J. Chem.

Thermodynamics 116 (2018) 7684

Contents lists available at ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Thermodynamic properties of myo-inositol

A.V. Knyazev a,, V.N. Emelyanenko b,c,, A.S. Shipilova a, D.H. Zaitsau c, M.I. Lelet a, S.S. Knyazeva a,
E.V. Gusarova a, M.A. Varfolomeev b
a
Lobachevsky University, Gagarin Prospekt 23/2, 603950 Nizhni Novgorod, Russia
b
Department of Physical Chemistry, Kazan Federal University, Kremlevskaya Str. 18, 420008 Kazan, Russia
c
Department of Physical Chemistry and Department, Science and Technology of Life, Light and Matter, University of Rostock, Dr.-Lorenz-Weg 1, D-18059 Rostock, Germany

a r t i c l e i n f o a b s t r a c t

Article history: In the present work, the temperature dependence of heat capacity of vitamin B8 (myo-inositol) has been
Received 2 July 2017 measured for the first time over the range from 8 K to 340 K by precision adiabatic vacuum calorimetry.
Received in revised form 24 August 2017 Based on the experimental data, the thermodynamic functions of the vitamin B8, namely, the heat capac-
Accepted 26 August 2017
ity, enthalpy H(T)H(0), entropy S(T)S(0) and Gibbs function G(T)H(0) have been determined for
Available online 30 August 2017
the range from T ? 0 K to 340 K. The value of the fractal dimension D in the function of multifractal gen-
eralization of Debyes theory of the heat capacity of solids was estimated and the character of heterody-
Keywords:
namics of structure was detected. The enthalpy of combustion (
2747.0 2.1) kJmol
1 of the vitamin B8
Vitamin B8
Myo-inositol
was measured for the first time using high-precision combustion calorimeter. The standard molar
Adiabatic vacuum calorimetry enthalpy of formation in the crystalline state (
1329.3 2.3) kJmol
1 of B8 at 298.15 K was derived from
Heat capacity the combustion experiments. Using combination of the adiabatic and combustion calorimetry results the
Combustion calorimetry thermodynamic functions of formation of the myo-inositol at T = 298.15 K and p = 0.1 MPa have been cal-
Thermodynamic functions culated. The low-temperature X-ray diffraction was used for the determination of coefficients of thermal
expansion.
2017 Elsevier Ltd.

1. Introduction namic functions of the myo-inositol with the purpose of describing

Myo-inositol (CAS: 87-89-8) is a sugar alcohol (isomer of glu-
cose) widely distributed in plant and animal tissues. It is found
in food, for example cereals with high bran content (buckwheat),
nuts, beans, and fruit [1]. It plays an important role as the struc-
tural basis for a number of secondary messengers in eukaryotic
cells, including inositol phosphates (phytic acid), phosphatidyli-
nositol and phosphatidylinositol phosphate lipids. Inositol itself
is not considered as a vitamin because it can be synthesized by
the human body. On the other hand, myo-inositol was classified
as a member of the vitamin B-complex (often called vitamin B8).
Patients suffering from clinical depression generally have
decreased levels of inositol in their cerebrospinal fluid [2].
This work is a continuation of systematic studies of vitamins B.
Earlier in the articles [36], we have investigated the thermody-
namic properties of vitamins Bn (n = 2, 3, 9, 12). The goals of this
work include calorimetric determination of the standard thermody-
Corresponding authors at: Department of Physical Chemistry, Kazan Federal
University, Kremlevskaya Str. 18, 420008 Kazan, Russia. Tel.: +49-381-498-6499;
fax +49-381-498-6524 (V.N. Emelyanenko); Tel.: +7-831-462-32-34; fax +7-831-
434-50-56 (A.V. Knyazev).
E-mail addresses: knyazevav@gmail.com (A.V. Knyazev), vladchimic@tut.by
(V.N. Emelyanenko).
biochemical and industrial processes with its participation.
2. Experimental
2.1. Sample
Myo-inositol was purchased from NutriVitaShop. For phase
identification, an X-ray diffraction pattern of the vitamin B8 sample
was recorded on a Shimadzu X-ray diffractometer XRD-6000 (CuKa
radiation, geometry h2h) in the 2h range from 5 to 60 with scan
increment of 0.02. The water content in myo-inositol was deter-
mined by Karl Fischer titration. The water content of the com-
pound is below the detection limit (0.05 wt%), so there is no
crystallization and sorption water in the compound. The X-ray
data, Karl Fischer titration and NutriVitaShop certificate led us to
conclude that the myo-inositol sample studied (the content of
impurities 0.1 wt%) was an individual crystalline compound
(monoclinic modification, space group P21/c [7]).
2.2. Apparatus and measurement procedure
To measure the heat capacity C op of the tested substance over
the range from 8 K to 340 K, a BKT-3.0 automatic precision

