Hello Vicente, Wash the CHCl3 with water to remove the ETOH then dry it over CaCl2 or K2CO3. then distillation over CaCl2 or P2O5.

Have a look at Purification of Laboratory Chemicals from DD Perrin and WL Armarego.

or, just buy a bottle of anhydrous CHCl3 from sigma aldrich: $100 fo 1L

Hello Vicente, Wash the CHCl3 with water to remove the ETOH then dry it over CaCl2 or K2CO3. then distillation over CaCl2 or P2O5.

Have a look at Purification of Laboratory Chemicals from DD Perrin and WL Armarego.

or, just buy a bottle of anhydrous CHCl3 from sigma aldrich: $100 fo 1L

I use the same procedure as Laurent Bornaghi. It really works for most applications.

Reflux over P2O5 for 1 hr (to sequester H2O and EtOH), and distill. First fraction (~5%) push in waste (it can be used for washings of receiver bottle).

For long-term storage keep dry CHCl3 in darkness under argon and silver chips (better is usage of silvered bottles).

I used a mixture of anhydrous CaCl2/anhydrous MgSO4/anhydrous Na2SO4 and molecular sieves in 1:1:1:1 proportions by weight. Alcohol is trapped quite good in calcium chloride, and the mix works quite well to capture the water and possibly other impurities.

Dry chloroform over molecular sieves & you can get it 99.9% dry. Don't use sodium for the purpose of drying chlorinated hydrocarbons. Other drying agents may include what the scholars mentioned above such as the sulfates.

Hello Marti ,first wash your solvent with water and than dry after that apply any( CaCl2 or P2O5 or Pb/Na or Molecular sieve 0.4 nm) drying agent. You can also apply Activated alumina which are very porous in nature and it available in form of Aluminium Oxide with high surface area for adsorption of liquid and gases without any change in form. Activated alumina may be regenerated to its original adsorption efficiency by heating to a temperature between (177-316°C).

Another method is simple distillation on rotavapour .

Hello, tank you very much for your helpful comments.

I washed a sample of CHCl3 (which contained 0.5-1% of EtOH) two times with water, then I dried the organic layer over oven dried K2CO3. Then filter over P2O5 and distill (discard first fraction ~5% ), then keep the distilled dry CHCl3 in darkness over activated 4A molecular sieves (owen dried) for short them storage.

I performed the reaction using this solvent and I worked nicely.

I store it over CaH2 and distill some whenever the need arises.

All the methods above would work. The question is why do you need it dry? Only very specific applications would require it really dry and free of protic impurities. In most cases where you need a dry halogenated solvent people use CH2Cl2 - much more stable and less reactive solvent.

Wash with 5% sulphuric acid, water and then with brine solution, dry it over anhydrous calcium chloride and distill over anhydrous potassium carbonate. Store it over oven dried 4A molecular sieves.

Reflux the commercially available chloroform over calcium hydride for about an hour. It will take care of any water in the solvent along with the ethanol stabilizing it. Then distil it in a stream of argon or nitrogen. As Beniamin Pintea suggested, you can keep the solvent in a flask over calcium hydride and distil portions of it as necessary. Be careful using septa though: they tend to swell and fall apart in presence of chloroform vapors. Good luck!

Remember that EtOH is a stabilizer. If you remove it, I advise you to hold the chloroform in a 100% dark bottle (use the aluminum foil to wrap the bottle). You should then be careful - without stabilizer it could product gases that raise the pressure in the bottle. Also advise the use of molecular sieves.

In my experience, you can use drying it in present of molecular sieves. don't use any more material to more purification. after 24 hrs drying on molecular sives you can receive to 99% purified CHCl3. after that, in the case of control safety, it should be better that use of distillation to receive to 99.9%.

Hello, use alumin Al2O3 neutral or basic, It is an efficient drying agent for cloroform and removal peroxides. 5% w/v loading giving extremely dry solvent. So, I suggest 48hrs drying on Al2O3, after filtration, use the distillation to achieve your purification

Add CaH2 and stir overnight followed by distillation. Store it over 4A Molecular seives.

