Azeotrope

Azeotrope (data)

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This page contains tables of azeotrope data for various binary and ternary mixtures of solvents. Data includes composition of mixture by weight (in binary azeotropes when only one fraction is given, it is the fraction of the second component), boiling point (b.p.) of components, boiling point of mixture, and specific gravity of mixture. Boiling points are at 760 mm Hg unless otherwise stated. Where the mixture separates into layers, values are shown for upper (U) and lower (L) layers.

Data is obtained from Lange's 10th edition^[1] and CRC 44th edition^[2] unless otherwise noted (see color code table).

Binary azeotropes

Data source color code
CRC & Lange's	CRC only	Lange's only	other (see references)

Azeotropes of water, b.p.=100 °C

2nd Component	b.p. of comp. (˚C)	b.p. of mixture (˚C)	% by weight	spef. grav
with various alcohols
ethanol	78.4	78.1	95.5	0.804
methanol^[3]	64.7	No azeotrope
n-propanol	97.2	87.7	71.7	0.866
iso-propanol	82.5	80.4	87.9	0.818
n-butanol	117.8	92.4	55.5 U 79.9 L 7.7	U 0.849 L 0.990
sec-butanol	99.5	88.5	67.9	0.863
iso-butanol	108.0	90.0	70.0 U 85.0 L 8.7	U 0.839 L 0.988
tert-butanol	82.8	79.9	88.3
allyl alcohol	97.0	88.2	72.9	0.905
benzyl alcohol	205.2	99.9	9
furfuryl alcohol	169.4	98.5	20
cyclohexanol^[4]	161.1	97.8	20
benzyl alcohol^[4]	205.4	99.9	9
with various organic acids
formic acid	100.8	107.3	77.5
acetic acid ^‡^[3]^[5]	118.1	No azeotrope
propionic acid	141.1	99.98	17.7	1.016
butyric acid	163.5	99.94	18.4	1.007
iso-butyric acid	154.5	99.3	21
with mineral acids
nitric acid	86.0	120.5	68	1.405
perchloric acid	110.0	203	71.6
hydrofluoric acid	19.9	120	37
hydrochloric acid	–84	110	20.24	1.102
hydrobromic acid	–73	126	47.5	1.481
hydroiodic acid	–34	127	57
sulfuric acid	290	338	98
with various alkyl halides
ethylene chloride	83.7	72	91.8
propylene chloride	96.8	78	89.4
chloroform	61.2	53.3	97.0 U 0.8 L 99.8	U 1.004 L 1.491
carbon tetrachloride	76.8	66.8	95.9 U 0.03 L 99.97	U 1.000 L 1.597
methylene chloride	40.0	38.8	99.6 U 2.0 99.9	U 1.009 L 1.328
with various esters
ethyl acetate	77.1	70.4	91.9 U 96.7 L 8.7	U 0.907 L 0.999
methyl acetate	57.0	56.1	95.0	0.940
n-propyl acetate^[4]	101.6	82.4	86
ethyl nitrate	87.7	74.4	78
with various other solvents
acetone ^‡^[3]^[5]	56.5 °C	No azeotrope
methyl ethyl ketone	79.6	73.5	89	0.834
pyridine	115.5	92.6	57	1.010
benzene	80.2	69.3	91.1 U 99.94 L 0.07	U 0.880 L 0.999
toluene	110.8	84.1	79.8 U 99.95 L 0.06	U 0.868 L 1.000
cyclohexane	80.7	69.8	91.5 U 99.99 L 0.01	U 0.780 L 1.00
diethyl ether	34.5	34.2	98.7	0.720
tetrahydrofuran^[3]	66	65	95
anisole	153.9	95.5	59.5
acetonitrile	82.0	76.5	83.7	0.818
chloral	97.75	95.0	93.0
hydrazine^[6]	113.5 °C	120.3 °C	68.5

^‡ CRC 44th ed. lists azeotropes for acetic acid/water and acetone/water, Lange's 10th ed. as well as numerous web sources indicate no azeotrope for these pairs.

