The vaporization enthalpy and vapor pressure of (d)-amphetamine and of several primary amines used as standards at T /K = 298 as evaluated by correlation gas chromatography and transpiration

Article abstract of DOI:10.1021/je400212t

The vapor pressures of several aliphatic and phenyl substituted primary amines at T/K = 298.15 are measured by transpiration studies, and their vaporization enthalpies are calculated. The results were combined with compatible literature values to evaluate both the vaporization enthalpy and vapor pressure of (d)-amphetamine by correlation gas chromatography. The results are compared to existing values either estimated or measured for racemic amphetamine. Vaporization enthalpies and vapor pressures at T/K = 298.15 of the following were measured by transpiration (kJ·mol^-1, p/Pa): 1-heptanamine, (49.75 ± 0.38, 291); 1-octanamine, (55.05 ± 0.29, 108); 1-decanamine, (64.94 ± 0.32, 12); benzylamine, (54.32 ± 0.32, 88); (dl)-α-methylbenzylamine, (55.26 ± 0.33, 82); 2-phenethylamine (57.51 ± 0.35, 43). The use of several of these materials as standards resulted in a vaporization enthalpy and vapor pressure for (d)-amphetamine at T/K = 298.15 of (58.2 ± 2.7) kJ mol^-1 and (38 ± 12) Pa.

Full text of DOI:10.1021/je400212t

Article
pubs.acs.org/jced
The Vaporization Enthalpy and Vapor Pressure of (d)‑Amphetamine
and of Several Primary Amines Used as Standards at T/K = 298 As
Evaluated by Correlation Gas Chromatography and Transpiration
Melissa Thornton and James Chickos*
Department of Chemistry and Biochemistry, University of Missouri-St. Louis, St. Louis, Missouri 63121, United States
Inna V. Garist,+ Mikhail A. Varfolomeev,§ Aleksei A. Svetlov,⊥ and Sergey P. Verevkin
Department of Physical Chemistry, University of Rostock, Dr-Lorenz-Weg-1, D-18059 Rostock, Germany
S
* Supporting Information
ABSTRACT: The vapor pressures of several aliphatic and
phenyl substituted primary amines at T/K = 298.15 are
measured by transpiration studies, and their vaporization
enthalpies are calculated. The results were combined with
compatible literature values to evaluate both the vaporization
enthalpy and vapor pressure of (d)-amphetamine by
correlation gas chromatography. The results are compared to existing values either estimated or measured for racemic
amphetamine. Vaporization enthalpies and vapor pressures at T/K = 298.15 of the following were measured by transpiration
(kJ·mol−1, p/Pa): 1-heptanamine, (49.75 0.38, 291); 1-octanamine, (55.05 0.29, 108); 1-decanamine, (64.94 0.32, 12);
benzylamine, (54.32 0.32, 88); (dl)-α-methylbenzylamine, (55.26 0.33, 82); 2-phenethylamine (57.51 0.35, 43). The use
of several of these materials as standards resulted in a vaporization enthalpy and vapor pressure for (d)-amphetamine at T/K =
298.15 of (58.2 2.7) kJ mol−1 and (38 12) Pa.
S-(+)-Amphetamine ((d)-α-methylphenethylamine) or (d)-2-
amino-1-phenylpropane is a drug that has been used recrea-
tionally, as a performance enhancer, an antidepressant, and as a
decongestant (Benzedrine, Smith Kline, and French).1 It is
highly regulated but generally available by prescription in the
United States in Adderall,2 a treatment for attention deficit
hyperactivity disorder (ADHD) in the form of an amine salt.
Despite the use and widespread misuse of this drug, relatively
little experimental thermochemical information is available in
the literature. An experimental measure of the vapor pressure of
(d)-amphetamine at T/K = 293 has been reported as (32 3)
Pa.3 At T/K = 298.15 a vapor pressure of 40 Pa is estimated by
ACD Laboratories software as cited by SciFinder Scholar.4 The
EPI Suite5 estimates a similar vapor pressure value. Estimates of
both the vaporization enthalpy and vapor pressures of this
material were evaluated by correlation gas chromatography.
The selection of standards for use by correlation gas
chromatography can significantly affect the quality of the
results obtained. Structurally similar standards with comparable
retention times are preferable. Data for suitable materials
currently available included benzylamine, (dl)-α-methylbenzyl-
amine, 2-phenethylamine, and 1-decanamine. Table 1 lists the
vaporization and vapor pressure data available in the literature
for these materials. The structure of these and some additional
primary amines studied are provided in Figure 1. Vapor
pressures at T/K = 298.15 were calculated from the available
pressure−temperature equations. Since the original data are
available in several different mathematical formats, all have been
converted to the same format for comparison purposes. Several
concerns arose upon examination of the data in this table.
