Azeotrope tables

Last updated

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

Contents

The data were obtained from Lange's 10th edition [1] and CRC Handbook of Chemistry and Physics 44th edition [2] unless otherwise noted (see color code table).

A list of 15825 binary and ternary mixtures was collated and published by the American Chemical Society. [3] An azeotrope databank is also available online through the University of Edinburgh. [4]

Binary azeotropes

Data source color code
CRC & Lange'sCRC onlyLange's onlyother (see references)

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

2nd Componentb.p. of
comp. (˚C)
b.p. of
mixture (˚C)
 % by
weight
spef.
grav
with various alcohols
ethanol 78.478.195.50.804
methanol [5] 64.7Doesn`t form azeotrope
1-propanol 97.387.771.70.866
2-propanol 82.580.487.70.818
n-butanol 117.892.455.5
U 79.9
L 7.7

U 0.849
L 0.990
sec-butanol 99.588.567.90.863
iso-butanol 108.090.070.0
U 85.0
L 8.7

U 0.839
L 0.988
tert-butanol 82.879.988.3
allyl alcohol 97.088.272.90.905
furfuryl alcohol 169.498.520
cyclohexanol [6] 161.197.820
benzyl alcohol [6] 205.499.99
with various organic acids
formic acid 100.8107.377.5
acetic acid [5] [7] 118.1No azeotrope
propionic acid 141.199.9817.71.016
butyric acid 163.599.9418.41.007
iso-butyric acid 154.599.321
with mineral acids
nitric acid 83.0120.5681.405
perchloric acid 110.020371.6
hydrofluoric acid 19.912037
hydrochloric acid –8411020.241.102
hydrobromic acid –7312647.51.481
hydroiodic acid –3412757
sulfuric acid 29033898
with various alkyl halides
ethylene chloride 83.77291.8
propylene chloride 96.87889.4
chloroform [8] 61.256.197.2
U 0.8
L 99.8

U 1.004
L 1.491
carbon tetrachloride 76.866.895.9
U 0.03
L 99.97

U 1.000
L 1.597
methylene chloride 40.038.899.6
U 2.0
99.9

U 1.009
L 1.328
with various esters
ethyl acetate 77.170.491.9
U 96.7
L 8.7

U 0.907
L 0.999
methyl acetate 57.056.195.00.940
n-propyl acetate [6] 101.682.486
isopropyl acetate [9] 88.775.988.9
ethyl nitrate 87.774.478
with various other solvents
acetone [5] [7] 56.5 °CNo azeotrope
methyl ethyl ketone 79.673.5890.834
pyridine 115.592.6571.010
benzene 80.269.391.1
U 99.94
L 0.07

U 0.880
L 0.999
toluene 110.884.179.8
U 99.95
L 0.06

U 0.868
L 1.000
cyclohexane 80.769.891.5
U 99.99
L 0.01

U 0.780
L 1.00
diethyl ether 34.534.298.70.720
tetrahydrofuran [5] 6664.2 [10] 95
anisole 153.995.559.5
acetonitrile 82.076.583.70.818
chloral 97.7595.093.0
hydrazine [11] 113.5 °C120.3 °C68.5
m-xylene [3] [12] 139.092.064.2

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.

Binary azeotropes of allyl alcohol, b.p.=97.0 °C

2nd Componentb.p. of
comp. (˚C)
b.p. of
mixture (˚C)
 % by
weight
spef.
grav
with various solvents
methyl butyrate 102.793.845
n-propyl acetate 101.694.247
benzene 80.276.882.60.874
toluene 110.892.450
cyclohexane 80.87480
carbon tetrachloride 76.872.388.51.450
ethylene chloride 83.779.982