http://dx.doi.org/10.1016/j.jct.2017.08.028
0021-9614/ 2017 Elsevier Ltd.
 A.V. Knyazev et al. / J. Chem. Thermodynamics 116 (2018) 7684 77

adiabatic vacuum calorimeter with discrete heating was used. The
calorimeter design and the operation procedure were described
earlier [8]. The calorimeter was tested by measuring the heat
capacity of high-purity copper and reference samples of synthetic
corundum and K-2 benzoic acid. The analysis of the results showed
that relative standard uncertainty of the heat capacity of the sub-
stance at helium temperatures was within 2%, then it decreased
to 0.5% as the temperature was increase to 40 K, and was equal
to 0.2% at T > 40 K.
An isoperibol bomb calorimeter described previously [9] was
used for the measurements of energies of combustion of the
myo-inositol. The solid sample of compound was weighed with a
microbalance of 10
6 g resolution. We used small polyethylene
pieces prepared from commercial 1 mL ampoules (Fa. NeoLab, Hei-
delberg, Germany). This was employed as an auxiliary material in
order to achieve complete combustion. The combustion products
were examined for carbon monoxide (Drger tube) and unburned
carbon, but none was detected. The energy equivalent of the

Table 1
Experimental values of isobaric heat capacities (JK
1mol
1) of myo-inositol, M = 180.156 gmol
1. po = 0.1 MPa.