Azeotropes of allyl alcohol, b.p.=97.0 °C

2nd Component	b.p. of comp. (˚C)	b.p. of mixture (˚C)	% by weight	spef. grav
with various solvents
methyl butyrate	102.7	93.8	45
n-propyl acetate	101.6	94.2	47
benzene	80.2	76.8	82.6	0.874
toluene	110.8	92.4	50
cyclohexane	80.8	74	80
carbon tetrachloride	76.8	72.3	88.5	1.450
ethylene chloride	83.7	79.9	82

Azeotropes of ethanol, b.p.=78.4 °C

2nd Component	b.p. of comp. (˚C)	b.p. of mixture (˚C)	% by weight	spef. grav
with various esters
ethyl acetate	77.1	71.8	69.2	0.863
methyl acetate	57.0	56.9	97
ethyl nitrate	87.7	71.9	56
isopropyl acetate^[4]	88.4	76.8	47
with various hydrocarbons
benzene	80.2	68.2	67.6	0.848
cyclohexane^[7]	80.7	64.9	69.5
toluene	110.8	76.7	32	0.815
n-pentane	36.2	34.3	95
n-hexane	68.9	58.7	79	0.687
n-heptane	98.5	70.9	51	0.729
n-octane	125.6	77.0	22
with various alkyl halides
ethylene chloride	83.7	70.5	63
chloroform	61.1	59.4	93	1.403
carbon tetrachloride	76.8	65.1	84.2	1.377
allyl chloride	45.7	44	95
n-propyl chloride	46.7	45.0	93
isopropyl chloride	36.3	35.6	97.2
n-propyl bromide	71.0	62.8	79.5
isopropyl bromide	59.8	55.6	89.5
n-propyl iodide	102.4	75.4	56
isopropyl iodide	89.4	71.5	73
methyl iodide	42.6	41.2	96.8
methylene chloride	40.1	39.85	95.0
ethyl bromide	38.0	37.0	97.0
trichloroethylene	87	70.9	73.0	1.197
trichlorotrifluoroethane (CFC 113)	47.7	43.8	96.2	1.517
tetrachloroethylene	121.0	76.75	37.0
with various other solvents
methyl ethyl ketone	79.6	74.8	60	0.802
acetonitrile	82.0	72.9	43.0	0.788
nitromethane	101.3	75.95	26.8
tetrahydrofuran^[8] P = 100 kPa	65.6	65.4	3.3
thiophene^[7]	84.1	70.0	55.0
carbon disulfide^[4]	46.2	42.4	92

Azeotropes of methanol, b.p.=64.7 °C

2nd Component	b.p. of comp. (˚C)	b.p. of mixture (˚C)	% by weight	spef. grav
with various esters
methyl acetate	57.0	53.8	81.3	0.908
ethyl acetate	77.1	62.3	56	0.846
ethyl formate	54.1	51.0	84
with various hydrocarbons
benzene	80.2	58.3	60.4	0.844
toluene	110.8	63.8	31	0.813
cyclohexane	80.8	54.2	62.8 U 97.0 L 39.0
n-pentane	36.2	30.8	91
n-hexane	68.9	50.6	72
n-heptane	98.5	59.1	48.5
n-octane	125.8	63.0	72.0
with various alkyl halides
ethylene chloride	83.7	61.0	68
chloroform	61.1	53.5	87.4	1.342
carbon tetrachloride	76.8	55.7	79.4	1.322
ethyl bromide	38.4	35.0	95.5
n-propyl chloride	46.6	40.5	90.5
isopropyl chloride	36.4	33.4	94
n-propyl bromide	71.0	54.5	79
isopropyl bromide	59.8	48.6	85.0
isopropyl iodide	89.4	61.0	62
trichloroethylene^[4]	87.2	60.2	64
tetrachloroethylene^[8]	121.1	63.5	40.6
trichlorotrifluoroethane (CFC 113)^[4]	47.7	39.9	94
with various other solvents
nitromethane	101.2	64.6	9
acetone	56.5	55.7	87.9	0.796
acetonitrile	82.0	63.45	19.0
carbon disulfide	46.2	37.7	86.0 U 50.8 L 97.2	U 0.979 L 1.261
isopropanol^[4]	82.5	64.0	20
tetrahydrofuran^[9] P = 984 mBar	65.6	60.7	69.0