Binary azeotropes of ethanol, b.p.=78.4 °C

2nd Componentb.p. of
comp. (˚C)
b.p. of
mixture (˚C)
 % by
weight
spef.
grav
with various esters
ethyl acetate 77.171.869.20.863
methyl acetate 57.056.997
ethyl nitrate 87.771.956
isopropyl acetate [6] 88.476.847
with various hydrocarbons
benzene 80.268.267.60.848
cyclohexane [13] 80.764.969.5
toluene 110.876.7320.815
n-pentane 36.234.395
n-hexane 68.958.7790.687
n-heptane 98.570.9510.729
n-octane 125.677.022
with various alkyl halides
ethylene chloride 83.770.563
chloroform 61.159.4931.403
carbon tetrachloride 76.865.184.21.377
allyl chloride 45.74495
n-propyl chloride 46.745.093
isopropyl chloride 36.335.697.2
n-propyl bromide 71.062.879.5
isopropyl bromide 59.855.689.5
n-propyl iodide 102.475.456
isopropyl iodide 89.471.573
methyl iodide 42.641.296.8
methylene chloride 40.139.8595.0
ethyl bromide 38.037.097.0
trichloroethylene 8770.973.01.197
trichlorotrifluoroethane (CFC 113)47.743.896.21.517
tetrachloroethylene 121.076.7537.0
with various other solvents
methyl ethyl ketone 79.674.8600.802
acetonitrile 82.072.943.00.788
nitromethane 101.375.9526.8
tetrahydrofuran [14]
P = 100 kPa
65.66596.7
thiophene [13] 84.170.055.0
carbon disulfide [6] 46.242.492

Binary azeotropes of methanol, b.p.=64.7 °C

2nd Componentb.p. of
comp. (˚C)
b.p. of
mixture (˚C)
 % by
weight
spef.
grav
with various esters
methyl acetate 57.053.881.30.908
ethyl acetate 77.162.3560.846
ethyl formate 54.151.084
with various hydrocarbons
benzene 80.258.360.50.844
toluene 110.863.8310.813
cyclohexane 80.845.262.8
U 97.0
L 39.0
n-pentane 36.230.891
n-hexane [15] 68.96071.6
n-heptane 98.559.148.5
n-octane 125.863.072.0
with various alkyl halides
methylene chloride 40.037.892.7
ethylene chloride 83.761.068
chloroform 61.153.587.41.342
carbon tetrachloride 76.855.779.41.322
ethyl bromide 38.435.095.5
n-propyl chloride 46.640.590.5
isopropyl chloride 36.433.494
n-propyl bromide 71.054.579
isopropyl bromide 59.848.685.0
isopropyl iodide 89.461.062
trichloroethylene [6] 87.260.264
tetrachloroethylene [14] 121.163.540.6
trichlorotrifluoroethane (CFC 113) [6] 47.739.994
with various other solvents
nitromethane 101.264.69
acetone 56.555.787.90.796
acetonitrile 82.063.4519.0
carbon disulfide 46.237.786.0
U 50.8
L 97.2

U 0.979
L 1.261
Isopropyl alcohol [6] 82.564.020
tetrahydrofuran [16]
P = 984 mBar
65.660.769.0

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

2nd Componentb.p. of
comp. (˚C)
b.p. of
mixture (˚C)
 % by
weight
spef.
grav
with various solvents
methyl butyrate 102.794.451
n-propyl formate 80.880.6597
n-propyl acetate 101.694.7490.833
benzene 80.277.183.1
toluene 110.892.447.50.836
n-hexane 68.965.796
carbon tetrachloride 76.873.188.51.437
ethylene chloride 83.780.781
n-propyl bromide 71.069.791

Binary azeotropes of acetic acid, b.p.=118.5 °C

2nd Componentb.p. of
comp. (˚C)
b.p. of
mixture (˚C)
 % by
weight
spef.
grav
with various solvents
benzene 80.280.05980.882
cyclohexane [6] 80.879.798
toluene 110.8105.0720.905
m-xylene 139.0115.427.50.908
mesitylene [17] 164.61183.6
n-heptane 98.592.370
n-octane 125.8109.050
isopropyl iodide 89.288.391
carbon tetrachloride 76.876.697
tetrachloroethylene 121.0107.461.5
ethylene bromide 131.7114.445
1,1-dibromoethane 109.5103.775.0
methylene bromide 98.294.884.0
pyridine 115.3139.765.01.024