While the vapor pressures for the first two entries for
benzylamine appear in very good agreement,7,8 the vaporization
enthalpies for these entries lie outside the uncertainties
reported. A third value is quite old and the last entry is
considerably different.9,10 Additionally, the constants reported
in the first entry for (dl)-α-methylbenzylamine do not
reproduce the vapor pressures reported;7 the vaporization
the vaporization enthalpy of (43.77
3.0)kJ·mol−1 are also
reported for amphetamine.4 Although a reference temperature
is not provided by the ACD Lab, the pressure of p/Pa =
101 326 that is cited implies that this value is the vaporization
enthalpy at the boiling temperature. Assuming this to be
correct, then adjustment to T/K = 298.15 using the protocol
described below results in a vaporization enthalpy of (58.2
5.9) kJ mol−1 for (d)-amphetamine. An experimental vapor-
ization enthalpy for (dl)-amphetamine of 53.4 kJ mol−1 has
been reported at the mean temperature, T/K = 343.6 The
original reference to this work is not available. Adjusted to T/K
= 298.15 also described below results in a value of (57.1 1.1)
kJ mol−1. In view of the lack of experimental data and the
limited amounts of (d)-amphetamine commercially available,
Received: March 3, 2013
Accepted: May 23, 2013
© XXXX American Chemical Society
A
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a
Table 1. Equation Parameters, Vaporization Enthalpies, and Vapor Pressures of Some Primary Amines from the Literature
T
ΔlgHm(Tm)
kJ·mol−1 (K)
ΔlgHm(298 K)
kJ·mol−1
p
b
compound
benzylamine
K range
A
B
Pa, 298.15 K
ref
283 to 313
293 to 363
302 to 458
298.15
25.5 0.2
25.8 0.1
19.557
6257 69
6340 38
5889
52.1 0.6 (298)
52.7 0.3 (328)
49.0 2.1 (380)
52.0 0.6
54.6 0.3
54.4 1.3
60.2
91
7
8
95
110
na
9, 10
11, 12
c
(dl)-α-methyl-benzylamine
283 to 318
292 to 318
273 to 352
333 to 353
22.3 0.1
22.08
6584 34
4414.8
54.7 0.3 (303)
36.7
55.0 0.3
37.3
1.2
7
1440
45
6
2-phenethylamine
(dl)-amphetamine
(d)-amphetamine
26.3 0.1
25.63
6704 30
6428
55.7 0.2 (313)
53.4 (343)
8
59
6
d
32
3
3
e
43.8 3.0 (475)
56.1 0.6 (380)
4
f
1-decanamine
329 to 431
443 to 473
20.55
17.01
6747 71
6110
11
13
13
6
g
h
50.8 (458)
a
b
c
Clausius−Clapeyron equation: ln(p/Pa) = A − B/(T/K). Evaluated and/or extrapolated to T/K = 298.15. Vapor pressure cited at T/K = 298.4; a
d
e
vapor pressure of p/Pa = 1.2 is calculated from the equation given. Vapor pressure at T/K = 293. Vaporization enthalpy estimate from ref 4;
f
boiling temperature experimental from ref 14. Experimental vapor pressures were fit to the following third order polynomial and extrapolated to T/
K = 298.15 K: ln(p/Pa) = AT −3 + BT−2 + CT + D. The vapor pressures at T/K = 298.15 were calculated from this polynomial. Constants for the
g
polynomial are provided in the Supporting Information. The vaporization enthalpy was calculated using vapor pressures calculated over the
temperature range noted and fit to the Clausius−Clapeyron equation. The vapor pressures were calculated from the Antoine equation, log (p/kPa)
= A′ − B′/(C′ + T), derived from measurements over the temperature range, T/K = (410 to 506); [A′, 6.4229; B′, 1844.7; C′, −76.05], ref 6.
h
EXPERIMENTAL SECTION
■
Materials. The origin of the standards and their purities are
listed in Table 2. The liquid samples of alkaneamines used in
Rostock were obtained from Aldrich and Fluka and further
purified by repetitive distillation in vacuum. The degree of
purity was determined by GC. No impurities (greater than
mass fraction 5 × 10−4) could be detected in samples for
thermochemical study. The products were analyzed on a
Hewlett-Packard gas chromatograph 5890 series II with a flame
ionization detector and Hewlett-Packard 3390A integrator.
Additional details are provided in the Supporting Information.
The materials used in St. Louis with the exception of
benzylamine were from the same supplier and of similar purity;
all were used as purchased. Benzylamine contained approx-
imately 7 minor components, all less than a mass fraction of
0.01. Sample purity is not an important issue with the
correlation gas chromatography technique since the chroma-
tography generally separates the impurities. The analysis of the
certified (d)-amphetamine (as the hemisulfate) as provided by
the supplier was approximately 0.735. Only one volatile peak
other than the solvents was observed in the free base when
analyzed by gas chromatography.
Figure 1. The structures of the amines investigated (top to bottom,
left to right): 1-heptanamine, 1-octanamine, 1-decanamine, (dl) α-
methylbenzylamine, 2-phenethylamine, and S-(d)-amphetamine.
enthalpy of the second entry seems unreasonably small.6 The
first vaporization enthalpy listed for 1-decanamine is also quite
old,13 and the second requires a large temperature adjustment
(17.5
2.6 kJ mol−1) from the mean temperature of
measurement to T/K = 298.15.6 Similarly, its vapor pressure
at T/K = 298.15 required a temperature extrapolation of the
Antoine equation of well over 100 K. In view of these concerns,
measurements for all these materials were repeated, including
those for 2-phenethylamine. Additional vaporization enthalpies
and vapor pressures for 1-heptanamine and 1-octanamine are
also reported to determine how well the linear 1-alkanamines
correlate in correlation gas chromatography experiments for the
reason described below.
S-(d)-Amphetamine (as the hemisulfate) reference standard
was purchased in a methanolic solution from Restek (cat no.
Table 2. Origin of the Standards and Targets and Their Analysis
mass fraction
GC
compound
benzylamine
CASRNs
supplier
Rostock
St. Louis
Rostock
a
100-46-9
618-36-0
111-68-2
64-04-0
Aldrich MCB
Aldrich
Aldrich
Fluka
0.99
0.99
0.99
0.99
0.995
0.96
0.99
0.99
> 0.995
> 0.995
> 0.995
> 0.995
> 0.995
(dl)-α-methylbenzylamine
1-heptanamine
b
2-phenethylamine
1-octanamine
AS
111-86-4
51-64-9
Aldrich
Restek
0.995
0.95
c
(d)-amphetamine
1-decanamine
reference standard
0.95
2016-57-1
Aldrich
> 0.99
a
b
c
Matheson, Coleman, and Bell. Analytical standard. Available as the hemisulfate in methanolic solution at 1000 μg/mL; purity level 0.735 as
described in the certificate; no other peaks were observed in the GC trace of the free base.