Chloroform forms phosgene during prolonged storage.

1. CHCl3 refluxed with P2O5 for overnight then distilled.

Add CaH2 in distilled chloroform stir for overnight again distilled and stored on molecular sieves.

I usually get dried chloroform by distilling chloroform with CaH2.

Read "Purification of Laboratory Chemicals" (Seventh Edition), p. 133. please:

Chloroform [67-66-3] M 119.4, b 61.2o, d15 1.49845, d10 1.47060, n15 1.44858. It reacts slowly with oxygen, or oxidising agents, when exposed to air and light, giving, mainly, phosgene, Cl2 and HCl. Commercial CHCl3 is usually stabilised with up to 1% of EtOH or of dimethylaminoazobenzene. Simplest purifications involve washing with water to remove the EtOH, drying with K2CO3 or CaCl2, refluxing with P2O5, CaCl2, CaSO4 or Na2SO4, and distilling. It must not be dried with sodium. The distilled CHCl3 should be stored in the dark to avoid photochemical formation of phosgene. In an alternative purification, CHCl3 (500ml) was shaken (mechanically) with several small portions of 12% H2SO4 for 1 hour, washed thoroughly with water, saturated NaHCO3, washed again with water, and dried over CaCl2 or K2CO3 (100g) for 1 hour before filtering and distilling. After further drying for a short time over P2O5, the CHCl3 was redistilled and stored over Drierite in the dark [Reynolds & Evans J Am Chem Soc 60 2559 1938]. EtOH can be removed from CHCl3 by passage through a column of activated alumina, or through a column of silica gel 4-ft long by 1.75-in diameter at a flow rate of 3ml/minute. (The alumina column, which can hold about 8% of its weight of EtOH, is regenerated by air drying and then heating at 600o for 6 hours. It is pre-purified by washing with CHCl3, then EtOH, leaving in conc H2SO4 for about 8 hours, washing with water until the washings are neutral, then air drying, followed by activation at 600o for 6 hours. Just before use it is reheated for 2 hours at 154o.) [McLaughlin et al. Anal Chem 30 1517 1958.] Carbonyl-containing impurities can be removed from CHCl3 by percolation through a Celite column impregnated with 2,4-dinitrophenylhydrazine (DNPH), phosphoric acid and water. (Prepared by dissolving 0.5g DNPH in 6ml of 85% H3PO4 by grinding together, then mixing with 4ml of distilled water and 10g of Celite.) [Schwartz & Parks Anal Chem 33 1396 1961]. Chloroform can be dried by distillation from powdered type 4A Linde molecular sieves. For use as a solvent in IR spectroscopy, chloroform is washed with water (to remove EtOH), then dried for several hours over anhydrous CaCl2 and fractionally distilled. This treatment removes material absorbing near 1600 cm–1. (Percolation through activated alumina increases this absorbing impurity). [Goodspeed & Millson Chem Ind (London) 1594 1967, Beilstein 1 IV 42.] Rapid purification: Pass through a column of basic alumina (Grade I, 10g/ml of CHCl3), and either dry by standing over 4A molecular sieves, or alternatively, distil from P2O5 (3% w/v). Store away from light (to avoid formation of phosgene which is tested by shaking with conc NH3 forming urea) and use as soon as possible.

A direct and simple way that I have used to dry chloroform is to add a sufficiency of phosphorus pentoxide and stir for about 1hr, then distil, This effectively removes the ethanol, Storage in a dark brown bottle under nitrogen or argon will avoid the light-induced aerial oxidation that is the basic problem of unstabilized chloroform.

