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Author: Subject: Calcium Hydroxide and Hydrochloric Acid Reaction
MrPhlopper
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[*] posted on 23-5-2013 at 09:02
Calcium Hydroxide and Hydrochloric Acid Reaction


For fun, I was trying to make a small quantity of Calcium Chloride according to this reaction:
Ca(OH)2 + 2HCl (aq) -> 2H20 + CaCl2

I added 4mL of 20% HCl onto 1 gram of dry Ca(OH)2. Unexpectedly, a small amount of a whiteish pungent smelling gas evolved from the reaction beaker. I terminated the reaction due to this unknown foul smelling gas. On my next attempt, I added an excess of water to make a solution of Ca(OH)2 before adding my 20% HCl, and everything went as planned with no gas evolution. I titrated to pH 7 and then partially evaporated it to let CaCl2 crystals form at the bottom.

My question is what was this gas and why did it form? My best guess is that it was HCl gas, though it’s possible it could’ve been Cl2 or H2 given the atoms involved in the reaction. The only explanation that I could come up with was that the dry Ca(OH)2 was more hydrophilic and pulled some of the water from the hydrochloric acid before the reaction could even proceed. The anhydrous HCl then went up as gas. I also know that HCl gas can also be produced by dropping hydrochloric acid on dry calcium chloride. Perhaps there is a similar reaction with dry calcium hydroxide? Or is it possible that calcium chloride, formed in the reaction, desiccated the HCl? I would’ve thought that the excess water in the nonconcentrated HCl solution would’ve been enough to prevent gas formation but perhaps I needed to use a lower concentration of HCl.

What do you guys think happened?
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DraconicAcid
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[*] posted on 23-5-2013 at 09:39


I suspect the heat evolved from the reaction would have boiled off some HCl.



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[*] posted on 23-5-2013 at 10:01


It's also possible that dropping the liquid on dry powder kicked some dust up, which then made it to your nose. Often when opening my bottle of NaOH, I get a whiff of something acrid - that's hydroxide dust that was disturbed when I scooped out what I needed.
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[*] posted on 23-5-2013 at 10:13


Adding a fairly concentrated, strong [in the Bronsted sense] acid like 20 % HCl to a solid strong alkali like Ca(OH)2 is nutty beyond description.

The Enthalpy of Neutralisation:

H3O+ + OH- === > 2 H2O

of - 57 kJ/mol (of acid) is enough to cause your acid to start boiling immediately, possibly almost explosively ('steam explosion').

And there's more enthalpy to be released too: with so little water present, the formed CaCl2 has no choice but to crystallise immediately, releasing more energy (heat). In the case of CaCl2 that may not have happened because it is highly soluble but there are always pockets of high concentration, where mixing is inefficient.

Anyone who wants to do neutralisation reactions using concentrated solutions should at a minimum estimate the end temperature of the mixture to avoid nasty surprises, like over-boiling and severe splattering. Trust me, I do this EVERY time when in doubt regarding the end temperature being possibly too high.

What you smelled was hydrochloric acid vapours. Very pungent and not great for your lungs either.

This bit:

Quote: Originally posted by MrPhlopper  
The only explanation that I could come up with was that the dry Ca(OH)2 was more hydrophilic and pulled some of the water from the hydrochloric acid before the reaction could even proceed. The anhydrous HCl then went up as gas.


... is simply nonsense.



[Edited on 23-5-2013 by blogfast25]




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woelen
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[*] posted on 23-5-2013 at 10:53


@blogfast25: Please be not so harsh. This action might be not the smartest thing, but MrPhlopper did this reaction on a small scale with just a single gram, so nothing serious happened. I agree that mixing strong bases with concentrated strong acids is not the wisest thing to do, but in such small amounts the effects will remain manageable. I'm quite sure that in your young and uneducated years you also sometimes did less wise things ;) I certainly did :)

@MrPhlopper: I indeed think that you smelled HCl-gas, whch escaped from the acid due to high temperatures. This gas is quite toxic, but the single whiff you obtained is too little to worry about. It is good that you terminated the experiment after you perceived the bad gas.

You can also learn something from this. Experimenting with chemicals is something which must be done with care and it is good to think about what might happen. Using small quantities also is a very good precaution. I also sometimes mix chemicals, even when I expect an extremely violent reaction, but if I do so, then I never use more than a few 100's of milligrams. At the moment I work with experiments on ClO2 (a highly explosive and quite toxic gas), but I only do these experiments with very small amounts. I did have a few explosions already, but these never are worse than loud WHOOSH sounds, due to the small scale of the experiments.
Another very important thing is that you never look into a test tube from above when a violent reaction may occur. If the content erupts into your eyes, then the experience can be disastrous. So, always point the open end of a test tube away from you.