Azeotropes of n-propanol, b.p.=97.2 °C

2nd Component	b.p. of comp. (˚C)	b.p. of mixture (˚C)	% by weight	spef. grav
with various solvents
methyl butyrate	102.7	94.4	51
n-propyl formate	80.8	80.65	97
n-propyl acetate	101.6	94.7	49	0.833
benzene	80.2	77.1	83.1
toluene	110.8	92.4	47.5	0.836
n-hexane	68.9	65.7	96
carbon tetrachloride	76.8	73.1	88.5	1.437
ethylene chloride	83.7	80.7	81
n-propyl bromide	71.0	69.7	91

Azeotropes of acetic acid, b.p.=118.5 °C

2nd Component	b.p. of comp. (˚C)	b.p. of mixture (˚C)	% by weight	spef. grav
with various solvents
benzene	80.2	80.05	98	0.882
cyclohexane^[4]	80.8	79.7	98
toluene	110.8	105.0	72	0.905
m-xylene	139.0	115.4	27.5	0.908
n-heptane	98.5	92.3	70
n-octane	125.8	109.0	50
isopropyl iodide	89.2	88.3	91
carbon tetrachloride	76.8	76.6	97
tetrachloroethylene	121.0	107.4	61.5
ethylene bromide	131.7	114.4	45
1,1-dibromoethane	109.5	103.7	75.0
methylene bromide	98.2	94.8	84.0
pyridine	115.3	139.7	65.0	1.024

Azeotropes of isopropanol, b.p.=82.5 °C

2nd Component	b.p. of comp. (˚C)	b.p. of mixture (˚C)	% by weight	spef. grav
with various esters
ethyl acetate	77.1	75.3	75	0.869
isopropyl acetate	91.0	81.3	40	0.822
with various hydrocarbons
benzene	80.2	71.9	66.7	0.838
toluene ^‡^[7]	110.8	80.6	42
cyclohexane	81.0	68.6	67.0	0.777
n-pentane	36.2	35.5	94
n-hexane	68.9	62.7	77
n-heptane	98.5	76.3	46
with various alkyl halides
carbon tetrachloride	76.8	69.0	82	1.344
chloroform	61.1	60.8	95.8
ethylene chloride	83.7	74.7	56.5
ethyl iodide	83.7	67.1	85
n-propyl chloride	46.7	46.4	97.2
n-propyl bromide	71.0	66.8	79.5
isopropyl bromide	59.8	57.8	88
n-propyl iodide	102.4	79.8	58
isopropyl iodide	89.4	76.0	68
tetrachloroethylene^[7]	121.1	81.7	19.0
with various other solvents
methyl ethyl ketone	79.0	77.5	68	0.800
diisopropyl ether	69	66.2	85.9
nitromethane	101.0	79.3	70

^‡ CRC and Lange's disagree on this azeotrope, but web source corroborates CRC

Azeotropes of formic acid, b.p.=100.8 °C

2nd Component	b.p. of comp. (˚C)	b.p. of mixture (˚C)	% by weight
with various hydrocarbons
benzene	80.2	71.7	69
toluene	110.8	85.8	50
m-xylene	139.0	94.2	29.8
n-pentane	36.2	34.2	90
n-hexane	68.9	60.6	72
n-heptane	98.5	78.2	56.5
n-octane	125.8	90.5	37
with various alkyl halides
chloroform	61.2	59.2	85
carbon tetrachloride	76.8	66.7	81.5
methyl iodide	42.6	42.1	94
ethyl bromide	38.4	38.2	97
ethylene chloride	83.6	77.4	86
ethylene bromide	131.7	94.7	48.5
n-propyl chloride	46.7	45.6	92
isopropyl chloride	34.8	34.7	98.5
n-propyl bromide	71.0	64.7	73
isopropyl bromide	59.4	56.0	86
with various other solvents
carbon disulfide	46.3	42.6	83

