Immiscible solvents

SOLVENTS     Immiscibility

Acetone can be mixed with any of the solvents listed in the column at left

Acetonitrile cyclohexane, heptane, hexane, pentane, 2,2,4-trimethylpentane

carbon tetrachloride

can be mixed with any of the solvents listed in the column at left except water

chloroform can be mixed with any of the solvents listed in the column at left except water

cyclohexane acetonitrile, dimethyl formamide, dimethyl sulfoxide, methanol, water

1,2-dichloroethane can be mixed with any of the solvents listed in the column at left except water

dichloromethane can be mixed with any of the solvents listed in the column at left except water

diethyl ether dimethyl sulfoxide, water

dimethyl formamide cyclohexane, heptane, hexane, pentane, 2,2,4-trimethylpentane, water

dimethyl solfoxide cyclohexane, heptane, hexane, pentane, 2,2,4-trimethylpentane, diethyl ether

1,4-dioxane can be mixed with any of the solvents listed in the column at left

ethanol can be mixed with any of the solvents listed in the column at left

ethyl acetate can be mixed with any of the solvents listed in the column at left except water

heptane acetonitrile, dimethyl formamide, dimethyl sulfoxide, methanol, water

hexane acetonitrile, dimethyl formamide, dimethyl sulfoxide, methanol, acetic acid, water

methanol cyclohexane, heptane, hexane, pentane, 2,2,4-trimethylpentane

methyl-tert-butyl ether

can be mixed with any of the solvents listed in the column at left except water

pentane acetonitrile, dimethyl formamide, dimethyl sulfoxide, methanol, water, acetic acid

1-propanol can be mixed with any of the solvents listed in the column at left

2-propanol can be mixed with any of the solvents listed in the column at left

tetrahydrofuran can be mixed with any of the solvents listed in the column at left

toluene can be mixed with any of the solvents listed in the column at left except water

2,2,4-trimethylpentane

acetonitrile, dimethyl formamide, dimethyl sulfoxide, methanol, water

watercarbon tetrachloride, chloroform, cyclohexane, 1,2-dichloroethane, dichloromethane, diethyl ether, dimethyl formamide, ethyl acetate, heptane, hexane, methyl-tert-butyl ether, pentane, toluene, 2,2,4-trimethylpentane

Solvents Drying and Drying Agents

Removing water from Solvents

There are various ways of removing water and other impurities from a solution. This can become a major task once the used reagents are also sensitive towards water e.g. Grignard reagents or enolates. If water is one of the products, it also has a detrimental effect on the yield and/or reaction rate. In those cases, drying agents like activated alumina¹, calcium hydride (CaH2), sodium metal (in combination with benzophenone which forms a dark blue ketyl radical), lithium aluminum hydride (LiAlH4) or phosphorous pentoxide (P4O10) are used to chemically destroy the water. The drying agents commonly used in the organic laboratories are the anhydrous forms of calcium chloride (CaCl2), sodium sulfate (Na2SO4) Calcium sulfate (CaSO4 (as Drierite) and magnesium sulfate (MgSO4).Organic liquids are considered to be wet if they contain water,but the organic liquid will still be a liquid after it is dried.

Activated Alumina

Activated alumina ¹ is a very porous form of aluminum oxide of high surface area which adsorbs liquids and gases without any change in form. Activated alumina will not soften or disintegrate when immersed in liquids. Activated alumina may be regenerated to its original adsorption efficiency by heating to a temperature between (177-316°C).

Activated alumina can be used for:

Reconditioning of mineral oils like transformer or insulating oils. Removal of oil vapor mist from compressed air. Drying of organic liquids to a moisture level of 10 ppm or below.Drying of various liquids such as Benzene, Carbon, Tetrachloride, Chlorobenzene, Ethyl Acetate, Transformer oil, Vegetable oils etc.

Solvents drying guide

TO DRY USE ONE OF THE FOLLOWING DRYING AGENTS

AlcoholsAnhydrous forms of potassium carbonate; anhydrous magnesium or calcium sulphate; quicklime.