Keep this warning in mind: The goddess of chemistry is a beautiful one, but you have to treat her with care. She can bite seriously.




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blogfast25
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[*] posted on 23-5-2013 at 11:56


Quote: Originally posted by woelen  
@blogfast25: Please be not so harsh. This action might be not the smartest thing, but MrPhlopper did this reaction on a small scale with just a single gram, so nothing serious happened.


And choosing that small scale was wise. Trouble is that some wouldn't have taken that precaution and could have suffered the consequences. Mixing Ca(OH)2 with 20 % HCl is like pouring it over KOH.

Runaways and unexpected exotherms are a common cause of accidents or at a very minimum experiments ruined. Not so long ago very experienced member 'Magpie' suffered a runaway due to an unaccounted exotherm when oxidising propylene glycol with nitric acid to malonic acid. There were no consequences but it could have ended very badly. Recently I suffered a small fire when very foolishly and absentmindedly treating potassium with methylated spirits. With unexpected heat one has to be careful, especially around potentially corrosive/toxic chemicals.

Maybe I was a bit too harsh but it's a labour of love, really...;)

[Edited on 23-5-2013 by blogfast25]




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amazingchemistry
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[*] posted on 23-5-2013 at 18:25


When estimating exothermicity, would it be as simple as looking up the enthalpy values of the reagents and of the expected products? What if we don't really know what the "expected" products should be?
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[*] posted on 24-5-2013 at 04:49


when you say foul i think H2S smell.. unless if there was impurities (in which could easily form H2S if there was sulfides present) then i dont see reason for H2S to form..

what you can try some other time is to put some ammonia next to the whole thing as described, in which you smelt something.. if its the HCl it will make a nice thick grey smoke of NH4Cl

i believe that there isnt much danger to adding an acid such as HCl (not even being 30 or 37% in this case) to a very insoluble hydroxide such as Ca(OH)2

now if we took 25% NH4OH and added 98% H2SO4 it would get pretty intense, but thats much more concentrated than HCl can get as store bought (:





~25 drops = 1mL @dH2O viscocity - STP
Truth is ever growing - but without context theres barely any such.

https://en.wikipedia.org/wiki/Solubility_table
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[*] posted on 24-5-2013 at 05:44


Quote: Originally posted by amazingchemistry  
When estimating exothermicity, would it be as simple as looking up the enthalpy values of the reagents and of the expected products? What if we don't really know what the "expected" products should be?


You need to really know what is reacting with what and what is being formed (and in what state: solid, liquid, gaseous or in solution) to be able to predict the change in enthalpy ΔH (heat released or absorbed during reaction) and in many cases that's not easy to do. 'On paper', knowing the Enthalpies of Formation of all reagents and reaction products allows you to calculate ΔH using Hess Law, as a simple addition/substraction. In practice these values aren't always known and several complications can arise from changes in state (melting, evaporating, solvation, crystallisation, etc). Often the value of ΔH is determined experimentally, using calorimetry, instead of from theory.

In the case of aqueous neutralisation reactions, one generally assumes only H3O+ + OH- === > 2 H2O proceeds and that most of the other ions present are just 'spectators' that don't influence ΔH. The calculation then becomes very simple and the end-temperature determined from ΔH = m Cp ΔT (*), assuming no heat losses or external heat sources.

(*) ΔH = m Cp ΔT: m mass of water present, Cp specific heat capacity of water, ΔT change in temperature of the solution.

In short, sometimes it's quite straightforward, sometimes it's rather challenging...



[Edited on 24-5-2013 by blogfast25]




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MrPhlopper
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[*] posted on 31-5-2013 at 08:40


Thanks for your replies everyone! The HCl gas as a result of the highly exothermic neutralization reaction seems plausible and consistent with what I observed.

I'm an inexperienced chemist and I agree this wasn't my best idea - I didn't consider the heat that would be released by the reaction. But fortunately nothing bad happened and I'll know better next time.
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chloric1
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[*] posted on 2-7-2015 at 05:33


You can use the heat of neutralization to your advantage. For example, strong ammonium hydroxide neutralize with strong HCl can make a strong ammonium chloride solution near its boiling point from room temperature acid and base. This would be quite handy for preparing slightly soluble ammonium salts such as the dichromate, vanadate, or perchlorate via saturated solutions of the sodium salts. Or if you want to reduce time to crystallize a salt. For example, neutralizing maybe a 40% sulfuric acid solution with strong solution of NaOH then putting in ice bath to crystallize the decahydrate.