Azeotropes of benzene, b.p.=80.1 °C

2nd Component	b.p. of comp. (˚C)	b.p. of mixture (˚C)	% by weight	spef. grav
cyclohexane	81.4	77.8	45.0	0.834
ethyl nitrate	88.7	80.03	12.0
methyl ethyl ketone	79.6	78.4	37.5	0.853
nitromethane	101.0	79.15	14.0
acetonitrile	82.0	73.0	34.0
n-heptane^[4]	98.5	80.0	1

Azeotropes of ethylene glycol, b.p.=197.4 °C

2nd Component	b.p. of comp. (˚C)	b.p. of mixture (˚C)	% by weight
with various solvents
ethyl benzoate	212.6	186.1	53.5
diphenyl	254.9	192.0	36
mesitylene	164.6	156.0	87
naphthalene	218.1	183.9	49
toluene	110.8	110.2	93.5
m-xylene	139.0	135.6	85
o-xylene	144.4	139.6	84.0
ethylene bromide	131.7	129.8	96
nitrobenzene	210.9	185.9	41
chlorobenzene	132.0	130.1	5.6
benzyl chloride	179.3	167.0	70
benzyl alcohol	205.1	193.1	44
anisole	153.9	150.5	89.5
acetophenone	202.1	185.7	48
aniline	184.4	180.6	76
o-cresol	191.1	189.6	73

Azeotropes of glycerol, b.p.=291.0 °C

2nd Component	b.p. of comp. (˚C)	b.p. of mixture (˚C)	% by weight	spef. grav
diphenyl	254.9	243.8	45
naphthalene	218.1	215.2	90

Azeotropes of acetone, b.p.=56.5 °C

2nd Component	b.p. of comp. (˚C)	b.p. of mixture (˚C)	% by weight	spef. grav
carbon disulfide	46.3	39.3	67.0	1.04
chloroform	61.2	64.7	80.0	1.268
cyclohexane	81.4	53.0	33.0
n-hexane	68.8	49.8	41
ethyl iodide	56.5	55.0	40.0
carbon tetrachloride^[7]	76.8	56.2	11.9

Miscellaneous azeotrope pairs

component 1	b.p. comp. 1 (˚C)	component 2	b.p. comp. 2 (˚C)	b.p. azeo. (˚C)	% wt comp. 1	% wt comp. 2	spec. grav.
acetaldehyde	21.0	diethyl ether	34.6	20.5	76.0	24.0	0.762
acetaldehyde	21.0	n-butane^[7]	–0.5	–7.0	16.0	84.0
acetamide	222.0	benzaldehyde	179.5	178.6	6.5	93.5
		nitrobenzene	210.9	202.0	24.0	76.0
		o-xylene	144.1	142.6	11.0	89.0
acetonitrile	82.0	ethyl acetate	77.15	74.8	23.0	77.0
acetonitrile	82.0	toluene^[8]	110.6	81.1	25.0	75.0
acetylene	–86.6	ethane	–88.3	–94.5	40.7	59.3
aniline	184.4	o-cresol	191.5	191.3	8.0	92.0
carbon disulfide	46.2	diethyl ether	34.6	34.4	1.0	99.0	0.719
		1,1-dichloroethane	57.2	46.0	94.0	6.0
		methyl ethyl ketone	79.6	45.9	84.7	15.3	1.157
		ethyl acetate^[4]	77.1	46.1	97	3
		methyl acetate^[4]	57.0	40.2	73	27
chloroform	61.2	methyl ethyl ketone	79.6	79.9	17.0	83.0	0.877
chloroform	61.2	n-hexane	68.7	60.0	72.0	28.0	1.101
carbon tetrachloride	76.8	methyl ethyl ketone	79.9	73.8	71.0	29.0	1.247
		ethylene dichloride	84.0	75.3	78.0	22.0	1.500
		ethyl acetate	77.1	74.8	57.0	43.0	1.202
cyclohexane	81.4	ethyl acetate	77.15	72.8	46.0	54.0
cyclohexane	81.4	ethyl nitrate	88.7	74.5	64.0	36.0
diethyl ether	34.6	methyl formate	31.50	28.2	44.0	56.0
diethyl ether	34.6	methylene chloride^[3]	40	40.8	30	70
nitromethane	101.0	toluene	110.8	96.5	55.0	45.0
tetrahydrofuran^[9]	65.6	chloroform	61.2	72.5	34.5	65.5
tetrahydrofuran^[9]	65.6	n-hexane	69	63.0	46.5	53.5
toluene	110.63	pyridine	115.3	110.2	78.0	22.0
propylene glycol^[10]	188.2	aniline	184.4	179.5	43	57
		o-xylene	144.4	135.8	10	90
		toluene	110.6	110.5	1.5	98.5