T/K C op /JK
1mol
1 T/K C op /JK
1mol
1 T/K C op /JK
1mol
1

Series 1 14.08 3.897 28.59 14.60

8.37 0.774 14.35 4.078 30.38 16.06
8.40 0.780 14.63 4.226 31.42 16.86
8.51 0.803 14.91 4.431 32.38 17.74
8.64 0.841 15.19 4.618 33.35 18.40
8.77 0.885 15.47 4.810 34.31 19.30
8.91 0.930 15.75 4.990 35.28 20.02
9.05 0.977 16.04 5.208 36.25 20.70
9.20 1.034 16.32 5.400 37.23 21.47
9.34 1.096 16.61 5.588 38.21 22.22
9.50 1.162 16.90 5.795 39.19 22.99
9.65 1.224 17.20 5.990 40.18 23.66
9.81 1.296 17.49 6.202 41.16 24.37
9.98 1.381 17.78 6.394 42.15 25.13
10.17 1.467 18.08 6.622 43.15 25.81
10.39 1.577 18.37 6.852 44.14 26.63
10.59 1.677 18.67 7.060 45.14 27.34
10.81 1.817 18.97 7.278 46.17 28.07
11.05 1.945 19.27 7.496 47.17 28.86
11.28 2.084 19.57 7.721 48.17 29.58
11.52 2.218 19.87 7.949 49.18 30.39
11.76 2.363 20.46 8.428 50.18 31.12
12.00 2.535 21.33 9.104 51.20 31.92
12.25 2.700 22.21 9.711 53.79 33.97
12.50 2.861 23.10 10.41 54.97 34.90
12.75 3.034 24.00 11.09 55.99 35.65
13.01 3.189 24.90 11.77 57.01 36.49
13.27 3.362 25.81 12.44 58.03 37.34
13.53 3.524 26.73 13.12 59.05 38.14
13.81 3.727 27.66 13.84 60.07 38.87
61.10 39.73 110.53 80.42 208.19 155.1
62.12 40.52 113.53 82.88 212.26 158.0
63.15 41.35 116.54 85.33 216.41 161.2
64.17 42.18 119.54 87.73 220.48 164.0
65.20 43.06 122.54 90.16 224.57 167.1
66.23 43.91 125.55 92.54 228.65 170.1
67.26 44.68 128.56 94.96 232.72 173.2
68.29 45.54 131.58 97.38 236.81 176.2
69.32 46.48 134.60 99.81 240.91 179.3
70.38 47.25 137.62 102.1 245.00 182.3
71.85 48.53 140.65 104.5 249.09 185.2
73.87 50.14 143.68 106.9 253.18 188.2
75.89 51.78 146.71 109.2 257.27 191.3
77.91 53.41 149.74 111.6 261.36 194.4
78.79 54.18 152.78 113.9 265.46 197.6
79.80 55.07 155.81 116.2 269.55 200.6
80.92 56.01 158.85 118.6 273.64 203.7
Series 2 161.89 120.9 277.73 206.6
79.15 54.64 164.97 123.2 281.90 210.0
81.14 56.14 168.01 125.5 285.98 212.8
83.15 57.79 171.06 127.7 290.07 215.9
85.15 59.59 174.10 130.0 294.15 219.0
87.15 61.09 177.15 132.3 298.22 222.0
89.15 62.93 180.20 134.4 303.01 226.0
91.14 64.62 183.25 136.7 308.39 230.0
93.14 66.21 186.30 138.9 313.76 234.0
95.13 67.80 189.35 141.2 319.12 237.9
97.12 69.47 192.40 143.5 324.46 241.9
99.11 71.03 195.46 145.6 329.77 246.0
101.58 73.24 198.52 147.8 335.05 250.1
104.56 75.65 201.57 150.1 340.30 253.9
107.54 78.02 204.63 152.3

ur(Cp(T)) = 2% (5 < T h2 0) K; 0.5% (20 < T h4 0) K; 0.2% (T > 40 K), u(T) = 0.01 K, ur(p) = 1% (level of confidence = 0.68).
78 A.V. Knyazev et al. / J. Chem. Thermodynamics 116 (2018) 7684

calorimeter ecalor = (14795.1 1.0) J K
1 was determined with a pies, H298, of the compound were computed with the thermody-
standard reference sample of benzoic acid (SRM 39 j, NIST). Correc- namic procedures [12,14] implemented in the data output.
tion for nitric acid formation was based on the titration with
0.1 moldm
3 NaOH (aq.). The relative atomic masses used for
the elements were calculated as the mean of the bounds of the 3. Results and discussion
interval of the standard atomic weights recommended by the
IUPAC commission in 2011 [10] for each of these elements. 3.1. Heat capacity