B
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Table 3. Vapor Pressures p and Enthalpies of Vaporization, ΔlgHm, Obtained by the Transpiration Method (R = 8.313
J·mol−1·K−1)
a
b
c
d
T/K
m/mg
V(N2)/dm3
flow of N2/dm3·h−1
p/Pa
(pexp − pcalc)/Pa
ΔlgHm/kJ·mol−1
1-heptanamine; ΔlgHm(298.15 K) = (49.75 0.38) kJ·mol−1
⎛
⎜
⎝
⎞
⎟
⎠
298.91
R
75059.34
(RT/K)
84.9
R
T/K
298.15
ln(p/Pa) =
−
−
ln
(5)
280.2
282.2
284.2
286.2
288.2
290.2
292.2
294.2
296.2
298.3
300.3
302.2
303.2
306.2
2.16
1.83
2.18
2.06
2.05
2.03
1.93
2.00
1.97
2.03
4.04
2.45
2.40
2.95
0.614
0.429
0.442
0.368
0.319
0.270
0.221
0.197
0.172
0.152
0.267
0.140
0.127
0.127
1.47
78.23
94.51
−0.22
2.84
51.27
51.10
50.94
50.77
50.60
50.43
50.26
50.09
49.92
49.74
49.57
49.41
49.32
49.07
1.36
1.47
1.47
1.47
1.47
1.47
1.47
1.47
1.52
1.52
1.52
1.52
1.52
108.83
123.19
140.76
164.13
190.74
221.91
248.84
288.48
328.82
379.97
409.78
502.65
2.00
−0.99
−3.20
−2.35
−1.31
0.91
−4.88
−4.09
−5.50
1.27
5.73
13.43
1-octanamine;ΔlgHm (298.15 K) = (55.05 0.29) kJ·mol−1
⎛
⎜
⎝
⎞
⎟
⎠
316.77
R
82836.99
(RT/K)
93.2
R
T/K
298.15
ln(p/Pa) =
−
−
ln
(6)
274.2
277.7
281.0
283.2
283.6
285.9
286.5
289.2
289.6
292.4
292.4
295.2
295.3
295.3
298.1
298.5
301.1
301.2
301.2
301.2
301.3
301.3
304.0
304.1
307.1
307.3
310.2
310.3
312.3
313.0
313.3
1.21
1.13
1.21
1.36
2.72
2.81
2.46
2.72
2.23
2.69
2.82
3.34
1.89
1.84
2.20
2.62
2.50
2.53
3.02
3.41
2.97
3.41
2.38
4.60
3.50
3.03
3.72
4.78
4.40
5.17
4.67
1.500
1.050
0.850
0.800
1.469
1.250
1.076
1.000
0.765
0.750
0.765
0.750
0.414
0.414
0.393
0.464
0.348
0.368
0.414
0.476
0.426
0.484
0.271
0.517
0.310
0.271
0.279
0.348
0.271
0.310
0.271
3.00
15.7
20.8
0.9
0.4
57.12
56.82
56.54
56.35
56.32
56.12
56.07
55.84
55.81
55.57
55.57
55.33
55.33
55.33
55.09
55.05
54.83
54.83
54.83
54.83
54.82
54.82
54.59
54.58
54.32
54.31
54.06
54.05
53.88
53.82
53.80
3.00
3.00
3.00
1.24
3.00
1.24
3.00
1.24
3.00
1.24
3.00
1.24
1.24
1.24
1.16
1.16
1.16
1.24
1.24
1.16
1.16
1.16
1.24
1.24
1.16
1.24
1.16
1.16
1.24
1.16
27.4
0.2
32.5
−0.3
0.8
34.7
42.8
1.7
42.8
−0.4
−2.1
−1.1
−1.6
−0.3
−2.0
−1.1
−3.3
−2.4
−3.9
1.8
51.7
54.5
67.7
69.0
84.0
85.6
83.4
104.7
106.4
135.3
129.4
136.9
134.1
131.2
132.8
165.3
166.7
211.3
210.2
249.4
257.8
305.1
312.1
323.8
−5.1
2.4
−0.5
−4.3
−2.7
0.8
1.0
6.8
2.8
−3.5
3.2
14.0
7.1
12.8
1-decanamine; ΔlgHm(298.15 K) = (64.94 0.32) kJ·mol−1
⎛
⎜
⎝
⎞
⎟
⎠
348.00
R
97651.03
(R/K)
109.7
R
T/K
298.15
ln(p/Pa) =
−
−
ln
(7)
299.1
300.2
301.3
304.0
2.52
2.33
2.63
2.41
3.000
2.564
2.564
1.909
3.27
13.0
14.0
15.8
19.5
0.3
0.0
0.4
0.2
64.85
64.72
64.60
64.31
3.27
3.27
3.27
C
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Table 3. continued
a
b
c
d
T/K
m/mg
V(N2)/dm3
flow of N2/dm3·h−1
p/Pa
(pexp − pcalc)/Pa
ΔlgHm/kJ·mol−1
306.2
307.3
308.6
310.2
312.2
313.2
315.1
316.2
317.2
320.0
320.9
323.2
324.3
324.3
327.2
330.1
330.1
332.8
332.8
333.1
333.1
335.9
335.9
338.9
338.9
341.9
341.9
343.0
2.38
2.78
2.58
2.28
2.96
2.33
1.09
2.27
2.27
2.15
1.28
2.33
2.15
2.16
1.88
3.29
3.30
3.34
2.91
2.97
2.99
3.86
3.87
4.91
4.86
5.60
5.53
6.75
1.603
1.637
1.364
1.091
1.266
0.841
0.364
0.682
0.631
0.504
0.273
0.445
0.364
0.364
0.273
0.375
0.375
0.309
0.273
0.281
0.281
0.300
0.281
0.300
0.284
0.281
0.281
0.309
5.06
3.27
1.09
3.27
5.06
2.52
1.09
1.78
2.52
1.78
1.09
1.78
1.09
1.09
1.09
1.13
1.09
1.09
1.09
1.13
1.09
1.13
1.09
1.13
1.09
1.13
1.09
1.13
22.8
26.2
−0.3
0.8
64.07
63.95
63.80
63.63
63.41
63.30
63.09
62.97
62.86
62.55
62.45
62.20
62.08
62.08
61.76
61.44
61.44
61.15
61.15
61.12
61.12
60.81
60.81
60.48
60.48
60.15
60.15
60.03
29.1
1.0
32.1
0.1
36.0
−1.5
2.0
42.6
46.0
−0.9
0.2
51.2
55.3
0.3
65.5
−2.2
−0.2
−4.9
−1.4
−1.0
−7.3
−3.2