Ternary azeotropes

Tables of various ternary azeotropes (that is azeotropes consisting of three components). Fraction percentages are given by weight.

Data source color code
CRC & Lange's	CRC only	Lange's only	other (see references)

Ternary azeotropes of water, b.p.=100 °C

2nd component	b.p. 2nd comp. (˚C)	3rd component	b.p. 3rd comp. (˚C)	b.p. azeo. (˚C)	% wt 1st	% wt 2nd	% wt 3rd	spec. grav
ethanol	78.4	ethyl acetate	77.1	70.3 °C	7.8	9.0	83.2	0.901
		cyclohexane	80.8	62.1	7	17	76
		benzene	80.2	64.9	7.4 U 1.3 L 43.1	18.5 U 12.7 L 52.1	74.1 U 86.0 L 4.8	U 0.866 L 0.892
		chloroform	61.2	55.5	3.5 U 80.8 L 0.5	4.0 U 18.2 L 3.7	92.5 U 1.0 L 95.8	U 0.976 L 1.441
		carbon tetrachloride	86.8	61.8	4.3	9.7	86.0
		carbon tetrachloride	86.8	61.8	3.4 U 44.5 L <0.1	10.3 U 48.5 L 5.2	86.3 U 7.0 L 94.8	U 0.935 L 1.519
		ethylene chloride	83.7	66.7	5	17	78
		acetonitrile	82.0	72.9	1.0	55.0	44.0
		toluene	110.6	74.4	12.0 U 3.1 L 20.7	37.0 U 15.6 L 54.8	51.0 U 81.3 L 24.5	U 0.849 L 0.855
		methyl ethyl ketone	79.6	73.2	11.0	14.0	75.0	0.832
		n-hexane	69.0	56.0	3.0 U 0.5 L 19.0	12.0 U 3.0 L 75.0	85.0 U 96.5 L 6.0	U 0.672 L 0.833
		n-heptane	98.4	68.8	6.1 U 0.2 L 15.0	33.0 U 5.0 L 75.9	60.9 U 94.8 L 9.1	U 0.686 L 0.801
		carbon disulfide	46.2	41.3	1.6	5.0	93.4
n-propanol	97.2	cyclohexane	80.8	66.6	8.5	10.0	81.5
		benzene	80.2	68.5	8.6	9.0	82.4
		carbon tetrachloride	76.8	65.4	5 U 84.9 L 1.0	11 U 15.0 L 11.0	84 U 0.1 L 88.0	U 0.979 L 1.436
		diethyl ketone	102.2	81.2	20	20	60
		n-propyl acetate	101.6	82.2	21.0	19.5	59.5
isopropanol	82.5	cyclohexane	80.8	64.3	7.5	18.5	74.0
		cyclohexane	80.8	66.1	7.5	21.5	71.0
		benzene	80.2 °C	66.5	7.5	18.7	73.8
		benzene	80.2 °C	65.7 °C	8.2 U 2.3 L 85.1	19.8 U 20.2 L 14.4	72.0 U 77.5 L 0.5	U 0.855 L 0.966
		methyl ethyl ketone	79.6	73.4	11.0	1.0	88.0	0.834
		toluene	110.6	76.3	13.1 U 8.5 L 61.0	38.2 U 38.2 L 38.0	48.7 U 53.3 L 1.0	U 0.845 L 0.930
allyl alcohol	97.0	n-hexane	69.0	59.7	5 U 0.5 L 64.4	5 U 3.6 L 34.8	90 U 95.9 L 0.8	U 0.668 L 0.964
		benzene	80.2	68.2	8.6 U 0.6 L 80.9	9.2 U 8.7 L 17.7	82.2 U 90.7 L 0.4	U 0.877 L 0.985
		cyclohexane	80.8	66.2	8	11	81
		carbon tetrachloride	76.8	65.2	5 U 71.7 L 0.8	11 U 25.6 L 10.1	84 U 2.7 L 89.1	U 0.777 L 1.464
benzene	80.1	acetonitrile	82.0	66.0	8.2	68.5	23.3
benzene	80.1	methyl ethyl ketone	79.6	68.2	8.8 U 0.6 L 94.7	65.1 U 71.3 L 0.1	26.1 U 28.1 L 5.2	U 0.858 L 0.992
methyl ethyl ketone	79.6	carbon tetrachloride	76.8	65.7	3.0 U 94.4 L 0.1	22.2 U 5.5 L 22.6	74.8 U 0.1 L 77.3	U 0.993 L 1.313
methyl ethyl ketone	79.6	cyclohexane	81.0	63.6	5.0 U 0.6 L 89.9	60.0 U 37.0 L 10.0	35.0 U 62.4 L 0.1	U 0.769 L 0.98
chloroform	61.2	methanol	64.65	52.6	4.0 U 27.0 L 3.0	81.0 U 32.0 L 83.0	15.0 U 41.0 L 14.0	U 1.022 L 1.399
chloroform	61.2	acetone^‡	56.5	60.4	4.0	57.6	38.4

