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J. Chem.

Thermodynamics 38 (2006) 1515–1522


www.elsevier.com/locate/jct

Thermochemical study of two anhydrous polymorphs of caffeine


Susana S. Pinto, Hermı́nio P. Diogo *

Centro de Quı́mica Estrutural, Complexo Interdisciplinar, Instituto Superior Técnico, 1049-001 Lisboa, Portugal

Received 14 February 2006; received in revised form 21 April 2006; accepted 26 April 2006
Available online 11 May 2006

Abstract

The mean values of the standard massic energy of combustion of caffeine in phase I (or alpha) and in phase II (or beta) measured by
static-bomb combustion calorimetry in oxygen, at T = 298.15 K, are Dcu (C8H10O2N4, I) = (21823.27 ± 0.68) J Æ g1 and Dcu
(C8H10O2N4, II) = (21799.96 ± 1.08) J Æ g1, respectively.
The standard (p = 0.1 MPa) molar enthalpy of formation in condensed phase for each form was derived from the corresponding
standard molar enthalpies of combustion as, Df H m ðC8 H10 O2 N4 ; cr; IÞ ¼ ð340:6  2:3Þ kJ  mol1 and Df H m ðC8 H10 O2 N4 ; cr; IIÞ
¼ ð345:1  2:3Þ kJ  mol1 .
The difference between the standard enthalpy of formation of the two polymorphs in condensed phase was also evaluated by using
reaction-solution calorimetry. The obtained result, 2.04 ± 0.25 kJ Æ mol1, is in agreement, within the uncertainty, with the difference
between the molar enthalpies of formation obtained from combustion experiments (4.5 ± 3.2) kJ Æ mol1, which can be considered as
an internal test for consistency of the results.
A value for the standard enthalpy of formation of caffeine in the gaseous state was proposed: Df H m ðC8 H10 O2 N4 ; gÞ ¼
ð229:7  6:1Þ kJ  mol1 , estimated from the values of the standard enthalpies of formation of both crystalline forms obtained in this
work, and the data on standard enthalpies of sublimation collected from the literature.
 2006 Elsevier Ltd. All rights reserved.

Keywords: Caffeine; Enthalpy of combustion; Enthalpy of formation; Differential scanning calorimetry; Solution calorimetry; Thermochemistry

1. Introduction lated by the Federal Food and Drug Administration


(FDA) and European Community.
Caffeine (3,7-dihydro-1,3,7-trimethyl-1H-purine-2,6- The crystalline hydrate of caffeine is known to be non-
dione), chemical structure shown in figure 1, commonly stoichiometric in terms the number of water molecules
designed as 1,3,7,trimethylxantine (CAS 58-08-2), is a com- coordinated [3]. This hydrate is converted to a b-anhydrous
ponent of coffee beans, tea leaves, and other plants includ- phase (sometimes referred as form II) under ambient tem-
ing rubiacea and theacea [1]. perature and atmospheric pressure conditions which, in
Pharmacologically, caffeine belongs to a group of stim- turn, changes enantiotropically to a trigonal phase a-anhy-
ulants called xanthines and is listed as an active ingredient drous caffeine (form I) at 155 C. Finally, an isotropic
in some stimulants, cold remedies, and various pain killers. liquid can be obtained heating this phase at 237 C (see fig-
It is actually the most used psychoactive drug with an esti- ure 2).
mated average consumption of 250 mg/day per capita [2]. Different polymorphs of a given substance often exhibit
Caffeine is also extensively used as a food additive regu- different physical properties like solubility, dissolution rate,
crystal form, and bioavailability or therapeutic benefit. The
*
incomplete characterisation of the polymorphic forms of
Corresponding author. Tel.: +351 21 841 9232; fax: +351 21 8464455/
57.
organic compounds is probably at the origin of the fre-
E-mail addresses: susanapinto@ist.utl.pt (S.S. Pinto), hdiogo@ist. quent discrepancies that are observed in the reported ther-
utl.pt (H.P. Diogo). modynamic data obtained in different laboratories, namely

