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Azeotrope tables

From Wikipedia, the free encyclopedia

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.

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

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

Binary 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[5] 64.7 Doesn't form azeotrope
1-propanol 97.3 87.7 71.7 0.866
2-propanol 82.5 80.4 87.7 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
isobutanol 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
furfuryl alcohol 169.4 98.5 20
cyclohexanol[6] 161.1 97.8 20
benzyl alcohol[6] 205.4 99.9 9
with various organic acids
formic acid 100.8 107.3 77.5
acetic acid [5][7] 118.1 No azeotrope
propionic acid 141.1 99.98 17.7 1.016
butyric acid 163.5 99.94 18.4 1.007
isobutyric acid 154.5 99.3 21
with mineral acids
nitric acid 83.0 120.5 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[8] 61.2 56.1 97.2
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[6] 101.6 82.4 86
isopropyl acetate[9] 88.7 75.9 88.9
ethyl nitrate 87.7 74.4 78
with various other solvents
acetone [5][7] 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
CPME[10] 106 83 83.7
MTBE[10] 55 52.9 96.5
diethyl ether 34.5 34.2 98.7 0.720
tetrahydrofuran[5] 66 64.2[11] 95
2-methyltetrahydrofuran[12][10] 80.2 71 89.4
anisole 153.9 95.5 59.5
acetonitrile 82.0 76.5 83.7 0.818
chloral 97.75 95.0 93.0
hydrazine[13] 113.5 °C 120.3 °C 68.5
m-xylene[3][14] 139.0 92.0 64.2

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 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

Binary 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[6] 88.4 76.8 47
with various hydrocarbons
benzene 80.2 68.2 67.6 0.848
cyclohexane[15] 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[16]
P = 100 kPa
65.6 65 96.7
2-methyltetrahydrofuran[12] 80.2 74.4 66
thiophene[15] 84.1 70.0 55.0
carbon disulfide[6] 46.2 42.4 92

Binary 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 60.5 0.844
toluene 110.8 63.8 31 0.813
cyclohexane 80.8 45.2 62.8
U 97.0
L 39.0
n-pentane 36.2 30.8 91
n-hexane[17] 68.9 60 71.6
n-heptane 98.5 59.1 48.5
n-octane 125.8 63.0 72.0
with various alkyl halides
methylene chloride 40.0 37.8 92.7
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[6] 87.2 60.2 64
tetrachloroethylene[16] 121.1 63.5 40.6
trichlorotrifluoroethane (CFC 113)[6] 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
isopropyl alcohol[6] 82.5 64.0 20
tetrahydrofuran[18]
P = 984 mBar
65.6 60.7 69.0
2-methyltetrahydrofuran[12] 80.2 62.7 43
MTBE[19] 55 51.3 68.6

Binary 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
2-methyltetrahydrofuran[12] 80.2 79.5 99

Binary 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[6] 80.8 79.7 98
toluene 110.8 105.0 72 0.905
m-xylene 139.0 115.4 27.5 0.908
mesitylene[20] 164.6 118 3.6
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

Binary azeotropes of Isopropyl alcohol, 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 [15] 110.8 80.6 42
cyclohexane 80.7 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[15] 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
2-methyltetrahydrofuran[12] 80.2 77 82

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

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

2nd Component b.p. of
comp. (˚C)
b.p. of
mixture (˚C)
% by
weight
spef.
grav
with various hydrocarbons
benzene 80.2 71.7 69
toluene 110.8 85.8 50
m-xylene 139.0 94.2 29.8
m-xylene[3][14] 139.0 92.8 28.2
o-xylene[3] 143.6 95.5 26
p-xylene[3] 138.4 ~95 30.0
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

Binary 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 80.74 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[6] 98.5 80.0 1

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

2nd Component b.p. of
comp. (˚C)
b.p. of
mixture (˚C)
% by
weight
spef.
grav
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

Binary 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

Binary 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 80.74 53.0 33.0
n-hexane 68.8 49.8 41
ethyl iodide 56.5 55.0 40.0
carbon tetrachloride[15] 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
n-butane[15] –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
toluene[16] 110.6 81.1 76.0 24.0
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[6] 77.1 46.1 97 3
methyl acetate[6] 57.0 40.2 73 27
chloroform 61.2 methyl ethyl ketone 79.6 79.9 17.0 83.0 0.877
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 80.74 ethyl acetate 77.15 72.8 46.0 54.0
ethyl nitrate 88.7 74.5 64.0 36.0
diethyl ether 34.6 methyl formate 31.50 28.2 44.0 56.0
methylene chloride[5] 40 40.8 30 70
nitromethane 101.0 toluene 110.8 96.5 55.0 45.0
tetrahydrofuran[18] 65.6 chloroform 61.2 72.5 34.5 65.5
n-hexane 69 63.0 46.5 53.5
toluene 110.63 pyridine 115.3 110.2 78.0 22.0
2-methyltetrahydrofuran[12] 80.2 none - -
propylene glycol[21] 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

[edit]

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
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
Isopropyl alcohol 82.5 cyclohexane 80.8 64.3 7.5 18.5 74.0
66.1 7.5 21.5 71.0
benzene 80.2 °C 66.5 7.5 18.7 73.8
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
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
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
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

[edit]
  1. ^ Lange's Handbook of Chemistry, 10th ed. pp. 1496–1505
  2. ^ CRC Handbook of Chemistry and Physics, 44th ed. pp. 2143–2184
  3. ^ a b c d e 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.
  4. ^ "Azeotrope Databank".
  5. ^ a b c d e "What is an Azeotrope?". B/R Corporation. Archived from the original on 24 April 2007. Retrieved 24 March 2007.
  6. ^ a b c d e f g h i j k l John Durkee (November 2000). "Binary Organic Azeotropes Useful for Solvent Cleaning" (PDF). metalfinishing.com. Retrieved 13 February 2011.[permanent dead link]
  7. ^ a b Hilmen, Eva-Katrine (November 2000). "Separation of Azeotropic Mixtures: Tools for Analysis and Studies on Batch Distillation Operation" (PDF). Norwegian University of Science and Technology, dept. of Chemical Engineering. Archived from the original (PDF) on 5 September 2004. Retrieved 24 March 2007.
  8. ^ Composition of Vapors from Boiling Binary Solutions J. J. Conti, D. F. Othmer, Roger Gilmont. J. Chem. Eng. Data, 1960, 5 (3), pp. 301–307 doi:10.1021/je60007a019
  9. ^ US4826576A, Berg, Lloyd & Yeh, An-I., "Separation of isopropyl acetate from isopropanol by extractive distillation", issued 1989-05-02 
  10. ^ a b c "Zeon Corporation" (PDF). Archived from the original (PDF) on 22 July 2011. Retrieved 5 August 2024.
  11. ^ "Modeling and optimization of pressure distillation to achieve pharma-grade THF".
  12. ^ a b c d e f "MeTHF training presentation" (PDF). Retrieved 31 July 2024.
  13. ^ Merck Index of Chemicals and Drugs, 9th ed. monograph 4653
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