Preparation of Chromium (III) Salts

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Discussion Overview

The discussion centers on the preparation of chromium (III) salts, specifically focusing on the dissolution of chromium (III) oxide (Cr2O3) in concentrated hydrochloric acid (HCl) to form chromium (III) chloride. Participants explore various methods, conditions, and reagents that may facilitate this reaction, including the potential need for heating and the use of alternative acids.

Discussion Character

  • Exploratory
  • Technical explanation
  • Debate/contested
  • Experimental/applied

Main Points Raised

  • One participant notes that Cr2O3 does not dissolve readily in concentrated HCl at room temperature and questions whether heating would help.
  • Another participant references a method involving the dissolution of hydrated chromium oxide in hydrochloric acid and mentions the potential for chlorine gas evolution when using dichromate.
  • Concerns are raised about the reactivity of pottery grade Cr2O3 compared to freshly precipitated hydrated oxide, with suggestions to try sulfuric acid and to mill the oxide into a fine powder.
  • One participant suggests that chromium metal produced from a thermite reaction with Cr2O3 and aluminum dissolves quickly in 30% HCl, proposing this as an alternative approach.
  • Another participant inquires about using charcoal for a thermite reaction due to the lack of aluminum and expresses interest in synthesizing sodium dichromate (Na2Cr2O7) instead.
  • Instructions for preparing potassium dichromate (K2Cr2O7) are provided, indicating that sodium salts can be substituted to produce Na2Cr2O7 using Cr2O3 without prior acid reaction.
  • A later reply questions the reagent grade of the chromium (III) oxide and suggests that aging or redox reactions might affect its reactivity.

Areas of Agreement / Disagreement

Participants express various viewpoints on the effectiveness of different acids and methods for dissolving Cr2O3, indicating that multiple competing views remain. The discussion does not reach a consensus on the best approach or the reasons for the observed lack of reactivity.

Contextual Notes

Participants mention potential limitations related to the reactivity of different grades of chromium (III) oxide, the effects of aging, and the need for specific conditions such as heating or milling the oxide. These factors remain unresolved in the discussion.

Who May Find This Useful

This discussion may be of interest to those involved in chemistry, particularly in the synthesis of chromium compounds, as well as individuals exploring methods for dissolving metal oxides in acids.

MaximumTaco
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OK, so i have Cr(III) Oxide, Cr2O3, and i wish to dissolve this in conc. HCl to form Cr(III) Chloride - however, at room temperature, this reaction just doesn't seem to work readily - i would have thought it would. Would heating facilitate the desired reaction? Would the use of another acid, such as conc. Sulphuric acid, react more readily with the oxide without the need for heat?
 
Chemistry news on Phys.org
Look here,
http://www.roguesci.org/theforum/chemistry-related/4725-review-chromium-compound-synthesis.html

A few quotes from the site,
Chromic chloride: May be prepared by dissolving hydrated chromium oxide in hydrochloric acid and evaporating off the liquid. It may also be prepared by adding, by weight, 1 part of either sodium or potassium dichromate to 6 parts of hydrochloric acid and gently heating for a few seconds to initiate the reaction. Chlorine gas will be evolved, so do this reaction is a well ventilated area.
Chromic trichloride classic method is to heat chromic oxide (Cr2O3) in a stream of sulphur chloride or carbon tet vapour in a tube furnace. Not very convenient. Dissolving Cr2O3 in concentrated hydrochloric acid and then evaporating to dryness produces a hydrate, if this is heated strongly it loses virtually all of the water but some decomposition to C2O3 occurs colouring the mass green. If the residue is heated to a high temperature, 700C seems in the right range, the chromic chloride sublimes leaving the chromic oxide behind.

I've had Cr2O3 sitting in a test tube with 30% hydrocloric acid for over 24 hours now, there seem to be nothing happening at all, the acid is still without any sign of turning Cr+3 - green. Is something wrong with the procedure Marvin mentioned or does it need high temperature or something? The difference between 30 and 37% can't be that great, can it?
I also can't see where anything I've quoted talks about adding Cr2O3 to hydrochloric acid. Nitro's method talks about chromium metal which I had previously thought not active enough to liberate hydrogen but I'm prepaired to suspend my disbelief on that count.

Pottery grade Cr2O3 is much much less reactive than the freshly precipitated hydrated oxide. Again I can't vouch for this, the closest experience I've had is with lapidary ceric oxide in my somewhat successful attempts to produce ceric sulphate, another potent oxidiser. I would be inclined to try sulphuric acid of different concentrations, starting with concentrated, and pounding the oxide into a very very find powder first. Reducing to chromium with aluminium is one possibility or its back to a furnace until you get enough in salt form to recycle.
Cr-metal from Cr2O3/Al thermite dissolves fast in 30% HCl.

You might try making some Chromium Oxide thermite to produce Chromium metal, then use this to prepare CrCl3.
 
I don't have Al to do a thermite reaction - i wonder if heating with charcoal will do it?

I'll try milling the powder very fine, and try conc. H2SO4 and see if it is any different.

I'm actually trying to synthesize Na2Cr2O7.
 
Here are instructions for the preparation of K2Cr2O7,
http://www.frogfot.com/synthesis/kdichromate.html
You easily substitute Sodium Salts into the reaction (as opposed to Potassium) to make it Na2Cr2O7.
Using this method, you could use your Cr2O3 as it is, without reacting it with acid first.
 
Last edited:
MaximumTaco said:
OK, so i have Cr(III) Oxide, Cr2O3, and i wish to dissolve this in conc. HCl to form Cr(III) Chloride - however, at room temperature, this reaction just doesn't seem to work readily - i would have thought it would. Would heating facilitate the desired reaction? Would the use of another acid, such as conc. Sulphuric acid, react more readily with the oxide without the need for heat?

What reagent grade of the chromium III oxide are you employing? You may need to recrystallize the oxide. Or at times, the sample may have aged to much and undergone chemical changes (redox reactions with oxygen for example). It may be the case that something is redoxing the Cr III in the sample.

Are you having trouble with the reaction overall or just the dissolution of the sample oxide?
 

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