−2.6
0.4
72.2
80.5
91.1
91.4
106.0
135.0
135.6
166.1
164.5
162.8
163.5
197.9
211.9
251.9
262.8
306.4
302.5
335.7
−1.2
−6.2
−5.5
−5.2
8.8
5.8
16.6
9.4
5.5
17.8
benzylamine; ΔlgHm (298.15 K) = (54.26 0.32) kJ·mol−1
⎛
⎜
⎝
⎞
⎟
⎠
283.56
R
73456.05
R(T/K)
64.40
R
T/K
298.15
ln(p/Pa) =
−
−
ln
(8)
Series 1 from 2006 (unpublished results)
275.5
278.6
281.5
284.5
287.6
290.5
293.5
296.5
298.4
301.3
303.4
303.4
304.3
307.4
308.3
308.4
310.3
313.4
1.16
1.25
1.46
1.74
1.89
2.10
2.21
2.41
1.77
2.35
9.39
3.62
3.01
3.51
9.83
3.80
4.32
5.36
1.937
1.624
1.494
1.299
1.137
1.043
0.841
0.706
0.470
0.478
1.696
0.660
0.510
0.478
1.272
0.495
0.478
0.495
1.94
14.37
18.28
23.07
31.35
38.74
46.95
60.98
78.84
86.90
0.30
−0.16
−0.52
1.08
55.72
55.52
55.33
55.14
54.94
54.75
54.56
54.36
54.24
54.06
53.92
53.92
53.86
53.66
53.60
53.60
53.48
53.28
1.95
1.95
1.95
1.95
2.02
2.02
2.02
1.88
1.91
5.09
1.98
1.91
1.91
5.09
1.98
1.91
1.98
−0.16
−1.96
−0.65
1.59
−1.99
4.03
113.71
127.69
126.34
136.29
169.27
178.08
176.71
208.16
249.07
0.36
−0.99
0.65
1.20
−0.60
−3.19
3.72
−1.82
benzylamine; ΔlgHm (298.15 K) = (54.39 0.32) kJ·mol−1
⎛
⎜
⎝
⎞
⎟
⎠
283.93
R
73594.45
R(T/K)
64.40
R
T/K
298.15
ln(p/Pa) =
−
−
ln
(9)
Series 2 from 2013
276.7
276.7
279.6
279.6
282.3
282.3
2.66
2.76
2.67
2.81
2.72
2.81
4.320
4.320
3.312
3.312
2.520
2.520
4.32
14.72
15.25
19.12
20.04
25.34
26.15
−0.67
−0.14
−0.75
0.16
55.78
55.78
55.59
55.59
55.41
55.41
4.32
4.32
4.32
4.32
4.32
0.31
1.12
D
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Table 3. continued
a
b
c
d
T/K
m/mg
V(N2)/dm3
flow of N2/dm3·h−1
p/Pa
(pexp − pcalc)/Pa
ΔlgHm/kJ·mol−1
285.7
285.7
288.0
288.0
291.6
291.6
294.2
294.2
297.7
297.7
300.3
300.3
303.3
303.5
306.1
306.3
309.4
309.5
312.2
312.3
312.3
315.6
2.70
2.61
2.37
2.37
2.26
2.26
2.09
2.09
2.05
2.05
1.89
1.89
2.40
2.00
2.33
1.81
2.38
2.34
2.91
3.63
3.74
3.62
1.823
1.823
1.403
1.403
0.976
0.976
0.747
0.747
0.574
0.574
0.431
0.431
0.431
0.365
0.365
0.276
0.294
0.276
0.294
0.368
0.368
0.276
4.21
4.21
4.21
4.21
1.72
1.72
1.72
1.72
1.72
1.72
1.72
1.72
1.72
1.46
1.46
1.10
1.17
1.10
1.17
1.10
1.10
1.10
34.58
33.41
1.62
0.44
55.20
55.20
55.05
55.05
54.82
54.82
54.65
54.65
54.42
54.42
54.25
54.25
54.06
54.05
53.88
53.87
53.67
53.66
53.49
53.48
53.48
53.27
39.34
−0.38
−0.38
0.94
39.34
53.62
53.62
0.94
64.87
0.46
64.87
0.46
82.47
−1.30
−1.30
−0.05
−0.05
2.85
82.47
101.48
101.48
128.31
126.00
146.86
151.35
187.10
195.07
228.39
227.18
233.88
301.64
−1.07
−6.27
−2.95
−3.82
2.73
−1.90
−5.41
1.30
14.22
α-methyl-benzylamine; ΔlgHm (298.15 K) = (55.26 0.33) kJ·mol−1
⎛
⎜
⎝
⎞
⎟
⎠
294.23
R
76812.64
R(T/K)
72.3
R
T/K
298.15
ln(p/Pa) =
−
−
ln
(10)
283.6
287.8
291.3
291.3
295.3
299.2
303.1
307.1
311.0
314.9
318.9
322.8
2.66
3.23
4.59
5.99
3.54
4.94
5.47
5.25
4.14
4.43
4.85
5.82
2.220
1.885
1.920
2.486
1.100
1.143
0.948
0.694
0.419
0.348
0.293
0.272
2.22
25.09
35.34
−0.67
−0.95
1.23
56.31
56.01
55.76
55.76
55.46
55.18
54.90
54.61
54.33
54.04
53.76
53.47
1.88
1.92
2.49
1.10
1.14
0.95
0.69
0.42
0.35
0.29
0.27
49.28
49.51
1.47
65.95
0.27
88.66
0.69
118.31
155.16
202.43
260.21
339.07
439.07
0.76
−0.07
−0.44
−4.18
−2.33
1.84
2-phenethylamine; ΔlgHm (298.15 K) = (57.51 0.35) kJ·mol−1
⎛
⎜
⎝
⎞
⎟
⎠
299.28
R
79837.30
R(T/K)
74.9
R
T/K
298.15
ln(p/Pa) =
−
−
ln
(11)
285.2
287.4
288.2
288.2
290.1
293.1
293.2
298.2
298.2
298.3
300.1
302.0
303.2
303.3
303.3
304.2
305.1
305.1
306.4
308.2
1.66
1.66
1.37
1.42
1.52
2.13
0.89
2.80
1.93
1.84
3.02
3.06
1.86
2.60
1.98
2.66
3.66
3.66
3.10
2.62
2.226
1.860
1.427
1.518
1.339
1.518
0.583
1.242
0.911
0.849
1.183
1.037
0.582
0.836
0.637
0.778
1.037
0.985
0.776
0.585
3.04
15.45
18.17
19.89
19.42
23.16
28.88
31.29