Binary azeotropes of Isopropyl alcohol, b.p.=82.5 °C

2nd Componentb.p. of
comp. (˚C)
b.p. of
mixture (˚C)
 % by
weight
spef.
grav
with various esters
ethyl acetate 77.175.3750.869
isopropyl acetate 91.081.3400.822
with various hydrocarbons
benzene 80.271.966.70.838
toluene [13] 110.880.642
cyclohexane 80.768.667.00.777
n-pentane 36.235.594
n-hexane 68.962.777
n-heptane 98.576.346
with various alkyl halides
carbon tetrachloride 76.869.0821.344
chloroform 61.160.895.8
ethylene chloride 83.774.756.5
ethyl iodide 83.767.185
n-propyl chloride 46.746.497.2
n-propyl bromide 71.066.879.5
isopropyl bromide 59.857.888
n-propyl iodide 102.479.858
isopropyl iodide 89.476.068
tetrachloroethylene [13] 121.181.719.0
with various other solvents
methyl ethyl ketone 79.077.5680.800
diisopropyl ether 6966.285.9
nitromethane 101.079.370

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

Binary azeotropes of formic acid, b.p.=100.8 °C

2nd Componentb.p. of
comp. (˚C)
b.p. of
mixture (˚C)
 % by
weight
spef.
grav
with various hydrocarbons
benzene 80.271.769
toluene 110.885.850
m-xylene 139.094.229.8
m-xylene [3] [12] 139.092.828.2
o-xylene [3] 143.695.526
p-xylene [3] 138.4~9530.0
n-pentane 36.234.290
n-hexane 68.960.672
n-heptane 98.578.256.5
n-octane 125.890.537
with various alkyl halides
chloroform 61.259.285
carbon tetrachloride 76.866.781.5
methyl iodide 42.642.194
ethyl bromide 38.438.297
ethylene chloride 83.677.486
ethylene bromide 131.794.748.5
n-propyl chloride 46.745.692
isopropyl chloride 34.834.798.5
n-propyl bromide 71.064.773
isopropyl bromide 59.456.086
with various other solvents
carbon disulfide 46.342.683

Binary azeotropes of benzene, b.p.=80.1 °C

2nd Componentb.p. of
comp. (˚C)
b.p. of
mixture (˚C)
 % by
weight
spef.
grav
cyclohexane 80.7477.845.00.834
ethyl nitrate 88.780.0312.0
methyl ethyl ketone 79.678.437.50.853
nitromethane 101.079.1514.0
acetonitrile 82.073.034.0
n-heptane [6] 98.580.01

Binary azeotropes of ethylene glycol, b.p.=197.4 °C

2nd Componentb.p. of
comp. (˚C)
b.p. of
mixture (˚C)
 % by
weight
spef.
grav
with various solvents
ethyl benzoate 212.6186.153.5
diphenyl 254.9192.036
mesitylene 164.6156.087
naphthalene 218.1183.949
toluene 110.8110.293.5
m-xylene 139.0135.685
o-xylene 144.4139.684.0
ethylene bromide 131.7129.896
nitrobenzene 210.9185.941
chlorobenzene 132.0130.15.6
benzyl chloride 179.3167.070
benzyl alcohol 205.1193.144
anisole 153.9150.589.5
acetophenone 202.1185.748
aniline 184.4180.676
o-cresol 191.1189.673

Binary azeotropes of glycerol, b.p.=291.0 °C

2nd Componentb.p. of
comp. (˚C)
b.p. of
mixture (˚C)
 % by
weight
spef.
grav
diphenyl 254.9243.845
naphthalene 218.1215.290

Binary azeotropes of acetone, b.p.=56.5 °C

2nd Componentb.p. of
comp. (˚C)
b.p. of
mixture (˚C)
 % by
weight
spef.
grav
carbon disulfide 46.339.367.01.04
chloroform 61.264.780.01.268
cyclohexane 80.7453.033.0
n-hexane 68.849.841
ethyl iodide 56.555.040.0
carbon tetrachloride [13] 76.856.211.9