0021-9614/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jct.2006.04.008
1516 S.S. Pinto, H.P. Diogo / J. Chem. Thermodynamics 38 (2006) 1515–1522

O tempered at 110 C, to avoid as much as possible the con-


CH3 tamination with form I. A schlenck tube, under an inert
H3C atmosphere, was used to prevent the adsorption of any
N
N residual moisture, when the sample was cooled to ambient
temperature. Greisser refers that is improbable to obtain
crystallographic pure form II without adulteration with a
O N
N low level of form I [8]. This fact leads Gavezzotti and co-
workers to argue that up to now, the failure to obtain an
ordered crystal phase, for the lower temperature form of
CH3
this molecule, is a consequence of its molecular features,
FIGURE 1. Caffeine molecule. namely the existence of an orientational disorder [9]. On
the other hand, the structure of the high temperature form
(I) was derived from X-ray powder diffraction measure-
phase II (or β) phase I (or α) Isotropic liquid ments recorded at 278 K, and it is believed that could be
______________|__________________|___________________
greatly disordered [8,10,11].

155οC 237οC 2.1.2. Form I


FIGURE 2. Schematic phase diagram of caffeine. Caffeine phase I was prepared by heating the phase II
above the melting temperature (ca. 240 C) inside a
schlenck tube (under a nitrogen flush) to avoid sublima-
heats of formation, heats of solution, and heats of sublima- tion, quenched to ca. 0 C, by using a ethanol/N2 mixture,
tion. According to Henck et al. it is presumed that more and then warmed to ambient temperature. The pellets for
than 50% of active ingredients of pharmaceutical products the combustion experiments were made quickly and kept,
show at least two polymorphic forms [4]. It is thus very under inert atmosphere, inside a refrigerator (5 C) for a
important, particularly to the pharmaceutical industry, to maximum period of 24 h. Due to its metastability, at room
be able to achieve an unambiguous characterisation of temperature, the process was repeated whenever necessary,
the solid phases, namely because the bioavailability of for example, if a systematic tendency in the specific energy
polymorphic forms can be different, and since the ratio of combustion was observed on successive combustion
yield/energetic must be maximised on economic grounds. runs. Although, Epple et al. [12] and Descamps and co-
The wide academic and industrial importance of the caf- workers [10,13], based on time- and temperature-resolved
feine molecule [5] contrasts with the lack of reliable exper- X-ray powder diffraction, and kinetic studies made by
imental values for the standard enthalpy of combustion Lehto and Laine [14] by using isothermal microcalorime-
and standard enthalpy of formation for the two anhydrous try, confirm that, at room temperature, the conversion
polymorphic forms. The present work is precisely a contri- form I ! form II is very slow.
bution to the thermodynamic characterisation of the pure
phases of anhydrous caffeine, using combustion calorime- 2.2. Apparatus
try and solution calorimetry.
Nevertheless, as far as we known, the only two values The elemental analysis was made with a Fisions Instru-
for the enthalpy of combustion of caffeine reported in the ments EA1108 apparatus, with typical claimed accuracy
literature in 1891 and 1893 (presumably for phase II) have errors of ±0.3% for carbon and nitrogen and ±0.1% for
merely a historic significance [6,7]. The first paper, pub- hydrogen.
lished by Stohmann and Langbein, does not indicate the The FT-IR spectra were obtained in a Shimadzu, model
origin and the purity of the sample used and no calorimet- 8400S spectrophotometer calibrated with polystyrene film.
ric details were given. The second one is the average of only The differential scanning calorimetry (DSC) measure-
two combustion measurements and the sample character- ments were acquired with a temperature-modulated TA
isation was only based on nitrogen determination. In addi- Instruments Inc. model 2920 MTDSC, in the conventional
tion, no Washburn corrections were applied by the authors mode. A helium purge rate 30 cm3/min was employed for
to the above results. all experiments. The samples were previously encapsulated
in seal aluminium pan and weighted (±107 g) on a
2. Experimental Mettler UMT2 ultra-micro balance. The baseline was cali-
brated by scanning the temperature range of the experi-
2.1. Sample purification ments with an empty pan. The temperature calibration
was performed acquiring the onset of the endothermic
2.1.1. Form II melting peak of several calibration standards, at a heating
Commercially obtained caffeine (USP grade from rate of 10 K Æ min1: n-decane (Tm = 246.49 K), n-octade-
Sigma) was recrystallised twice from distilled water, dried cane (Tm = 301.39 K), hexatriacontane (Tm = 349.09 K),
in vacuum (p  1.5 Æ 103 Pa) for 24 h at 80 C, and then indium (Tm = 429.75 K), and tin (Tm = 505.08 K). The
S.S. Pinto, H.P. Diogo / J. Chem. Thermodynamics 38 (2006) 1515–1522 1517