46.48
43.34
44.30
51.96
60.07
65.32
64.14
63.28
69.55
71.77
75.50
81.76
92.58
0.23
−0.21
0.22
58.48
58.31
58.25
58.25
58.11
57.89
57.88
57.51
57.51
57.50
57.36
57.22
57.13
57.12
57.12
57.06
56.99
56.99
56.89
56.76
4.46
3.06
3.04
4.46
3.04
1.35
1.36
3.04
2.55
3.09
3.11
3.04
1.36
2.55
3.11
3.11
3.11
1.37
1.35
−0.25
0.10
−0.61
1.55
2.26
−0.88
−0.27
0.75
0.90
0.57
−1.10
−1.96
−0.21
−2.79
0.94
−0.25
−0.84
E
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Journal of Chemical & Engineering Data
Article
Table 3. continued
a
b
c
d
T/K
m/mg
V(N2)/dm3
flow of N2/dm3·h−1
p/Pa
(pexp − pcalc)/Pa
ΔlgHm/kJ·mol−1
308.2
310.4
311.2
313.2
313.4
314.2
317.2
318.2
318.4
320.2
323.2
3.90
3.13
3.18
4.59
2.85
3.08
2.16
7.06
3.06
2.60
2.93
0.911
0.601
0.543
0.708
0.449
0.459
0.242
0.759
0.337
0.242
3.04
1.39
1.02
3.04
1.35
1.02
1.04
3.04
1.35
1.04
1.04
87.80
106.74
120.07
133.12
131.06
137.40
181.78
189.10
187.78
218.66
265.45
−5.62
−2.54
4.45
56.76
56.59
56.53
56.38
56.37
56.31
56.08
56.01
55.99
55.86
55.63
0.21
−3.70
−4.99
7.25
2.51
−1.31
5.72
0.225
6.82
a
b
c
Saturation temperature; uncertainty 0.1 K. Mass of transferred sample condensed at T/K = 243. Volume of nitrogen used to transfer mass m of
d
sample. Vapor pressure at temperature T. Calculated from m and the residual vapor pressure at the cooling temperature T/K = 243; uncertainty in
pressure within 3 % of the reported value.
a
Table 4. Compilation of Some Thermodynamic Properties of Some Primary Amines
l
T
ΔlgHm(Tm) (Tm/K)
kJ·mol−1(K)
−ΔlgCp (Cp )
ΔlgHm(298.15 K)
kJ·mol−1
p
b
compounds
benzylamine
M
T
K range
J·mol−1·K−1
Pa, 298.15 K
ref
283 to 300
293 to 363
302 to 458
298.15
52.0 0.6 (298)
52.7 0.3 (328)
48.96 (380)
52.1 0.6
54.6 0.3
54.4 1.3
60.2
91
95
110
na
7
8
DM
66.6 (215.6)
value (avg)
9, 10
11, 12
T
T
276 to 313
277 to 316
54.5
54.4
54.3 0.3
54.4 0.3
54.4 0.2
50.0 0.1
50.2 1.4
49.8 0.4
50.0 0.2
55.0 0.3
55.3 0.3
36.7
88
87
90
this work
this work
1-heptanamine
C
298.15
23
c
BP
T
327 to 430
280 to 306
43.4 0.6 (379)
50.2 0.4 (293)
84.9 (285.7)
84.9 (285.7)
value (avg)
287
13
291
this work
289
d
α-methyl-benzylamine
T
T
283 to 318
284 to 323
292 to 318
54.7 0.3 (301)
54.9
1.2
7
73.2(241)
73.2(241)
value
82
this work
6
36.8 (305)
1440
82
55.2 0.4
56.8 0.2
57.5 0.3
57.2 0.3
55.5 2.3
54.6 0.5
55.1 0.3
55.1 0.5
57.1 1.1
58.2 5.9
2-phenethyl-amine
1-octanamine
DM
T
273 to 352
285 to 323
55.7 0.2(313)
44
8
74.9(247.5)
value (avg)
93.2 (317.6)
43
this work
44
c
BP
EB
T
308 to 453
344 to 494
274 to 313
47.8 0.4 (381)
43.5 0.4 (419)
55.3 0.3 (294)
136
13
c
122
24
93.2 (317.6)
value (avg)
81.5 (272.9)
81.5 (272.9)
108
108
59
this work
(dl)-amphetamine
(d)-amphetamine
na
333 to 353
53.4
6
est
GC
43.8 3.0 (475)
4
e
32.3
6
c
1-decanamine
443 to 473
329 to 431
299 to 343
50.8 (458)
109.7 (381.4)
109.7 (381.4)
109.7 (381.4)
value (avg)
68.3
2.6
13
6
f
BP
T
56.1 0.6 (380)
64.9 (321)
65.1 0.6
64.9 0.3
65.0 0.2
11
13
12
this work
12
a
b
Values in bold are the values used in calculating the mean. Uncertainties in the mean represent 1 standard deviation of the values in bold. Method
used for measurement: DM, MKS differential manometer; T, transpiration; C, calorimetry; BP, point as a function of pressure; EB, ebulliometer; na,
c
not available; est, estimated; GC, adsorption−desorption gas chromatography. Extrapolated to T/K = 298.15 K from temperature range noted.
d
e
f
Calculated from the equation provided; vapor pressure reported: in p/Pa = 123.4 (T/K = 298.4). Vapor pressure at T/K = 293. Calculated from
the vapor pressures provided over the range noted; see Supporting Information for the polynomial used for the calculation.