2.3. Quartz-crystal microbalance technique The C op measurements were carried out between 8 K and 340 K
(see Table 1). The mass of the sample loaded in the calorimetric
The Quartz Crystal Micrabalance (QCM) technique with the ampoules of the BKT-3.0 device was 0.5418 g. A total of 183 exper-
open surface (Langmuir-type) sublimation was used for recording imental C op values was obtained in two series of experiments
of the temperature dependence of the sublimation rate. The (Fig. 1). The heat capacity of the sample varied from 20% to 50%
detailed description of the QCM technique can be found elsewhere
[11].
Table 2
Briefly, the solid sample of myo-inositol was dissolved in twice-
Coefficients in the fitting polynomials for myo-inositol.
distilled water and obtained solution poured in an open cavity
inside of the thermostat block. After heating the solution to T/K 8.550 40340
polynomials type 2 1
363 K the water was gently vapourized and the solid film of stud-
ied compound with high thermal contact with the thermostat A 2.75883052 2.74353336
B 1.50843836 7.33676608
block. Water was fully removed from the film by exposing to vac-
C
0.387259434 8.38636574
uum (10
5 Pa) for 1 h at temperature 393 K. Thus obtained solid D
3.92957686 10
2
1.88654864
film with good thermal contact with metal thermostat was used E
0.130532770 0.207067559
for further investigation. Directly over the solid film of the sample F
4.3305869310
2
1.1054668310
2
placed the QCM sensor. When studied sample is heated and G 0.408506536 2.3012111410
4
H 1.19473626
exposed to vacuum a certain amount of sample sublimes and
I 0.636570563
deposited on the surface of the quartz crystal. The mass increase
Dm on the QCM surface produces the shift of the vibrational fre-
quency Df. The experimentally determined with QCM technique
temperature dependence of the frequency change rate (df/dt) Deviation from fitting curve / %
was used to evaluate the sublimation enthalpy by using the
Clausius-Clapeyron equation. The frequency shift rates were con-
verted into the absolute vapour pressures according to the proce-
dure published before [11]. Nevertheless, the ambiguity in the
surface area of the sample and calibration uncertainty gives the
final uncertainty of the absolute vapour pressure is comparable
to the absolute vapour pressure but the level of vapour pressures T/K
can be estimated. The initial frequency shift rates were used to
evaluate of the sublimation enthalpy for myo-inositol and, there-
fore, the uncertainty of the absolute vapour pressures does not
affect the uncertainty of the sublimation enthalpy.

2.4. Calculation

Quantum chemical calculations were performed with the Gaus- Fig. 2. Temperature dependence of the deviation from fitting curve.

sian 09 series software [12]. Energies of molecules involved in this

study were calculated using the G3MP2 method [13]. The enthal-
Cp / JK-1mol-1

Cp / JK-1mol-1

T/K
T/K

Fig. 3. Comparison of the low-temperature heat capacity between myo-inositol

Fig. 1. Temperature dependence of heat capacity of myo-inositol. (circles) and a-D-glucose (squares).
 A.V. Knyazev et al. / J. Chem. Thermodynamics 116 (2018) 7684 79

Table 3
Thermodynamic functions of crystalline myo-inositol, M = 180.156 gmol
1, po = 0.1 MPa.

T/K C op T/(JK
1mol
1) H T
H 0/(kJmol
1) S T/(JK
1mol
1)
[G T
H 0]/(kJmol
1)

0 0 0 0 0
5 0.0950 0.000095 0.0237 0.000024
6 0.1967 0.00024 0.0492 0.000059
7 0.3623 0.000509 0.0910 0.000128
8 0.6094 0.000989 0.1546 0.000248
9 0.9596 0.00176 0.2451 0.000446
10 1.387 0.00306 0.3742 0.000687
15 4.502 0.01730 1.491 0.005053
20 8.030 0.04852 3.261 0.01671
25 11.83 0.09808 5.458 0.03837
30 15.78 0.1671 7.964 0.07181
35 19.73 0.2559 10.69 0.1184
40 23.57 0.3642 13.58 0.1790
45 27.22 0.4911 16.57 0.2543
50 30.99 0.6366 19.63 0.3448
60 38.84 0.9855 25.97 0.5725
70 46.97 1.414 32.56 0.8650
80 55.23 1.925 39.37 1.224
90 63.55 2.519 46.36 1.653
100 71.84 3.196 53.48 2.152
110 80.06 3.956 60.72 2.723
120 88.17 4.797 68.03 3.367
130 96.15 5.719 75.40 4.084
140 104.0 6.720 82.82 4.875
150 111.7 7.798 90.26 5.740
160 119.4 8.954 97.71 6.680
170 126.9 10.19 105.2 7.694
180 134.3 11.49 112.6 8.784
190 141.7 12.87 120.1 9.947
200 149.1 14.32 127.6 11.19
210 156.4 15.85 135.0 12.50
220 163.7 17.45 142.4 13.89
230 171.1 19.13 149.9 15.35
240 178.5 20.87 157.3 16.88
250 185.9 22.70 164.8 18.49
260 193.4 24.59 172.2 20.18
270 200.9 26.56 179.6 21.94
273.15 203.2 27.20 182.0 22.51
280 208.4 28.61 187.1 23.77
290 216.0 30.73 194.5 25.68
298.15 222.1 32.52 200.6 27.29
300 223.5 32.93 202.0 27.66
310 231.1 35.20 209.4 29.72
320 238.7 37.55 216.9 31.85
330 246.2 39.98 224.3 34.06
340 253.7 42.48 231.8 36.34