enthalpy scale was also calibrated using indium (fusion defragmentation pattern is in excellent accordance with
enthalpy, Dlcr H m ¼ 28:71 J  g1 ) [15]. the NIST Data Base [19].
The 1H n.m.r. spectra were obtained in a Varian 300 The melting peak of caffeine in phase I was characterised
MHZ spectrometer. by DSC, and it was found that the onset temperature is
The gas-chromatography/mass spectrometry (GC/MS) Ton = 509.6 K and the temperature of the maximum is
analysis was carried out on an Agilent 6890 gas chromato- Tmax = 510.2 K at a heating rate of 10 K/min (see figure
graph joined to an Agilent 5973N mass detector. 3). The corresponding enthalpy of fusion was found to be
X-ray diffraction measurements were made with a Phil- Dlcr H m ðC8 H10 O2 N4 Þ ¼ 21:9 kJ  mol1 , which is in agree-
lips PW 1710-type angle dispersive powder diffractometer. ment with the literature values which span in a range of
The diffractograms were obtained with Ni-filtered Cu Ka- 3.4 kJ/mol, from 20.1 to 23.5 kJ/mol [11,20,21].
radiation (k = 0.15418 nm, voltage 40 kV, current 30 mA) DSC was also used to characterise the conversion
over the range 5 6 2h 6 32 with scan speed of 1 (2h/ between polymorphs. Muller and Greisser [8] pointed out
min) and step size 0.016 of 2h. that the purity of stable form II can be estimated based
The combustion calorimetric experiments were achieved on the experimental value obtained by DSC for the
using a micro-combustion calorimeter previously described enthalpy of transition form II ! form I. These authors cor-
[16]. The energy equivalent of the calorimeter and its stan- related the amount of phase I as an impurity present in
dard deviation, e0 = (1895.27 ± 0.33) J Æ K1, were deter- phase II with the enthalpy of phase transition observed
mined from the combustion of benzoic acid (B.D.H. at ca. 155 C in a DSC experiment [8] (figure 4). For a pure
thermochemical standard) whose standard massic energy sample of phase II a value of DHtrans (II ! I) = 4.025
of combustion under the certificate conditions was ± 0.006 kJ/mol can predicted. The DSC result for our sam-
(26433 ± 4) J Æ g1. n-Hexadecane (Aldrich, mass fraction ple gives DHtrans (II ! I) = 4.02 ± 0.03 kJ/mol (20.71 J/g)
0.99) was used as a combustion aid only for experiments on which indicates a phase purity better than 99.9%. The dif-
phase I. The analysis of the HNO3(aq), formed from traces fraction patterns obtained on our samples of phase I are
of atmospheric N2 initially present inside the bomb, was very close those published by Descamps and co-workers
made with a Dionex 4000i ion chromatography apparatus [11,13]. Furthermore, for phase II, a characteristic peak
[16b]. (2h = 28.4) is observed, which is absent in form I. This
The reaction-solution calorimeter and the general oper- X-ray powder diffractogram of phase II is in accordance
ating procedure used in the experiments have been to one reported by Laine et al. [22] and Descamps and
described in a previous publication [17]. The calorimeter co-workers [11]. The 1H n.m.r. spectra, in CDCl3 solution,
consisted basically of a transparent Dewar vessel closed obtained in a 300 MHz spectrometer, agrees very well with
by a lid, which supported a stirrer, a quartz crystal ther- that reported in reference [23]: 1H n.m.r. (CDCl3/TMS):
mometer probe, a resistor for electrical calibration, and d = 7.50 (m, CH, 1H), 4.01 (d, CH3, 3H), 3.55 (s, CH3,
an ampoule breaking system. The assembled vessel was 3H), 3.37 (s, CH3, 3H). Finally, the FT-IR spectra were
immersed in a thermostatic water bath whose temperature obtained for both phases of caffeine, and it was found that
was controlled at 298 ± 103 K by a Tronac PTC-40 unit. all the individual vibrational bands reported by York et al.
In a typical experiment a thin walled glass ampoule (vol- [3] are detected in the spectrum of form II carried out in the
ume ca. 2.5 ml) was weighed to ±105 g on a Mettler present work.
AT201 balance, filled with the sample using an apparatus
to maintain the inert atmosphere [18] and sealed with a
torch. The two resulting pieces (closed ampoule + part of
the neck) were weighed and the mass of sample obtained
by subtracting the mass of the empty ampoule. 0