34020) in 1 mg quantities. Evaporation of the methanol
followed by addition of a drop of 1 M NaOH generated the free
base which was extracted with hexane and analyzed by gas
chromatography. A small KOH pellet was then added to the
organic solution to remove any moisture. The hexane solution
was then transferred to a second vial and allowed to evaporate.
A dilute methanolic solution containing all the standards was
then added dropwise to a highly concentrated hexane solution
of the free base and analyzed until comparable concentrations
of (d)-amphetamine and standards were achieved. Methanolic
solutions of (d)-amphetamine and standards appeared to give
better peak shapes for the chromatograms run at the lower
temperatures. Experiments performed on the 1-aminoalkanes
F
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Journal of Chemical & Engineering Data
Article
Table 5. A Summary of the Correlations of Three Primary 1-Alkanamines
ΔHtrn(434 K)
kJ·mol−1
ΔlgHm(298 K) (lit)
kJ·mol−1
ΔlgHm(298 K) (calc)
run 1
slope T/K
intercept
kJ·mol−1
1-heptanamine
1-octanamine
1-decanamine
−4280.0
−4677.8
−5316.9
10.553
10.974
11.458
35.58
38.89
44.20
50.0 0.2
55.1 0.5
65.0 0.2
49.7 4.6
55.5 4.8
64.8 5.1
Δ1gHm(298.15 K)/kJ·mol−1 = (1.75 0.09)ΔHtrn(434 K) − (12.6) 5.5)
r2 = 0.9976
(12)
ΔlgHm(298 K) (lit)
ΔHtrn(429 K)
kJ·mol−1
ΔlgHm(298 K) (calc)
kJ·mol−1
run 2
slope T/K
intercept
kJ·mol−1
1-heptanamine
−4526.6
−4827.3
−5302.3
11.114
11.315
11.426
37.63
40.13
44.08
50.0 0.2
55.1 0.5
65.0 0.2
49.7 7.0
55.6 7.2
64.8 7.5
1-octanamine
1-decanamine
Δ1gHm(298.15 K)/kJ·mol‐1 = (2.34 0.13)ΔHtrn(429 K) − (38.4 5.1)
r2 = 0.9971
(13)
Δ1gHm(298.15K)/( kJ·mol−1)
= Δ1gHm(Tm) + [(10.58 + 0.26*Cp(1)/( J·mol−1 K−1)
were run in pentane. In both cases, the solvent also served as
the nonretained reference.
METHODS
(Tm/K − 298.15)]/1000
Temperature adjustments for 1-decanamine,6 (dl)-amphet-
amine,6 and the estimated values for (d)-amphetamine4
discussed above are provided in Table 4.
(2)
■
Rostock − Transpiration Measurements. Vapor pres-
sures of alkaneamines were determined using the method of
transpiration. Details of this method have been published
elsewhere.15,16 Additional details of these experiments are
provided in the Supporting Information.
Uncertainties. All uncertainties associated with temper-
ature adjustments using eq 2 were calculated as follows: an
uncertainty of 16·(Tm/K − 298.15 K)/1000 kJ·mol−1 was
St. Louis: Correlation Gas Chromatography. Measure-
ments of vaporization enthalpy and vapor pressure by
correlation gas chromatography have also been reported
recently.17,18 Details pertaining to these experiments are also
available in the Supporting Information as are the retention
times of all analytes. Adjusted retention times, ta, for each
analyte in the mixture were calculated from each respective
retention time and the retention time of the solvent, which was
not retained by the column, by difference. The adjusted
retention time, a measure of the time an analyte spends on the
column, has been shown to be inversely proportional to its
vapor pressure off the column. A plot of ln(to/ta) vs 1/T where
to is the reference time, 60 s, results in a linear relationship in
which the slope of the line measures the enthalpy of transfer of
the analyte from the column to the gas phase divided by the gas
constant, −ΔHtrn/R. This enthalpy is related to the vapor-
ization enthalpy (ΔlgHm(T)) by eq 1, where ΔHintr(Tm) is the
interaction enthalpy of the analyte with the column.19 Provided
suitable standards are chosen, ΔlgH(T) (where T can represent
another temperature including T/K = 298.15), is found to
correlate linearly with ΔHtrn(Tm). The equation describing the
correlation can then be applied to evaluate the vaporization
enthalpy of the target, in this case (d)-amphetamine.
associated with the second term of eq 2. The uncertainties
2
associated with combined properties were calculated as (u1
+
u2 + ...)0.5 where u represents the uncertainty in each term.
Uncertainties in the vaporization enthalpies and vapor
pressures evaluated by correlation in the following tables
were calculated from the uncertainties in both the slope and
intercept.
2
RESULTS AND DISCUSSION
■
Vapor Pressures and Vaporization Enthalpies. Vapor
pressures of alkaneamines measured in this work are reported
in Table 3 and the results were treated with eqs 3 and 4,
respectively
R ln psat = a + b/T + ΔlgCp ln[T/T ]
o
(3)
i
ΔlgHm(T) = −b + ΔlgCpT
(4)
where pisat is vapor pressure; a and b are adjustable parameters;
To is an arbitrarily chosen reference temperature (To is 298.15
K in this work); and ΔlgCp is the difference of the molar heat
capacities of the gaseous and the liquid phase calculated using
the second term of eq 2. Values of ΔlgCp (see Tables 3 and 4)
were calculated from the isobaric molar heat capacities Cp(l) of
alkanamines using the group contribution method of Acree and
Chickos.20,21 Experimental results and parameters a and b are
listed in Table 3. Vapor pressures derived from the
transpiration method have been reliable within 3% and their
accuracy was governed by reproducibility of the GC analysis.15
The temperature dependence of vapor pressure for the amines
studied is provided as eqs 5 to 11 in Table 3. To assess the
uncertainty of the vaporization enthalpy, the experimental data
were approximated with the linear equation ln(pisat) = f(T−1)
ΔHtrn(Tm) = Δ1gHm(Tm) + ΔHintr(Tm)
(1)
Temperature Adjustments. The temperature adjustments
of vaporization enthalpy to T/K = 298.15 discussed above were
achieved using eq 2.20 The term Cp(l) in this equations refers to
the heat capacity of the liquid at T/K = 298.15 which has been
estimated using a group additivity approach.21
G
dx.doi.org/10.1021/je400212t | J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data
Article
surface. After careful drying in an oven at t/°C = 110, they were
used for loading with the sample into the saturator.