Alkyl halidesAryl halides

Anhydrous calcium chloride; anhydrous forms of sodium sulphate, magnesium sulphate, or calcium sulphate; sodium pentoxide.

Saturated andAromatic hydrocarbons

Anhydrous calcium chloride or sulphate; metallic sodium; phosphorus pentoxide.

AldehydesAnhydrous sodium sulphate; anhydrous magnesium or calcium sulphate.

KetonesAnhydrous sodium sulphate; anhydrous magnesium or calcium sulphate; anhydrous potassium carbonate.

Organic bases(amines)

Solid potassium or sodium hydroxide; quicklime; barium oxide.

Organic acidsAnhydrous sodium sulphate; anhydrous magnesium or calcium sulphate.

Solvents: Properties and Drying agents

SolventBoiling

Pt.°C

DensityFlash

Pt.°C

Drying agent

Acetone 56 0.791 -18 K2CO3; Molecular sieve 0.3nm; CaCl2

Acetic acid 118 1.049 +40 P2O5; CuSO4

Acetic anhydride 136 1.082 +49 CaCl2

Acetonitrile 82 0.782 +6CaCl2; P2O5; K2CO3; calcium hydride; Molecular sieve 0.3nm

Aniline 184 1.022 +76 KOH; BaO

Anisole 154 0.995 +51 CaCl2; Na; distillation

Benzene 80 0.879 -10CaCl2; distillation; Na; Pb/Na; ; calcium hydride; Na wire; Molecular sieve 0.4nm

1-Butanol 117 0.810 +29 K2CO3; distillation

2-Butanol 100 0.808 +24 K2CO3; distillation

tert-Butanol 82 0.882 +11 CaO; Freezing

n-Butyl acetate 127 0.882 +33 MgSO4;

Carbon disulphide 46 1.263 -30 CaCl2P2O5;

Carbon tetrachloride 77 1.594 none distillation; P2O3; Pb/Na; Molecular sieve 0.4nm

Chlorobenzene 132 1.106 +29 CaCl2; distillation;P2O5

Chloroform 62 1.486 none CaCl2; P2O5; Pb/Na; Molecular sieve 0.4nm

Cyclohexane 81 0.799 none Na; Na/Pb; LiAlH4; Molecular sieve 0.4nm

Cyclohexanone 155 na na Distillation

Decahydronaphthalene(Dekalin)

~190 0.886 <54 CaCl2; Na; Pb/Na

Dichloromethane 40 1.325 none CaCl2; Pb/Na; calcium hydride; Molecular sieve 0.4nm

Dicyclopentadiene:(cyclopentadiene dimer)

170 na naRefractionation: distillate at 40 - 42°C. (Use at once! or keep in dry ice/acetone bath no longer than 1 Hr.)

Diethyl carbonate 126 0.975 +25 Na2SO4; K2CO3

Diethylene glycoldibutyl ether

225 0.885 +118 CaCl2; Na

Diethylene glycol dimethyl ether

155165

0.906 +70 CaCl2; Na

Diethyl ether 34 0.714 -40CaCl2; Na; Pb/Na; LiAlH4; Na wire/benzophenone; Molecular sieve 0.4nm

Di-isopropyl ether 68 0.726 -23 CaCl2; Na; Molecular sieve 0.4nm

Dimethyl formamide 153 0.950 +62 distillation; Molecular sieve 0.4nm

Dimethyl sulfoxide 189 1.101 +95 distillation; Molecular sieve 0.4nm

1,4 Dioxane 101 1.034 +11.8 CaCl2; Na; Molecular sieve 0.4nm

Ethanol 79 0.791 +12 CaO; Mg; MgO; Molecular sieve 0.3nm

Ethyl acetate 77 0.901 -4K2CO3; P2O5; Na2SO4; calcium hydride; Molecular sieve 0.4nm

Ethylenediamine:(1-2 diaminoethane)

118 na na Simple distillation.