-5
2.3. Sample characterisation
-10
Heat Flow

The results of elemental analysis (average of two inde- -0.4

pendent runs) show acceptable agreement with theoretical -15 -0.6


-0.8
values for carbon, hydrogen, and nitrogen for both -20 -1
samples: -1.2
-25 -1.4
-1.6
For C8H10O2N4 calculated: C, 49.48; H, 5.19; N 28.85. -30
365 415 465
T /K
Found (phase I): C, 49.67; H, 5.28; N 28.85.
Found (phase II): C, 49.68; H, 5.25; N 28.89. -35
300 340 380 420 460 500
T /K
The GC/MS of the purified caffeine, dissolved in dichlo-
romethane, indicates a purity better than 99.9% and the FIGURE 3. DSC scan of caffeine at a heating rate of 10 K/min. The inset
MS of the peak shows a parent ion at m/z = 194. This shows the thermal event relative to phase transition (II ! I).
1518 S.S. Pinto, H.P. Diogo / J. Chem. Thermodynamics 38 (2006) 1515–1522

105 ð285:830  0:040Þ kJ  mol1 [25], the following values of


the standard formation enthalpies at 298.15 K were
85 derived:
Df H m ðC8 H10 O2 N4 ; cr; IÞ ¼ ð340:6  2:3Þ kJ  mol1
% of phase II

65
and
45 Df H m ðC8 H10 O2 N4 ; cr; IIÞ ¼ ð345:1  2:3Þ kJ  mol1 :
From these standard enthalpies of formation at
25 298.15 K of the anhydrous phases of caffeine we conclude
that the enthalpy of reaction associated to the transforma-
5 tion depicted in the following equation:
0.5 1.5 2.5 3.5 4.5
C8 H10 O2 N4 ðcr; IIÞ ¼ C8 H10 O2 N4 ðcr; IÞ ð2Þ
Htrans (kJ/mol)
at the same temperature is DrH = (4.5 ± 3.2) kJ Æ mol1.
0

