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

2,2,4trimethylpentane

acetonitrile, dimethyl formamide, dimethyl sulfoxide, methanol, water

water

carbon 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 alumina, calcium hydride (CaH 2), 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 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 (177-316C).
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

Alcohols

Anhydrous forms of potassium carbonate; anhydrous magnesium or

calcium sulphate; quicklime.

Alkyl halides
Aryl halides

Anhydrous calcium chloride; anhydrous forms of sodium sulphate,

magnesium sulphate, or calcium sulphate; sodium pentoxide.

Saturated and
Aromatic
hydrocarbons

Anhydrous calcium chloride or sulphate; metallic sodium; phosphorus

pentoxide.

Aldehydes

Anhydrous sodium sulphate; anhydrous magnesium or calcium

sulphate.

Ketones

Anhydrous sodium sulphate; anhydrous magnesium or calcium

sulphate; anhydrous potassium carbonate.

Organic bases
(amines)

Solid potassium or sodium hydroxide; quicklime; barium oxide.

Organic acids

Anhydrous sodium sulphate; anhydrous magnesium or calcium

sulphate.

Solvents: Properties and Drying agents

Solvent

Boiling
Flash
Pt.
Density Pt.
C
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

+6

CaCl2; 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

-10

CaCl2; 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

na

Refractionation: distillate at 40 - 42C. (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

155
165

0.906

+70

CaCl2; Na

Diethyl ether

34

0.714

-40

CaCl2; 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

-4

K2CO3; 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

-23

Na; 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

na

calcium 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

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

CaCl2; Na

Storage of Incompatible Chemicals

Substance

Incompatible with

Acetic acid

Chromium 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 metals

Water, 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 nitrate

Acids, powdered metals, flammable liquids, chlorates, nitrates, sulfur, fineparticulate 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

Chlorine

Ammonia, acetylene, butadiene, butane, methane, propane, hydrogen,

petroleum benzine, benzene, powdered metals

Chlorates

Ammonium 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 liquids

Ammonium 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

Hydrocarbons
butane, propane,
benzene etc.

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

Hydrogen fluoride

Ammonia (laboratory gas or solutions)

Hydrogen peroxide

Copper, 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 acid

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

Nitroparaffins

Inorganic bases, amines

Oxalic acid

Silver, mercury, mercury salts

Perchloric acid

Acetic 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 peroxide

Methanol, 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 & Acetaldehyde

Small 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 vapor

Aluminum 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 acid

A 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.