Miscellaneous azeotrope pairs

component 1b.p.
comp. 1 (˚C)
component 2b.p.
comp. 2 (˚C)
 b.p.
azeo. (˚C)
 % wt
comp. 1
 % wt
comp. 2
spec.
grav.
acetaldehyde 21.0 diethyl ether 34.620.576.024.00.762
n-butane [13] –0.5–7.016.084.0
acetamide 222.0 benzaldehyde 179.5178.66.593.5
nitrobenzene 210.9202.024.076.0
o-xylene 144.1142.611.089.0
acetonitrile 82.0 ethyl acetate 77.1574.823.077.0
toluene [14] 110.681.176.024.0
acetylene –86.6 ethane –88.3–94.540.759.3
aniline 184.4 o-cresol 191.5191.38.092.0
carbon disulfide 46.2 diethyl ether 34.634.41.099.00.719
1,1-dichloroethane 57.246.094.06.0
methyl ethyl ketone 79.645.984.715.31.157
ethyl acetate [6] 77.146.1973
methyl acetate [6] 57.040.27327
chloroform 61.2 methyl ethyl ketone 79.679.917.083.00.877
n-hexane 68.760.072.028.01.101
carbon tetrachloride 76.8 methyl ethyl ketone 79.973.871.029.01.247
ethylene dichloride 84.075.378.022.01.500
ethyl acetate 77.174.857.043.01.202
cyclohexane 80.74 ethyl acetate 77.1572.846.054.0
ethyl nitrate 88.774.564.036.0
diethyl ether 34.6 methyl formate 31.5028.244.056.0
methylene chloride [5] 4040.83070
nitromethane 101.0 toluene 110.896.555.045.0
tetrahydrofuran [16] 65.6 chloroform 61.272.534.565.5
n-hexane 6963.046.553.5
toluene 110.63 pyridine 115.3110.278.022.0
propylene glycol [18] 188.2 aniline 184.4179.54357
o-xylene 144.4135.81090
toluene 110.6110.51.598.5

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'sCRC onlyLange's onlyother (see references)

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

2nd componentb.p.
2nd comp. (˚C)
3rd componentb.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 °C7.89.083.20.901
cyclohexane 80.862.171776
benzene 80.264.97.4
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 61.255.53.5
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 86.861.84.39.786.0
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 83.766.751778
acetonitrile 82.072.91.055.044.0
toluene 110.674.412.0
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 79.673.211.014.075.00.832
n-hexane 69.056.03.0
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 98.468.86.1
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 46.241.31.65.093.4
n-propanol 97.2 cyclohexane 80.866.68.510.081.5
benzene 80.268.58.69.082.4
carbon tetrachloride 76.865.45
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 102.281.2202060
n-propyl acetate 101.682.221.019.559.5
Isopropyl alcohol 82.5 cyclohexane 80.864.37.518.574.0
66.17.521.571.0
benzene 80.2 °C66.57.518.773.8
65.7 °C8.2
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 79.673.411.01.088.00.834
toluene 110.676.313.1
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 69.059.75
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 80.268.28.6
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 80.866.281181
carbon tetrachloride 76.865.25
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 82.066.08.268.523.3
methyl ethyl ketone 79.668.28.8
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 76.865.73.0
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
cyclohexane 81.063.65.0
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 64.6552.64.0
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
acetone 56.560.44.057.638.4

Saddle azeotrope

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

2nd componentb.p.
2nd comp. (˚C)
3rd componentb.p.
3rd comp. (˚C)
 b.p.
azeo. (˚C)
 % wt
1st
 % wt
2nd
 % wt
3rd
spec.
grav
acetone 56.5 chloroform 61.2 57.523.030.047.0
methyl acetate 57.053.717.45.876.80.898
cyclohexane 81.451.516.043.540.5
methyl acetate 57.1 carbon disulfide 46.237.0
cyclohexane 81.450.817.848.633.6
n-hexane 69.045.014.027.059.00.73

Saddle azeotrope

Related Research Articles

<span class="mw-page-title-main">Distillation</span> Method of separating mixtures

Distillation, or classical distillation, is the process of separating the components or substances from a liquid mixture by using selective boiling and condensation, usually inside an apparatus known as a still. Dry distillation is the heating of solid materials to produce gaseous products ; this may involve chemical changes such as destructive distillation or cracking. Distillation may result in essentially complete separation, or it may be a partial separation that increases the concentration of selected components; in either case, the process exploits differences in the relative volatility of the mixture's components. In industrial applications, distillation is a unit operation of practically universal importance, but is a physical separation process, not a chemical reaction. An installation used for distillation, especially of distilled beverages, is a distillery. Distillation includes the following applications:

<span class="mw-page-title-main">Azeotrope</span> Mixture of two or more liquids whose proportions do not change when the mixture is distilled

An azeotrope or a constant heating point mixture is a mixture of two or more components in fluidic states whose proportions cannot be altered or changed by simple distillation. This happens because when an azeotrope is boiled, the vapour has the same proportions of constituents as the unboiled mixture. Azeotropic mixture behavior is important for fluid separation processes.