FIGURE 4. Relationship between the DHtrans (II ! I) and the percentage Let us note that this value of DrH0 agrees, within the
of form II (data from Muller and Greisser [8]). uncertainty interval, with that obtained by DSC
(4.02 ± 0.03 kJ Æ mol1) at the transition temperature
3. Results and discussion (155 C = 388.15 K). In order to check the internal consis-
tency of this result, we chose a different estimation method,
Appendix A presents the detail of the calorimetric pro- based on the measurement of the dissolution enthalpies of
cedures and data treatment. Individual values of the stan- both phases of anhydrous caffeine in the same solvent. We
dard massic energy of combustion of anhydrous caffeine thus measured the enthalpy associated with the dissolution
form I and form II are indicated in tables A1 and A2, process of each phase of caffeine (200–500 mg) in 125 ml of
and the mean values are: a mixture of ethanol/chloroform (60:40), where this partic-
Dc u ðC8 H10 O2 N4 ; IÞ ¼ ð21823:27  0:68Þ J  g1 ular solvent mixture was chosen since the dissolution pro-
cess was found to be reasonably fast. Tables B1 and B2
and show the results of five and six independent runs carried
Dc u ðC8 H10 O2 N4 ; IIÞ ¼ ð21799:96  1:08Þ J  g1 ; out on phase I and phase II, respectively. The values of
the dissolution enthalpies are Dsol H m ¼ ð11:89  0:20Þ kJ
where the uncertainty quoted represents the standard devi- mol1 for phase I and (13.93 ± 0.15) kJ Æ mol1 for phase
ation of the mean. All presented molar quantities are based II. Given that the final state of the dissolution of each
on the 2001 standard atomic masses [24]. The Dcu values polymorph in the solvent mixture is identical, the difference
obtained in this work, and above indicated, refer to the between those values of the dissolution enthalpy,
reaction: 2.04 ± 0.25 kJ Æ mol1, can be identified with the enthalpy
C8 H10 O2 N4 ðcr; I or IIÞ þ 19=2 O2 ðgÞ ¼ of reaction (2). It is to be noted that this value is inside
the confidence interval of the enthalpy of the same reaction
8 CO2 ðgÞ þ 5 H2 OðlÞ þ 2 N2 ðgÞ ð1Þ
calculated as the difference of the formation enthalpies of
and lead, respectively, to the molar values: the crystalline phases (4.5 ± 3.2 kJ Æ mol1), which tells in
favour of a good internal consistency of the thermody-
Dc U m ðC8 H10 O2 N4 ; IÞ ¼ ð4237:87  1:98Þ kJ  mol1 ;
namic data obtained in the present work. Due to its
Dc H m ðC8 H10 O2 N4 ; IÞ ¼ ð4236:63  1:98Þ kJ  mol1 ; destructive character and time consuming the combustion
calorimetry is not a first choice technique to determine
and to
the expected small difference between the standard enthal-
Dc U m ðC8 H10 O2 N4 ; IIÞ ¼ ð4233:35  2:00Þ kJ  mol1 ; pies of formation of polymorphs. However, this technique
Dc H m ðC8 H10 O2 N4 ; IIÞ ¼ ð4231:89  2:00Þ kJ  mol1 ; offers an interesting way to validate the values supplied by
other thermal techniques.
both at T = 298.15 K. The symbols Dc U m and Dc H m Several values of the enthalpy of sublimation of the two
denote, respectively, the standard energy and the standard anhydrous phases of caffeine, at different temperatures, are
molar enthalpy of combustion. As recommended, the reported in the literature [26]. The most recent values were
uncertainties quoted represent twice the overall standard reported by Greisser et al. [27]: Dgcr H m ðC8 H10 O2 N4 ; IÞ
deviation of the mean and include the contributions from ¼ 104:8  0:2 kJ  mol1 at T = 439 K and Dgcr H m ðC8 H10
the calibration with benzoic acid and from the energy of O2 N4 ; IIÞ ¼ 113:6  0:2 kJ  mol1 at T = 369 K, where
combustion of n-hexadecane in the case of phase I. From the uncertainties denote the standard deviation of the
the Dc H m ðC8 H10 O2 N4 ; IÞ and Dc H m ðC8 H10 O2 N4 ; IIÞ mean. The enthalpy of sublimation at 298.15 K for phase
values indicated above, together with Df H m ðCO2 ; gÞ ¼ I and phase II of caffeine can be calculated from the
ð393:51  0:13Þ kJ  mol1 [25] and Df H m ðH2 O; lÞ ¼ reported values at a different T by using [28]:
S.S. Pinto, H.P. Diogo / J. Chem. Thermodynamics 38 (2006) 1515–1522 1519