Ethylene glycol 197 1.109 +111 distillation; Na2SO4

Ethylene glycol monoethyl ether

135 0.930 +41 distillation

Ethylene glycol monomethyl ether

125 0.965 +52 distillation

Ethyl formate 54 0.924 -20 MgSO4; Na2SO4;

Formamide 211 1.134 155 Na2SO4; CaO

Glycerol 290 1.260 +176 distillation

Heptane 98 0.684 -4 calcium hydride; Na wire

n-Hexane 69 0.659 -23Na; Pb/Na; LiAlH4; calcium hydride; Na wire/benzophenone; Molecular sieve 0.4nm

Isobutanol 108 0.803 +28 K2CO3; CaO; Mg;

Isobutyl methyl ketone 117 0.801 +15.5-4 K2CO3;

Methanol 65 0.792 +11 Mg; CaO; Molecular sieve 0.3nm

Methyl acetate 57 0.933 -10 K2CO3; CaO;

1-Methyl-2-pyrrolidone 202 1.026 +95 Na2SO4; distillation; Molecular sieve 0.4nm

Methyl Ethyl ketone 80 0.806 -44 K2CO3;

Nitrobenzene 211 1.204 +92 CaCl2; P2O5; distillation;

n-Pentane 36 0.626 -49 Na; Pb/Na;calcium hydride; Na wire

Pet ether mixture na nacalcium hydride; Na wire/benzophenone; Molecular sieve type 4A

1- Propanol 97 0.804 +15 CaO; Mg

2-Propanol 82 0.785 +12 CaO; Mg; Molecular sieve 0.3nm

Pyridine 116 0.982 +20 KOH; BaO; Molecular sieve 0.4nm

Tetrahydrofuran 66 0.887 -17.5 Molecular sieve 0.4nm

Tetrahydronaphthalene(Tetralin)

208 0.973   CaCl2; Na

Thionyl chloride 48 na na Redistill.

Toluene 111 0.867 +4 distillation; Ca; CaCl2; Na; Molecular sieve 0.4nm

Trichloroethylene 87 1.462 none distillation; Na2SO4; K2CO3

Xylene 137/140 -0.86 +25 distillation; Na; CaCl2; Molecular sieve 0.4nm

Storage of Incompatible Chemicals

Substance Incompatible with

Acetic acidChromium oxide, nitric acid, perchloric acid, peroxides, permanganates, alcohol, ethylene glycol

Acetic anhydride Hydroxyl-containing compounds e.g. ethylene glycol, perchloric acid

Acetone Concentrated nitric acid and sulphuric acid mixtures, hydrogen peroxide

Acetylene Chlorine, bromine, fluorine, copper, silver, mercury

Activated carbon Calcium hypochlorite, oxidizing agents

Alkali metalsWater, carbon tetrachloride and other halogenated alkanes, carbon dioxide, halogens. (Do not use water or foam extinguishers for fires involving these metals Use the appropriate class D extinguisher.

Aluminium All oxidizing agents, acids, alkalis, halogenated hydrocarbons, peroxides

Aluminium alkyls water

Ammonia, liquid or gas

Mercury (e.g. in pressure gauges), chlorine, calcium hypochlorite, iodine, bromine, hydrogen fluoride

Ammonium nitrateAcids, powdered metals, flammable liquids, chlorates, nitrates, sulfur, fine-particulate organic or combustible materials

Aniline Nitric acid, hydrogen peroxide

Arsenic materials Any reducing agent

Azides Acids

Bromine see chlorine

Calcium oxide Water

Carbon activated Calcium hypochlorite, other oxidants

ChlorineAmmonia, acetylene, butadiene, butane, methane, propane, hydrogen, petroleum benzine, benzene, powdered metals

ChloratesAmmonium salts, acids, powdered metals, sulfur, fine-particulate organic or combustible substances

Chromium (V1) oxide, chromic acid

Acetic acid, naphthalene, camphor, glycerol, petroleum benzine, alcohols, flammable liquids

Copper Acetylene, hydrogen peroxide

Cumene hydroperoxide

Acids, both organic and inorganic

Cyanides Acids

Flammable liquidsAmmonium nitrate, chromium (VI) oxide, hydrogen peroxide, nitric acid, sodium peroxide, halogens, chromic acid.

