolving hydrochloric acid in sulfuric acid, suggesting the reaction H2SO4 + HCl = HSO3Cl + H2O.
  • Another participant challenges this idea, recommending thionyl chloride-mediated chlorination of sulfuric acid as a more effective method, while also mentioning alternatives like phosphorus trichloride and phosphorus pentachloride.
  • There is a debate regarding the relative strengths of HCl and H2SO4, with some participants asserting that HCl is stronger, while others argue based on acid dissociation constants that sulfuric acid should be stronger.
  • One participant cites discrepancies in pKa values from various textbooks, questioning why the equilibrium in the reaction 2NaCl + H2SO4 ⇌ 2HCl + Na2SO4 shifts leftward, complicating the understanding of acid strength.
  • Another participant suggests that the eagerness of an acid to participate in reactions is a simple explanation for acid strength, but acknowledges that the situation is more complex.
  • One participant expresses skepticism about the proposed reactions and the behavior of acids in solution, emphasizing the tendency of strong acids to dissociate in water.

Areas of Agreement / Disagreement

Participants express differing views on the strength of hydrochloric acid compared to sulfuric acid, with no consensus reached on the theoretical methods for obtaining chlorosulphonic acid. The discussion remains unresolved regarding the implications of acid strength on chemical equilibria.

Contextual Notes

Participants reference various acid dissociation constants and textbooks, indicating that there may be limitations in the available data and definitions used in the discussion. The complexity of acid behavior in reactions is acknowledged but not fully resolved.

dextercioby
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Hello,

I have a question.Can one (theoretically) obtain Chlorsulphonic acid by disolving chlorhydric acid into sulphuric acid like follows:
H_{2}SO_{4} +HCl=HSO_{3}Cl+H_{2}O.

If not,how can one obtain the Chlorsulphonic acid?
 
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It is not wrong, as hydrochloric acid is stronger than sulfuric acid, but dehydration spoils the logic behind this; so I recommend that you try thionyl chloride-mediated chlorination of sulfuric acid:

SOCl_2+HO-SO_2-OH \longrightarrow Cl-SO_2-OH + SO_2 + HCl

There are some alternatives to thionyl chloride, but this is the best. You may also use phosphorus trichloride (which gives phosphite acid, H_3PO_3) or phosphorus oxytrichloride (which gives phosphate acid, H_3PO_4), or even phosphorus pentachloride (giving phosphorus oxytrichloride and then phosphate acid), etc.
 
chem_tr said:
It is not wrong, as hydrochloric acid is stronger than sulfuric acid, but dehydration spoils the logic behind this; so I recommend that you try thionyl chloride-mediated chlorination of sulfuric acid:

SOCl_2+HO-SO_2-OH \longrightarrow Cl-SO_2-OH + SO_2 + HCl

There are some alternatives to thionyl chloride, but this is the best. You may also use phosphorus trichloride (which gives phosphite acid, H_3PO_3) or phosphorus oxytrichloride (which gives phosphate acid, H_3PO_4), or even phosphorus pentachloride (giving phosphorus oxytrichloride and then phosphate acid), etc.

Okay,thenx for the info provided.But yet,i have another question:
I remember that sulphuric acid's first acid constant is larger than the chlorhydric's one,and smaller than the ones by iodhydric acid,perchloric and permanganic acids.
So,that,but not only that,should make sulphuric acid stronger than the chlorhydric one,right??
 
It is not correct. I am clearly sure that HCl is more powerful than H2SO4[\sub]. Oxygen does not readily give proton away; even if it is attached to an ametal like phosphorus or boron.
 
chem_tr said:
It is not correct. I am clearly sure that HCl is more powerful than H2SO4[\sub]. Oxygen does not readily give proton away; even if it is attached to an ametal like phosphorus or boron.


You're right,i've searched through many textbooks upon the various theories for acids and bases,but the numbers,awkwardly,do not match.For instance,the numbers in "Lehrbuch der Chemie" (7 authors,VEB Deutscher Verlag fur Grundstoffindustrie,Leipzig,1971) are pK_{S} \sim -3 for the sulphuric acid for the reaction
H_{2}SO_{4}+H_{2}O\rightleftharpoons HSO_{4}^{-}+H_{3}O^{+}
,while for the hydrochloric one pK_{S} \sim -7,in between which there is a huge gap.In other books (French ones and Pauling's one) the gap between these numbers was smaller,but either way,they stated that the hydrocloric acid is stronger than the sulphuric one.The question ithat arises is this one;
If the hydrochloric acid is stronger than the sulphuric one,why does the chemical equilibrium in the reaction:
2NaCl+H_{2}SO_{4} \rightleftharpoons 2HCl+Na_{2}SO_{4} shift leftwards,so that u cannot obtain sulphuric acid from hydrochloric acid and the sulphuric acid's salts?
 
Last edited:
The powerful the acid, the eager to be involved in reaction... It is just that simple, I think.
 
chem_tr said:
The powerful the acid, the eager to be involved in reaction... It is just that simple, I think.

It ain't that simple.Not only hydrochloric acid's stronger than the sulphuric one.Yet one cannot obtain sulphuric acid from its salts and a stronger acid.There has to be a deeper explanation...I am sure of it.
It's just that i don't see it...
 
In response to the first post,

See if this makes sense to you, assuming that your proposed reaction takes place to a significant yield (relative to the dissociation reaction of each of the strong acids)...we have an acid solution, furthermore by adding sufuric acid (or vice versa) to the solution decreases its pH. It is essentially what your saying, I believe this will not happen. Remember that the acids in consideration have a very strong tendendcy to dissociate in water, increasing pH.
 

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