Dgcr H m ð298:15 KÞ ¼ Dgcr H m ðT Þ þ Dgcr C p;m ð298:15  T Þ; We suggest to consider the average between those values
ð3Þ as the best value of the standard enthalpy of formation
of caffeine in gaseous state: Df H m ðC8 H10 O2 N4 ; gÞ ¼
where Dgcr C p;m
represents the difference between the molar ð229:7  6:1Þ kJ  mol1 .
heat capacity of gaseous and crystalline caffeine for each
phase. Since no experimental values of Dgcr C p;m for the
two anhydrous forms of caffeine are presently available in 4. Concluding remarks
the literature, we decided to estimate those values on the
basis of a prediction method proposed by Chickos et al. In this work we have prepared and characterised by ele-
[29]. This method uses an empirical equation (see equation mental analysis, X-ray powder diffraction, DSC, GC-MS,
(4)) that was derived from a huge set of experimental values and FT-IR two phases of anhydrous caffeine (I or a, and
relative to a large number of organic molecules: II or b). By using static-bomb combustion calorimetry in
oxygen the standard massic energies of combustion and
Dgcr C p;m =ðJ  K1  mol1 Þ ¼ 0:75  0:15 C p;m ðcrÞ; ð4Þ the standard enthalpies of combustion were determined.
From these values, the corresponding standard molar
where C p;m
ðcrÞ is the molar heat capacity, at T = 298.15 K,
enthalpies of formation were derived for both condensed
of the crystalline phase. The published C p;m values of the
phases. Combining these data with literature values for the
crystalline phases of anhydrous caffeine [10,20] refer to
standard enthalpies of sublimation allowed the estimation
temperatures different from 298.15 K, so that the values
of the standard enthalpy of formation in the gaseous phase.
at this temperature were obtained by fitting and extrapolat-
Different approaches were used to test the internal consis-
ing the reported values. From the obtained values:
tency of the results. The first one used reaction-solution cal-
Cp;m ðC8 H10 O2 N4 ; cr; IÞ ¼ 267:2 J  K1  mol1 at 298:15 K orimetry for determining of enthalpy of solution of each
phase of caffeine in a mixture of ethanol/chloroform
and (60:40). From these measurements it was found that the dif-
ference between the enthalpies of solution of the two crystal-
Cp;m ðC8 H10 O2 N4 ; cr; IIÞ ¼ 173:4 J  K1  mol1 at 298:15 K
line polymorphs at room temperature is (2.04 ± 0.25)
kJ Æ mol1 which is comparable to (4.02 ± 0.03 kJ Æ mol1)
we calculated, using equation (4), Dgcr C p;m ðC8 H10
obtained by DSC at 155 C (328.15 K), and to (4.5 ± 3.2)
O2 N4 ; cr; IÞ ¼ ð40:8  33:0Þ J  K1  mol1 for phase I
kJ Æ mol1 obtained by combustion calorimetry at 298.15
and Dgcr C p;m ðC8 H10 O2 N4 ; cr; IIÞ ¼ ð26:8  33:0Þ J  K1 
K. This agreement within the uncertainty interval, obtained
mol1 for phase II, both at T = 298.15 K. The uncertainty
by three independent calorimetric techniques, is an indica-
of ±33.0 J Æ K1 Æ mol1 quoted above was obtained con-
tion of the reliability of the enthalpies of formation obtained
sidering the standard deviation of the empirical coefficients
for the two polymorphs in condensed phase.
of equation (4) [29]. Finally, introducing these values in
The values of the standard enthalpies of formation, in
equation (3) leads to:
condensed phase, obtained in this work, together the corre-
Dgcr H m ðC8 H10 O2 N4 ; IÞ ¼ 110:5  4:7 kJ  mol1 at 298:15 K; sponding standard enthalpies of sublimation, allowed the
suggestion of a value for the standard enthalpy of formation
and of caffeine in the gaseous state: Df H m ðC8 H10 O2 N4 ; gÞ
¼ ð229:7  6:1Þ kJ  mol1 . This result is relevant, for
Dgcr H m ðC8 H10 O2 N4 ; IIÞ ¼ 115:52:3 kJ  mol1 at 298:15 K:
example, for computational energetic screening studies on
drug discovery development [30]. Finally, it should be
It should stressed that Greisser et al. [27] reported the
stressed that an accurate determination of enthalpies of com-
values of 115 kJ Æ mol1 and 119 kJ Æ mol1 for the stan-
bustion and formation of a solid demands the knowledge of
dard enthalpy of sublimation at T = 298.15 K for phase I
the purity of phase of the used material.
and phase II, respectively, without indication of the uncer-
tainty associated.
Finally, the results obtained in this work for the stan- Acknowledgements
dard enthalpy of formation in condensed phase for each
polymorph of caffeine, together with the values of the stan- The authors are indebted for Prof. Moura Ramos for
dard enthalpy of sublimation ðDgcr H m Þ, allow the determi- very useful discussions. A grant (SFRH/BD/12330/2003)
nation of the standard enthalpy of formation of caffeine from Fundação para a Ciência e a Tecnologia is gratefully
in the gaseous phase, Df H m ðgÞ. From the values relative acknowledged by S.S. Pinto.
to phase I we obtained Df H m ðC8 H10 O2 N4 ; gÞ ¼ ð230:1
5:2Þ kJ  mol1 , while the value Df H m ðC8 H10 O2 N4 ; gÞ ¼ Appendix A. Details on the calorimetric combustion
ð229:6  3:3Þ kJ  mol1 was obtained using the thermo- experimental procedures and data treatment
dynamic properties of phase II. The very good agreement
between these values is again another evidence for the In a typical calorimetric experiment, a pellet of caf-
internal consistency of the results presented in this work. feine with a diameter of ca. 4 mm was placed in a platinum
1520 S.S. Pinto, H.P. Diogo / J. Chem. Thermodynamics 38 (2006) 1515–1522