ur(Cp(T)) = 2% (5 < T h2 0) K; 0.5% (20 < T h4 0) K; 0.2% (T > 40 K). ur(function values) = 2% (T < 40 K); 0.5% (40 < T h8 0) K; 0.2% (80 < T h3 4 0) K., ur(p) = 1% (level of
confidence = 0.68).

Table 4
Results for combustion experiments at T = 298.15 K (p = 0.1 MPa) for myo-inositol.a.

m (substance)/g 0.326994 0.349616 0.185533 0.330813 0.300834 0.175381 0.718940

m0 (cotton)/g 0.001275 0.001206 0.001093 0.001102 0.001040 0.001015 0.001110
m00 (polyethylene)/g 0.404867 0.346619 0.453702 0.352508 0.424407 0.516725 0.321436
DTc/K 1.60840 1.44839 1.61524 1.44829 1.64209 1.80212 1.75084
(ecalor)(
DTc)/J
23796.4
21437.4
23897.7
21427.7
24294.9
26662.6
25903.8
(econt)(
DTc)/J
26.73
24.14
26.67
23.69
27.16
30.45
30.18
DUdecomp HNO3/J 36.43 33.45 37.03 36.43 34.04 39.42 38.82
DUcorr/J 9.88 9.24 8.70 9.04 9.82 9.61 12.23

m0 Dcu0 /J 21.60 20.44 18.52 18.67 17.62 17.20 18.81

m00 Dcu00 /J 18768.54 16068.22 21032.40 16341.32 19674.36 23953.82 14900.91
Dcu (cr)/(Jg
1)
15249.9
15245.8
15241.0
15253.0
15244.9
15241.1
15249.2

Dcu (cr)/(Jg
1) 15246.4
u(Dcu)/Jg
1 1.7 b
a
The definition of the symbols assigned according to ref [22] as follows: m(substance), m0 (cotton) and m00 (polyethylene) are, respectively, the mass of compound burnt, the
mass of fuse (cotton) and auxiliary polyethylene used in each experiment, masses were corrected for buoyancy; V(bomb) = 0.32 dm3 is the internal volume of the calorimetric
bomb; pi(gas) = 3.04 MPa is the initial oxygen pressure in the bomb; mi(H2O) = 1.00 g is the mass of water added to the bomb for dissolution of combustion gases;
DTc = Tf
Ti + DTcorr is the corrected temperature rise from initial temperature Ti to final temperature Tf, with the correction DTcorr for heat exchange during the experiment;
econt is the energy equivalents of the bomb contents in their initial eicont and final states efcont, the contribution for the bomb content is calculated with (econt)(
DTc) = (eicont)
(Ti
298.15) + (efcont)(298.15
Tf + DTcorr.). DUdecomp HNO3 is the energy correction for the nitric acid formation. DUcorr is the correction to standard states.
b
The standard deviations of the mean.
80 A.V. Knyazev et al. / J. Chem. Thermodynamics 116 (2018) 7684

Table 5
Thermochemical data at T = 298.15 K (p = 0.1 MPa) for myo-inositol.

Df Sm (cr)/ Df Gm (cr)/

    
Df Hm (cr)/ Df Hm (cr)/ Dcrg Hm / Df Hm (g)/ Df Hm (g)calc c/
kJmol
1 kJmol
1 JK
1mol
1 kJmol
1 kJmol
1 kJmol
1 kJmol
1

2771.1 [27]
1304.9 [27]

2788.6 [28]
1287.4 [28]

2746.72.1 a
1329.32.3 b
1232.53.5
9623 173.91.2
1155.42.6
1156.54.9
a
The expanded uncertainty with 0.95 level of confidence include the expanded uncertainties of calibration, the combustion energies of the auxiliary materials, ratio
between masses of compound and auxiliary materials.
b
The expanded uncertainty at 95% confidence level was evaluated accounting the uncertainties of the enthalpy of combustion Dc H0m and the uncertainty of the enthalpies
of formation for resulting H2O (liq) and CO2 (g).
c
G3MP2 calculation with procedure from atomization reaction.