Fluorine Extremely aggressive; store separately! Isolate from everything!

Hydrazine Hydrogen peroxide, nitric acid, any other oxidant

Hydrocarbonsbutane, propane, benzene etc.

Fluorine, chlorine, bromine, chromium (VI) oxide, sodium peroxide

Hydrogen fluoride Ammonia (laboratory gas or solutions)

Hydrogen peroxideCopper, chromium, iron, metals and metal salts, alcohols, acetone, organic substances, aniline, nitromethane, combustible substances (solid or liquid)

Hydrogen sulphide Fuming nitric acid, oxidizing gases

Hypochlorites Acids, activated carbon

Iodine Acetylene, ammonia (laboratory gas or solutions)

Mercury Acetylene, ammonia

Nitrates and nitrites Acids

Nitric acidAcetic acid, aniline, chromium (VI) oxide, prussic acid, hydrogen sulfide, flammable liquids and gases

Nitroparaffins Inorganic bases, amines

Oxalic acid Silver, mercury, mercury salts

Perchloric acidAcetic anhydride, bismuth and its alloys, alcohols, paper, wood, grease. oil, (all organics)

Peroxides, organic Acids (organic and inorganic), avoid friction, store cold.

Phosphorus Sulfur, compounds containing oxygen, e.g. chlorates, air, oxygen

Phosphorus pentoxide

Alcohols, strong bases, water

Potassium Carbon tetrachloride,carbon dioxide, water

Potassium chlorate see chlorate

Potassium perchlorate

see chlorate

Potassium permanganate

Glycerol, ethylene glycol, benzaldehyde, sulfuric acid

Silver Acetylene, oxalic acid tartaric acid, ammonium compounds

Sodium see alkali metals

Sodium peroxideMethanol, ethanol, glacial acetic acid, acetic anhydride, benzaldehyde, carbon disulfide, glycerol, ethylene glycol, ethyl acetate, methyl acetate, furfural

Sulphides Acids

Sulphuric acid Potassium chlorate, potassium perchlorate, potassium permanganate

sulphur Metals, all oxidizing agents

Zinc All oxidizing agents, acids, alkalis, halogenated hydrocarbons, peroxides

Reactions of incompatible chemicals

Chemicals Stored Together Possible Reaction

1. Acetic acid & AcetaldehydeSmall amounts of acetic acid will cause the acetaldehyde to polymerize, releasing heat.

2. Acetic anhydride & Acetaldehyde Reaction can be violently explosive

3. Aluminum metal & ammonium nitrate

A potential explosive.

4. Aluminum & bromine vaporAluminum foil reacts with bromine vapor at room temperature and incandesces.

5. Ammonia vapor & bromine vapor Unstable nitrogen tribromide is formed, explosion may result.

6. Ammonium nitrate & acetic acidA mixture may result in ignition, especially if acetic acid is concentrated.

7. Cupric sulfide & cadmium chlorate

Will explode on contact.

8. Hydrogen peroxide & ferrous sulfide

Forms a vigorous, highly exothermic reaction.

9. Hydrogen peroxide & lead II or IV oxide

Violent, possibly explosive reaction.

10. Lead perchlorate & methyl alcohol

Forms an explosive mixture if agitated.

11. Lead sulfide & hydrogen peroxide

Vigorous, potentially explosive reaction.

12. Mercury II nitrate & methanol May form mercury fulminate - an explosive.

13. Nitric acid & phosphorus Phosphorus burns spontaneously in the presence of nitric acid.

14. Potassium cyanide & potassium peroxide

A potentially-explosive mixture if heated.

15. Sodium nitrate & sodium thiosulfate

A mixture of the dry materials can result in an explosion.

References :1. Merck chemical company.2. Chemical Safety Office, Risk Management Department, University of Vermont.3. Hazards in the Chemical Laboratory, 4th. edition. 1986. Bretherick.