Deactivation of the glass beads appears to be a prerequisite
for reproducible measurements on amines. The disagreement
of our results for benzylamine and (dl)-α-methylbenzylamine in
a previous work7 is apparently due at least in part to this reason.
Correlation Experiments with n-Alkanamines. As an
additional validation of the values measured for the 1-
alkanamines, experiments were also performed to determine
how well the vaporization enthalpies correlated with the
corresponding enthalpies of transfer as measured by correlation
chromatography. Previous work has demonstrated that
homologous series correlate exceptionally well in these
experiments (i.e., ref 17 and references cited). The results for
the 1-alkanamines evaluated in these experiments are reported
in Table 5 (runs 1 and 2) and illustrated by the circles in Figure
2 for run 1. The uncertainties in the figure represent two
standard deviations of the mean value of the standards reported
in Table 4. Equations 12 and 13 listed below each correlation in
Table 5 describe the correlation observed. The vaporization
enthalpy values obtained by correlation are nearly within the
small uncertainty associated with the mean values reported in
Table 4. The linearity of the results seem entirely consistent
with expectations and corroborate the values measured by
transpiration. These results are summarized for runs 1 and 2 in
the last two columns of Table 7. The rather large uncertainties
associated with eqs 12 and 13 are likely due to the few
compounds included in these correlations.
Figure 2. Plots of vaporization enthalpies at T/K = 298 against the
enthalpies of transfer at Tm/K = 434 for run 1 for the C7, C8, and C10
n-alkanamines (•) and for benzyl-, α-methylbenzyl-, phenethyl- and 1-
■
decanamine ( ) for run 3 at T/K = 414 by correlation gas
chromatography. The error bars for both runs represent two standard
deviations of the mean value used for the standards.
using the method of least-squares. The uncertainty in the
enthalpy of vaporization was assumed to be identical with
deviation of experimental ln(pisat) values from this linear
correlation.
Table 4 summarizes the vaporization enthalpies from this
work and those from the literature. The values in bold are those
used in calculating the average value used in the correlation gas
chromatography experiments. The transpiration measurements
on amines in this work have been performed as usual in
accordance with the well-established procedure previously
described15,16 However, previous work has established that
amines are very reactive on the glass beads used in the
experiments and that some sort of stabilization of the amines
was required.22 Consequently, the glass beads used in
transpiration experiments have been washed with 0.1 N
NaOH in order to suppress any possible acidity of the glass
Vaporization Enthalpy of (d)-Amphetamine. Table 6
(runs 3 and 4) summarizes the vaporization enthalpy results for
results for (d)-amphetamine obtained by correlation using both
aromatic and aliphatic primary amines other than aniline and its
derivatives. Work not previously described suggested that
primary aliphatic amines do not correlative as well with
aromatic amines such as aniline and its derivatives. Two
independent sets of correlations are described by eqs 15 and 16
and are listed below each respective correlation. Complete
details are provided in the Supporting Information and the
results from Table 6 are also summarized in Table 7. The
Table 6. Results of the Correlations for (d)-Amphetamine
ΔHtrn(414 K)
kJ·mol−1
ΔlgHm(298 K) (lit)
kJ·mol−1
ΔlgHm(298 K) (calc)
kJ·mol−1
run 3
benzylamine
slope T/K
intercept
−4271.6
−4415.2
−4680.1
−4766.3
−5579
10.209
10.388
10.733
10.796
12.216
35.51
36.71
38.91
39.63
46.38
54.4 0.2
55.2 0.4
57.1 0.3
54.1 1.9
55.3 1.9
57.5 2.0
58.2 2.0
64.9 2.2
(dl)-α-methylbenzylamine
2-phenethylamine
(d)-amphetamine
1-decanamine
65.0 0.2
Δ1gHm(298.15 K)/kJ·mol−1 = (0.99 0.04)ΔHtrn(414 K) + (18.9 1.4)
r2 = 0.9974
(14)
ΔlgHm(298 K) (lit)
ΔHtrn(424 K)
kJ·mol−1
ΔlgHm(298 K) (calc)
kJ·mol−1
run 4
slope T/K
intercept
kJ·mol−1
benzylamine
−4280.89
−4420.53
−4728.26
−4761.47
−5565.67
10.2
10.4
10.8
10.8
12.2
35.59
36.75
39.31
39.58
46.27
54.4 0.2
55.2 0.4
57.2 0.3
54.0 3.3
55.2 3.3
57.8 3.4
58.1 3.4
64.8 3.7
(dl) α-methylbenzylamine
2-phenethylamine
(d)-amphetamine
1-decanamine
65.0 0.2
Δ1gHm(298.15 K)/kJ·mol−1 = (1.01 0.6)ΔHtrn(424 K) − (18.1 2.4)
r2 = 0.9927
(15)
H
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Journal of Chemical & Engineering Data
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Table 7. A Summary of the Vaporization Enthalpies in kJ·mol−1 of Both Standards and Target at T/K = 298.15
run 1
run 2
run 3
run 4
average
lit
benzylamine
54.1 1.9
54.0 3.3
54.1 2.6
49.7 5.8
55.3 2.6
57.7 2.6
55.6 6.0
58.2 2.7
64.8 4.6
54.4 0.2
50.0 0.2
55.2 0.4
57.1 0.6
54.7 0.3
57.1 1.1
65.0 0.2
1-heptanamine
49.7 4.6
49.7 7.0
(dl) α-methylbenzylamine
2-phenethylamine
1-octanamine
55.3 1.9
57.5 2.0
55.2 3.3
57.8 3.4
55.5 4.8
64.8 5.1
55.6 7.2
64.8 7.5
a
(d)-amphetamine
1-decanamine
58.2 2.0
64.9 2.2
58.1 3.4
64.8 3.7
a
Vaporization enthalpy for (dl)-amphetamine.