1
C op =J  K
1  mol A B  T=K=30 C  fT=K=30g2
D  fT=K=30g3 E  fT=K=30g4
F  fT=K=30g5 G  fT=K=30g6 1

1
lnfC op =J  K
1  mol g A B  lnfT=K=30g C  ln fT=K=30g
2

Fig. 4. Scheme of myo-inositol synthesis.
of the total heat capacity of calorimetric (ampoule + substance)
over the range between 8 K and 340 K. The experimental points
of C op within the temperature interval (8.5340) K were fitted by
means of the least-squares method and polynomial equations
(Eqs. (1) and (2)) of the C op versus temperature have been obtained.
The corresponding coefficients (A, B, C, etc.) are given in Table 2
3 4
D  ln fT=K=30g E  ln fT=K=30g
5 6
F  ln fT=K=30g G  ln fT=K=30g
7 8
H  ln fT=K=30g I  ln fT=K=30g
2
Partitioning into 2 intervals of the temperature dependence of
the heat capacity contributes to the best smoothing of the experi-
mental curve. Their root mean square deviation from the averaging
C op = f(T) curve was 0.15% within the range T = (8 to 40) K, 0.075%
from T = (40 to 80) K and 0.050% between T = (80 and 340) K
(Fig. 2). The experimental values of the molar heat capacity of
myo-inositol over the range from 8 K to 340 K and the averaging
C op = f(T) plot are presented in Fig. 1. The heat capacity C op of this
substance gradually increases with rising temperature and does
not show any peculiarities. It should be noted that the temperature
dependences of the heat capacity of myo-inositol and a-D-glucose
[15], which has a similar chemical composition as inositol, in the
temperature intervals (1025) K and (160340) K practically coin-

Table 6
Results of the temperature dependence of frequency shift rate dfdt
1 of the QCM and corresponding product of condensation coefficient, sample surface roughness and vapor

pressure (acpsat) for myo-inositol, as well as, sublimation enthalpy Dcrg Hm (T) determination.a

dfdt
1/Hzs
1 106acpsat/Pa T
1/K
1 Rln(acpsat/po)


Run T/K Dcrg Hm /kJmol
1
  
Inacpsat =po
72325 T0 T0 = 376.8 K
RT 0
T
T10
33:5 T
1
In T 0
172771 1 T
R R

Dcrg Hm (298.15 K) = 175.4 1.8 kJmol
1
1 398.01 0.3998 179 0.002512
167.5 172.1
393.27 0.2099 93 0.002543
172.9 172.2
388.37 0.1092 48 0.002575
178.4 172.4
383.43 0.05456 24 0.002608
184.2 172.5
378.50 0.02744 12 0.002642
190.0 172.7
373.57 0.01370 5.9 0.002677
195.8 172.9
368.65 0.006540 2.8 0.002713
202.0 173.0
363.67 0.003173 1.4 0.002750
208.1 173.2
358.68 0.001310 0.56 0.002788
215.5 173.4
353.69 0.0006094 0.26 0.002827
221.9 173.5
2 400.64 0.5620 252 0.002496
164.6 172.0
395.88 0.3050 136 0.002526
169.8 172.1
391.09 0.1636 72 0.002557
175.0 172.3
386.20 0.08093 36 0.002589
180.9 172.5
381.32 0.04096 18 0.002622
186.6 172.6
376.35 0.01968 8.5 0.002657
192.8 172.8
371.37 0.00985 4.2 0.002693
198.6 173.0
366.36 0.004489 1.9 0.002730
205.2 173.1
361.38 0.002052 0.87 0.002767
211.7 173.3
356.29 0.0009518 0.40 0.002807
218.2 173.5
a
the expanded uncertainties are U(T) = 0.02 K, Ur(dfdt
1) = 0.01, Ur(acp*sat) = 1 for confidence level = 0.95, k  2.
 A.V. Knyazev et al. / J. Chem. Thermodynamics 116 (2018) 7684 81