crucible (containing n-hexadecane in the experiments on the initial and final states of the bomb process, respectively;
phase I) and weighed to 107 g in a Sartorius 4504 Mp8- Ti and Tf represent the initial and final temperatures of the
1 ultra-micro balance. The crucible with the sample was experiment; DTc is the contribution to the observed tem-
adjusted to the sample holder in the bomb head. A volume perature rise of the calorimeter proper due to the heat
of 50 lL of deionised water from a Milipore system (con- exchanged with the surroundings and the heat dissipated
ductivity 60.1 lS) was introduced in the bomb body. The by the temperature sensor; DUign is the electrical energy
stainless-steel bomb of 17.95 cm3 internal volume was supplied for ignition of the sample; DUIBP is the internal
closed and purged twice by charging it with oxygen (Ar energy change associated with the bomb process under iso-
Liquide N45, mass fraction >0.9995) at a pressure of thermal conditions, at T = 298.15 K; DUR represents the
1.01 MPa and then venting the overpressure. The bomb sum of all corrections necessary to reduce DUIBP to the
was then charged with oxygen at a pressure of 3.04 MPa standard state; DU(HNO3) is the energy change associated
and transferred to the inside of the calorimeter proper. with the formation of nitric acid; DU(aux) and
The combustion of the sample was initiated by discharge DU(C8H10O2N4) are the contributions of n-hexadecane
of a 2200 lF capacitor through a platinum wire (Johnson and caffeine to the energy of the isothermal bomb process,
Matthey; mass fraction: 0.9995) with a diameter of respectively; and, finally, Dcu (C8H10O2N4) is the standard
0.05 mm. massic energy of combustion of caffeine.
The results of the calorimetric combustion experiments The values of Ti, Tf, and DTc were calculated by using a
are shown in tables A1 and A2, where m(C8H10O2N4) is computer program based on the Regnault–Pfaundler
the mass of caffeine; m(aux) is the mass of n-hexadecane method [16a] and DUIBP was obtained from:
used as combustion auxiliary; n(HNO3) is the amount of
DU IBP ¼eo ðT i  T f þ DT c Þ þ ei ðT i  298:15Þþ
substance of nitric acid formed in the bomb process; ei
and ef are the energy equivalents of the bomb contents in ef ð298:15  T f þ DT c Þ þ DU ign : ðA:1Þ