Table 8. Correlation of ln (to/ta)avg with ln (p/po) at T/K = 298.15 for Runs 1 and 2 (po = 101 325 Pa)
ln (to/ta)avg runs 1 and 2
ln (p/po) exp
ln (p/po) calc
p/Pa calc
p/Pa exp
1-heptanamine
1-octanamine
1-decanamine
−3.926
−4.792
−6.366
−5.86
−6.844
−9.041
−6.957
−7.881
−9.035
307 166
98 59
289
108
12
12
9
runs 1 and 2:
ln(p/p ) = (1.32 0.07) ln((to/ta) − (0.64 0.34) r2 = 0.9974
(16)
o
Vapor pressures: 1-Alkanamines. The vapor pressure of
the 1-alkanamines were calculated by correlating ln (p/po)
against ln (to/ta)avg. The p/Pa term refers to the vapor pressures
of the standards at T/K = 298.15 from Table 4, po/Pa =
101 325 and ln (to/ta)avg represents the average value calculated
from the slope and intercept of both target and standards
correlated in runs 1 and 2 of Table 5. The ln(to/ta)avg, term was
evaluated by first calculating to/ta for both runs at T/K =
298.15, averaging the resulting values and then converting the
average to the natural logarithm. The result of the correlation is
summarized in Table 8 and illustrated by the triangles in Figure
3. The calculated values agree quite well with those from Table
4. The uncertainty in the value by correlation gas
chromatography was estimated from the uncertainty in both
the slope and intercept of eq 16. As noted above, the fairly large
uncertainty associated with the vapor pressures calculated likely
reflects the few data points included in the correlation.
Vapor Pressures: (d)-Amphetamine at T/K = 298.15.
The vapor pressures of the standards and of (d)-amphetamine
were evaluated similarly using the results from runs 3 and 4 of
Table 6 The results are summarized in Table 9 and the
correlation of the standards is illustrated by the solid circles in
Figure 3. The solid square in the figure represents the results
obtained for (d)-amphetamine. The values calculated for the
standards are listed in the last two columns of Table 9 and are
in very good agreement with the experimental values from
Table 4. A vapor pressure of p/Pa = (38 12) at T/K = 298.15
is calculated for (d)-amphetamine, which compares with the
following previous values: p/Pa = 32 measured at T/K = 293 by
Figure 3. A plot of ln (p/po) of the standards against the
corresponding values of ln(to/ta) measured for the standards at T/K
= 298.15. The triangles represent the results obtained for the n-
alkanamines of runs 1 and 2. The solid circles (•) represent the results
■
from runs 3 and 4. The solid square ( ) represents the corresponding
value obtained for (d)-amphetamine at T/K = 298.15. The equations
of the lines calculated by a linear regression are given by eq 16 and 17.
vaporization enthalpy of (58.2 2.7) kJ·mol−1 evaluated in this
work for (d)-amphetamine is within experimental error with
both the value of (57.1 1.1) obtained by extrapolation of the
vaporization enthalpy of (dl)-amphetamine6 and the estimated
value of (58.2 5.9) kJ·mol−1 also obtained by extrapolation
from the boiling temperature.4
Table 9. Correlation of ln(to/ta)avg with ln(p/po) at T/K = 298.15 K for Runs 3 and 4 (po = 101 325 Pa)
ln (to/ta)avg runs 3 and 4
ln (p/po) exp
ln (p/po) calc
p/Pa calc
p/Pa exp
benzylamine
−4.138
−4.424
−5.010
−5.180
−6.482
−7.026
−7.124
−7.742
−6.957
−7.211
−7.731
−7.881
−9.035
96 28
75 22
44 14
38 12
90
82
44
(dl)-α-methylbenzylamine
2-phenethylamine
(d)-amphetamine
1-decanamine
a
b
32 , 40
−9.041
12
4
12
runs 3 and 4:
ln(p/p ) = (0.89 0.04) ln((to/ta) − (3.29 0.22) r2 = 0.9952
(17)
o
a
b
Vapor pressure for (d)-amphetamine at T/K = 293.3 Estimated.5
I
dx.doi.org/10.1021/je400212t | J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data
Article
adsorption-thermal desorption gas chromatography,3 or p/Pa =
40 estimated by ACD software.4 This can be compared to a
value of p/Pa = 59 obtained by extrapolation as described
above for racemic amphetamine also at T/K = 298.15.6 The
uncertainty in the vapor pressure of (d)-amphetamine was
evaluated as described above for the 1-alkanamines using the
uncertainties in eq 17.
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■
The vapor pressure and vaporization enthalpies of a series of
some aliphatic and aromatic primary amines were measured by
transpiration and the results compared to existing values in the
literature. Vaporization enthalpy results on the aliphatic amines
were also evaluated by correlation gas chromatography. Mean
values for these materials were then used to evaluate similar
properties for (d)-amphetamine. Due to restrictions on the
commercial availability of (d)-amphetamine, these experiments
illustrate a unique application of correlation gas chromatog-
raphy to provide two thermochemical properties on amounts
not easily measurable by other methods.
ASSOCIATED CONTENT
■
S
* Supporting Information
Details of the transpiration, and correlation gas chromatog-
raphy studies, and tables of retention times. This material is
available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: jsc@umsl.edu.
Notes
The authors declare no competing financial interest.
+On leave from Mogilev State University of Food Technolo-
gies, Mogilev, Belarus.
§On leave from Department of Physical Chemistry,Chemical
Institute, Kazan (Volga region) Federal University, Kazan,
Russia.
⊥On leave from Chemical Department, Samara State Technical
University, Molodogvardeyskaya 244, Samara 443100, Russia.
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dx.doi.org/10.1021/je400212t | J. Chem. Eng. Data XXXX, XXX, XXX−XXX