Francis Johnson,

Stony Brook

We are frequently using dry chloroform for Vilsmeier Haack reaction with Phosphorus tribromide, DMF and suitable ketones. We are using anhyd. Calcium Chloride for preliminary drying (after digesting over it for 5-6 hours distilling it). After distillation we are again distilling it by adding sufficient amount phosphorus pentoxide and redistilling it protecting from moisture. For our work it is sufficiently pure. Normally we do not store it for prolonged time..

The best way to do this with the minimum of effort is to pass the chloroform through basic alumina to remove HCl and EtOH.  Then distill from P2O5 onto microwave activated 4A molecular sieves and some silver foil or silver wire.  Store in the dark and use within a week.

CHCl3 (and other similar solvents) has a bad tendency to foam when evaporating after using it as extractant from aqueous phases. CHCl3 can be dryed with any of the common (non-basic!)  drying agents, like suggested above. I would also strongly recommend reading books about this, I can add Vogel's claccic book to the ones listed above. 

So, common drying agents, like MgSO4. For reagent use, peter Caruso's recommendation above is excellent.

 I know about a case in the old days in my old U, , where someone (must have been a very ignorant person) pressed Na wire directly into CHCl3. After some delay, the whole thing exploded violently and a person lost his hand. There used to be scars in the masonry. As students, we were told this story as a warning. 

I've actually SEEN someone squeeze Na wire into CHCl3 in an attempt to dry it.  From memory the solution started boiling immediately with copius evolution of H2 and CCl2.

I recall that  In one of the earlier editions (1940's) of Partington's "Inorganic Chemistry" there is an experiment where tit is recommended (with caution) to form by gentle heating  an amalgam with  pea-sized  amounts of sodium and potassium in a large test tube. Chloroform was then to be added and the tube then tossed some distance. The author states that when the tube hits the ground there is a violent explosion. Not to be repeated unless you are highly dextrous!!!

                                Francis Johnson

Well, "war stories" do have a didactic effect!   

However, the Lassaignes test (decomposing with Na) on Chloroform seemed to go reasonably safely; probably due to the amount and proportion of reagents. I do not recall anything dangerous with that, neither doing it nor teaching it in practical courses..

just be carefully, side effect of chloroform drying with p2o5 is production of phosgene.

With dry calcium dichloride

Mole sieves, I use them all the time. You can also by chloroform that stablized with amylene instead of ethanol (which is what I use) then I just add a handful of 3A mole sieves. Works great.

I am using DriSolv Chloroform after degassing with Freeze Thaw Pump. I stored in a dark brown bottle.

Distillation over CaH2 or P2O5 works well

Simply i put chloroform with CaCl2 for overnight, then reflux for 3 hour and then collect the distilled chloroform by distillation method.

dry over calcium hydride

Distillation over Calcium hydride or phosphorus pentaoxide is pretty ok especially for the HPLC grade. Personally, I heat/reflux this for couple of hours before collecting the distillate. To ensure complete elimination of water especially for highly moisture sensitive reactions, I do use freshly activated molecular sieves when carrying out the reaction.

I always used Calcium hydride for the distillation of the HPLC grade.

Use molecular sieves 4a or 3a to get any dry solvent..................................

Use CuSO4 or molecular sieves.