^‡Saddle azeotrope

Ternary azeotropes of methanol, b.p.=64.65 °C

2nd component	b.p. 2nd comp. (˚C)	3rd component	b.p. 3rd comp. (˚C)	b.p. azeo. (˚C)	% wt 1st	% wt 2nd	% wt 3rd	spec. grav
acetone	56.5	chloroform^‡	61.2	57.5	23.0	30.0	47.0
		methyl acetate	57.0	53.7	17.4	5.8	76.8	0.898
		cyclohexane	81.4	51.5	16.0	43.5	40.5
methyl acetate	57.1	carbon disulfide	46.2	37.0
		cyclohexane	81.4	50.8	17.8	48.6	33.6
		n-hexane	69.0	45.0	14.0	27.0	59.0	0.73

^‡Saddle azeotrope

References

^ Lange's Handbook of Chemistry, 10th ed. pp1496-1505
^ CRC Handbook of Chemistry and Physics, 44th ed. pp 2143-2184
^ ^a ^b ^c ^d ^e "What is an Azeotrope?". B/R Corporation. http://www.solvent--recycling.com/azeotrope_1.html. Retrieved 24 March 2007.
^ ^a ^b ^c ^d ^e ^f ^g ^h ⁱ ^j ^k ^l "Binary Organic Azeotropes Useful for Solvent Cleaning". metalfinishing.com. November 2000. http://www.metalfinishing.com/_virtual/article-downloads/Table%201_a2648.pdf. Retrieved 13 February 2011.
^ ^a ^b Hilmen, Eva-Katrine (November 2000). "Separation of Azeotropic Mixtures: Tools for Analysis and Studies on Batch Distillation Operation". Norwegian University of Science and Technology, dept. of Chemical Engineering. http://www.chemeng.ntnu.no/thesis/download/2000/hilmen/Thesis_Hilmen.pdf. Retrieved 24 March 2007.
^ Merck Index of Chemicals and Drugs, 9th ed. monograph 4653
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