[Edited on 7/2/2015 by chloric1]




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[*] posted on 29-7-2015 at 03:54


Hello MrPhlopper :)

I had a possibly similar experience making a small amount of MgCl2 from Mg and HCl.

Got distracted by the postman and didn't realize I hadn't diluted my 37% HCL :o

Had about 5g of Mg in a test tube and only added maybe 1/4-1/2ml of HCl before similar foul smelling white smoke started pouring out!

Continence of the test tube never came close to coming out of the top but made me crap my pants for half a second before I realized what I had done!

Ran away and waited for the smoke to clear and repeated the experiment with sufficiently diluted acid :)

Glad you are OK and be safe :-)

[Edited on 29-7-2015 by Dangle89]
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[*] posted on 2-8-2015 at 16:34


Quote: Originally posted by woelen  
@blogfast25:

Using small quantities also is a very good precaution. I also sometimes mix chemicals, even when I expect an extremely violent reaction, but if I do so, then I never use more than a few 100's of milligrams. At the moment I work with experiments on ClO2 (a highly explosive and quite toxic gas)


wow, check the MMS people, most totally ignorant of what they have at hand and I only read some minor domestic "issues" of 1 or 2 persons. so what you are doing with ClO2 my friend? :)
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[*] posted on 3-8-2015 at 07:16


pneumatician lolwut? What are you doing on a computer?



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Dangle89
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[*] posted on 4-8-2015 at 04:01


Quote: Originally posted by pneumatician  

wow, check the MMS people, most totally ignorant of what they have at hand and I only read some minor domestic "issues" of 1 or 2 persons. so what you are doing with ClO2 my friend? :)


Sorry this might be a stupid question but what is the MMS? Is that another country's version of the MSDS?

Googled it and only got the long name for picture messaging :P

Cheers

Dangle :)
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[*] posted on 4-8-2015 at 06:41


Miracle Mineral Supplement / or Solution.
https://en.m.wikipedia.org/wiki/Miracle_Mineral_Supplement
A particularly dangerous snake oil remedy. A solution of sodium chlorite. It is activated by addition of a food grade acid and taken internaly by unwitting fools or victims of fools.

"MMS is falsely promoted as a cure for HIV,malaria, hepatitis viruses, the H1N1 flu virus,common colds, autism, acne, cancer, and much more."

[Edited on 4-8-2015 by Bot0nist]




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[*] posted on 4-8-2015 at 07:04


My explanation is also:neatrulisation or acid-base reactions are quite exothermic.Calcium oxide hydrolysis/dissolution is exothermic(can reach water to boil)
The reaction between sodium hydroxide solution (20%) and sulphuric acid (50%)is so exotherm that this is splattering the solution everywhere.

Back tho your question.Use Ca(OH)2 suspension and add the HCl INTO the Ca(OH)2.
The smell is HCl vapour and H2S.Commercial grade lime almost always have sulphide/polysulphide impurities.
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[*] posted on 4-8-2015 at 09:19


Quote: Originally posted by Zyklon-A  
pneumatician lolwut? What are you doing on a computer?

and you, what are doing with your soul?

lolwut?
http://theactionelite.com/site/wp-content/uploads/2013/11/lo...
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[*] posted on 4-8-2015 at 09:21


Quote: Originally posted by Bot0nist  
Miracle Mineral Supplement / or Solution.
https://en.m.wikipedia.org/wiki/Miracle_Mineral_Supplement
A particularly dangerous snake oil remedy. A solution of sodium chlorite. It is activated by addition of a food grade acid and taken internaly by unwitting fools or victims of fools.

"MMS is falsely promoted as a cure for HIV,malaria, hepatitis viruses, the H1N1 flu virus,common colds, autism, acne, cancer, and much more."

[Edited on 4-8-2015 by Bot0nist]


try to edit this article in wikishit, in a moment is again the official shit.

http://g2cforum.org/
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[*] posted on 4-8-2015 at 21:54


Commercial lime contains significant amounts of calcium carbonate, particularly if it's old and has been stored poorly (reacting with the CO2 from the atmosphere).

I strongly suspect what you observed was simple the vigorous production of CO2 from the acidification of calcium carbonate impurity which carried with it HCl aerosols... very nasty on the nose (and everything else) :mad:

If so, the reaction is simply:

CaCO3(s) + 2HCl(aq) => CaCl2(aq) + CO2(g) + H2O(l)




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