Chloroform [67-66-31 M 119.4, b 61.2O, d15 1.49845, d10 1.47060, n15 1.44858. Reacts slowly with oxygen or oxidising agents, when exposed to air and light, giving, mainly, phosgene, C12 and HCl. Commercial CHC13 is usually stabilized by addn of up to 1% EtOH or of dimethylaminoazobenzene. Simplest purifications involve washing with water to remove the EtOH, drying with K2CO3 or CaC12, refluxing with P2O5, CaC12, CaS04 or Na2S04, and distilling. It must not be dried with sodium. The distd CHC13 should be stored in the dark to avoid photochemical formation of phosgene. As an alternative purification, CHC13 can be shaken with several small portions of conc H2SO4, washed thoroughly with water, and dried with CaC12 or K2CO3 before filtering and distilling. EtOH can be removed from CHC13 by passage through a column of activated alumina, or through a column of silica gel 4-ft long by 1.75-in diameter at a flow rate of 3ml/min. (The column, which can hold about 8% of its weight of EtOH, is regenerated by air drying and then heating at 6Oo0 for 6h. It is pre-purified by washing with CHC13, then EtOH, leaving in conc H2SO4 for about 8hr, washing with water until the washings are neutral, then air drying, followed by activation at 600° for 6h. Just before use it is reheated for 2h to 154O.) [McLaughlin, Kaniecki and Gray AC 30 1517 19581. Carbonyl-containing impurities can be removed from CHC13 by percolation through a Celite column impregnated with 2,4-dinitrophenylhydrazine, phosphoric acid and water. (Prepared by dissolving 0.5g DNPH in 6ml of 85% H3P04 by grinding together, then mixing with 4ml of distilled water and log of Celite.) [Schwartz and Parks AC 33 1396 19611. Chloroform can be dried by distn from powdered type 4A Linde molecular sieves. For use as a solvent in IR spectroscopy, chloroform is washed with water (to remove EtOH), then dried for several hours over anhydrous CaC12 and fractionally distd. This treatment removes material absorbing near 1600 cm-l. (Percolation through activated alumina increases this absorbing impurity). [Goodspeed and Millson

Chemistry & Industry (London) 1594 19671

Using molecular sieves is so useful try to heat up the molecular sieves first under vacuum and then leave it to cool down and transfer it to RBF and add the fresh chloroform and insert insert N2 for 5 min the uset in the next day

The more easy way is destilation from calcium carbide

Normally, I use the same procedure with DCM.

I reflux the solvent with calcium chloride for couple of hours before collecting the distillate under inert atmosphere (nitrogen atmosphere).

Use CaH2 or calcium carbide

Chloroform [67-66-31 M 119.4, b 61.2O, d15 1.49845, d10 1.47060, n15 1.44858. Reacts slowly with oxygen or oxidising agents, when exposed to air and light, giving, mainly, phosgene, C12 and HCl. Commercial CHC13 is usually stabilized by addn of up to 1% EtOH or of dimethylaminoazobenzene. Simplest purifications involve washing with water to remove the EtOH, drying with K2CO3 or CaC12, refluxing with P2O5, CaC12, CaS04 or Na2S04, and distilling. It must not be dried with sodium. The distd CHC13 should be stored in the dark to avoid photochemical formation of phosgene. As an alternative purification, CHC13 can be shaken with several small portions of conc H2SO4, washed thoroughly with water, and dried with CaC12 or K2CO3 before filtering and distilling. EtOH can be removed from CHC13 by passage through a column of activated alumina, or through a column of silica gel 4-ft long by 1.75-in diameter at a flow rate of

3ml/min. (The column, which can hold about 8% of its weight of EtOH, is regenerated by air drying and then heating at 6Oo0 for 6h. It is pre-purified by washing with CHC13, then EtOH, leaving in conc H2SO4 for about 8hr, washing with water until the washings are neutral, then air drying, followed by activation at 600° for 6h. Just before use it is reheated for 2h to 154O.) [McLaughlin, Kaniecki and Gray AC 30 1517 19581. Carbonyl-containing impurities can be removed from CHC13 by percolation through a Celite column impregnated with 2,4-dinitrophenylhydrazine, phosphoric acid and water. (Prepared by dissolving 0.5g DNPH in 6ml of 85% H3P04 by grinding together, then mixing with 4ml of distilled water and log of Celite.) [Schwartz and Parks AC 33 1396 19611. Chloroform can be dried by distn from powdered type 4A Linde molecular sieves. For use as a solvent in IR spectroscopy, chloroform is washed with water (to remove EtOH), then dried for several hours over anhydrous CaC12 and fractionally distd. This treatment removes material absorbing near 1600 cm-l. (Percolation through activated alumina increases this absorbing impurity). [Goodspeed and Millson Chemistry & Industry (London) 1594 19671