<span class="mw-page-title-main">Azeotropic distillation</span> Any of a range of techniques used to break an azeotrope in distillation

In chemistry, azeotropic distillation is any of a range of techniques used to break an azeotrope in distillation. In chemical engineering, azeotropic distillation usually refers to the specific technique of adding another component to generate a new, lower-boiling azeotrope that is heterogeneous, such as the example below with the addition of benzene to water and ethanol.

<span class="mw-page-title-main">Extractive distillation</span>

Extractive distillation is defined as distillation in the presence of a miscible, high-boiling, relatively non-volatile component, the solvent, that forms no azeotrope with the other components in the mixture. The method is used for mixtures having a low value of relative volatility, nearing unity. Such mixtures cannot be separated by simple distillation, because the volatility of the two components in the mixture is nearly the same, causing them to evaporate at nearly the same temperature at a similar rate, making normal distillation impractical.

This page provides supplementary chemical data on acetone.

This page provides supplementary chemical data on ethanol.

This page provides supplementary chemical data on methanol.

A zeotropicmixture, or non-azeotropic mixture, is a mixture with liquid components that have different boiling points. For example, nitrogen, methane, ethane, propane, and isobutane constitute a zeotropic mixture. Individual substances within the mixture do not evaporate or condense at the same temperature as one substance. In other words, the mixture has a temperature glide, as the phase change occurs in a temperature range of about four to seven degrees Celsius, rather than at a constant temperature. On temperature-composition graphs, this temperature glide can be seen as the temperature difference between the bubble point and dew point. For zeotropic mixtures, the temperatures on the bubble (boiling) curve are between the individual component's boiling temperatures. When a zeotropic mixture is boiled or condensed, the composition of the liquid and the vapor changes according to the mixtures's temperature-composition diagram.

Batch distillation refers to the use of distillation in batches, meaning that a mixture is distilled to separate it into its component fractions before the distillation still is again charged with more mixture and the process is repeated. This is in contrast with continuous distillation where the feedstock is added and the distillate drawn off without interruption. Batch distillation has always been an important part of the production of seasonal, or low capacity and high-purity chemicals. It is a very frequent separation process in the pharmaceutical industry.

The McCabe–Thiele method is a technique that is commonly employed in the field of chemical engineering to model the separation of two substances by a distillation column. It uses the fact that the composition at each theoretical tray is completely determined by the mole fraction of one of the two components. This method is based on the assumptions that the distillation column is isobaric—i.e the pressure remains constant—and that the flow rates of liquid and vapor do not change throughout the column. The assumption of constant molar overflow requires that:

In thermodynamics and chemical engineering, the vapor–liquid equilibrium (VLE) describes the distribution of a chemical species between the vapor phase and a liquid phase.

This page provides supplementary chemical data on benzene.

This page provides supplementary chemical data on ethylene glycol.

This page provides supplementary chemical data on diethyl ether.

This page provides supplementary chemical data on 1-Propanol (n-propanol).

This page provides supplementary chemical data on carbon disulfide.

This page provides supplementary chemical data on o-Xylene.

This page provides supplementary chemical data on m-Xylene.

This page provides supplementary chemical data on trichloroethylene.

<span class="mw-page-title-main">Residue curve</span>

A residue curve describes the change in the composition of the liquid phase of a chemical mixture during continuous evaporation at the condition of vapor–liquid equilibrium. Multiple residue curves for a single system are called residue curves map.

References

  1. Lange's Handbook of Chemistry, 10th ed. pp. 1496–1505
  2. CRC Handbook of Chemistry and Physics, 44th ed. pp. 2143–2184
  3. 1 2 3 4 5 Lee H. Horsley, ed. (1 June 1973). Azeotropic Data—III. Advances in Chemistry Series No. 166. Vol. 116. American Chemical Society. doi:10.1021/ba-1973-0116. ISBN   9780841201668.
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