TABLE A1
Results of the calorimetric combustion experiments on anhydrous caffeine, form I (C8H10O2N4)
Experiment 1 2 3 4 5 6
m(C8H10O2N4, I)/mg 34.5575 28.2855 32.3060 41.1013 46.7722 21.1121
m(aux)/mg 2.3244 2.0540 2.2645 2.0841 2.2755 1.9331
n(HNO3) · 105/mol 3.25 3.60 2.75 3.10 3.60 3.40
ei/(J Æ K1) 1.180 1.172 1.177 1.186 1.194 1.162
ef/(J Æ K1) 1.232 1.214 1.226 1.247 1.263 1.194
Ti/K 298.23056 298.27753 298.09865 298.08960 298.06605 298.06228
Tf/K 298.72161 298.69530 298.58950 298.66552 298.70513 298.44299
DTc/K · 102 3.55 3.88 6.06 4.87 4.16 8.73
DUign/J 1.76 1.76 1.76 1.76 1.76 1.76
DUibp/J 862.12 716.83 814.10 998.00 1131.17 554.31
DU(HNO3)/J 1.94 2.15 1.64 1.85 2.15 2.03
DU(aux)/J 105.41 96.90 106.83 98.32 107.35 91.20
DUR/J 0.65 0.52 0.60 0.77 0.88 0.39
DU(C8H10O2N4, I)/J 754.12 617.26 705.03 897.06 1020.79 460.69
Dcu (C8H10O2N4, I)/(J Æ g1) 21822.18 21822.49 21823.50 21825.58 21824.72 21821.14

TABLE A2
Results of the calorimetric combustion experiments on anhydrous caffeine, form II (C8H10O2N4)
Experiment 1 2 3 4 5
m(C8H10O2N4, II)/mg 23.8140 38.1108 39.4286 44.2060 36.3405
n(HNO3) · 105/mol 3.5 5.24 5.0 4.70 4.76
ei/(J Æ K1) 1.160 1.175 1.178 1.183 1.174
ef/(J Æ K1) 1.189 1.223 1.228 1.241 1.219
Ti/K 298.22072 298.07941 298.11363 298.08107 298.10354
Tf/K 298.55794 298.58125 298.62242 298.64233 298.58312
DTc/K · 102 6.11 6.09 5.27 3.24 5.91
DUign/J 1.76 1.76 1.76 1.76 1.76
DUibp/J 521.69 834.49 863.25 967.30 795.78
DU(HNO3)/J 2.09 3.13 2.99 2.81 2.84
DUR/J 0.41 0.70 0.71 0.80 0.65
DU(C8H10O2N4, II)/J 519.19 830.66 859.55 963.69 792.29
Dcu (C8H10O2N4, II)/J Æ g1 21801.88 21795.92 21800.16 21799.98 21801.85
S.S. Pinto, H.P. Diogo / J. Chem. Thermodynamics 38 (2006) 1515–1522 1521

TABLE B1
Results of the reaction-solution calorimetric experiments relative to solution of caffeine phase I in a mixture of ethanol/chloroform (60:40)
m(C8H10O2N4)/mg n · 103/mol e/(J Æ K1) DTad/K Dsol H m =ðkJ  mol1 Þ
360.87 1.858 370.19 0.0562 11.202
389.81 2.007 349.48 0.0714 12.435
424.42 2.186 327.03 0.0812 12.149
498.49 2.567 339.52 0.0913 12.076
470.48 2.423 327.76 0.0877 11.870
ÆDsolHm/(kJ Æ mol1)æ = (11.89 ± 0.20) kJ Æ mol1

TABLE B2
Results of the reaction-solution calorimetric experiments relative to solution of caffeine phase II in a mixture of ethanol/chloroform (60:40)
m(C8H10O2N4)/mg n · 103/mol e/JK1 DTad/K Dsol H m =ðkJ  mol1 Þ
235.90 1.211 337.12 0.0517 14.358
327.65 1.687 316.93 0.070 13.174
190.37 0.980 334.73 0.0422 14.420
185.88 0.957 322.34 0.0408 13.752
287.10 1.478 327.25 0.0634 14.030
223.89 1.153 334.61 0.0462 13.399
hDsol H m =ðkJ  mol1 Þi ¼ ð13:93  0:15Þ kJ  mol1

The standard state corrections, DUR, were derived as rec- References


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