Table 7

Compilation of data on standard enthalpies of sublimation, Dcrg Hm , of myo-inositol.
a  
Method Trange/K (Dcrg Hm /Tav)/kJmol
1 K_1 Dcrg Hm (298.15)/kJmol
1 Ref.

C 474.2 167.0 2.0 172.9 2.0 [29]

TE 461493 154.8 160.8 4.0 [30]
TE 454472 165.4 170.9 4.0 [31]
ME 462.1 168.0 173.5 4.0 [31]
ME 438.3458.1 174.0 2.7 179.1 2.7 [32]
QCM 353.7400.6 172.8 1.8 175.4 1.8 this work
weighted mean value 173.9 1.2 b
a
Methods: C calorimetry; QCM quartz-crystal microbalance; TE torsion-effusion; ME mass effusion Knudsen method. The expanded uncertainty of the mean with
0.95 level of confidence is used.
b
Weighted mean value from bold values. Value was recommended for further thermochemical calculations.

Fig. 5. Plot of unit cell parameter vs. temperature for myo-inositol.

cide (Fig. 3). Differences in the heat capacity of compounds in the
temperature interval (25160) K are due to the difference in the
structure of the compounds and the number of hydrogen bonds
in the crystals. It should be noted that the difference between
the heat capacity of myo-inositol and a-D-glucose reaches 15% in
the temperature interval 25160 K [15].
From the experimental C op values within the range (2550) K,
the value of the fractal dimension D of the myo-inositol was eval-
uated. According to the fractal theory of the heat capacity [16], D is
the most important parameter that specifies the character of
heterodynamics of the substance structure. For solids of a chain
structure the relation C op versus T at lower temperatures is propor-
82 A.V. Knyazev et al. / J. Chem. Thermodynamics 116 (2018) 7684

tional to T1, of a layer structure to T2 and of steric one to T3 [17]. In
the fractal theory of the heat capacity, an exponent on T is the heat
capacity function is denoted by D and is called the fractal dimen-
sion. This follows specifically from Eq. (3) [16]:
 D
T
C v 3DD 1kNcD 1nD 1  ; 3
hmax
where N is the number of atoms in a formula unit, k the Boltzmann
constant, c(D + 1) the c-function, n(D + 1) the Riemann n-function,
and hmax is the characteristic temperature. As follows from infer-
ences [16], D can be evaluated from the experimental data on the
temperature-dependent heat capacities from a slope of the corre-
sponding rectilinear sections of the plot lnCv versus lnT. Without a
substantial uncertainty it may be assumed that at T < 50 K C op = Cv.
From the lnCv versus lnT plot and Eq. (3) it was found that in the
range (2550) K, D = 1.5, hmax = 271.5 K for myo-inositol. With these
values of D and hmax Eq. (3) reproduces the experimental C op values
over the temperature range mentioned with an uncertainty of
0.34%. The D-value points to the chain structure of myo-inositol
[1719].
reproduces the C op values of myo-inositol at T < 9 K with the same
relative standard uncertainty.
The calculations of H(T)H(0) and S(T)S(0) were made by
the numerical integration of Cp = f(T) and Cp = f(lnT) curves,
respectively, and the Gibbs function G(T)H(0) was estimated
from the enthalpies and entropies at the corresponding tempera-
tures [17]. It was suggested that the relative standard uncertainty
of the function values was 2% at T < 40 K, 0.5% between 40 K and
80 K and 0.2% in the range from 80 K to 340 K.
3.3. Combustion calorimetry. Thermodynamic characteristics of myo-
inositol formation
Experimental results from combustion experiments with the
myo-inositol are given in Table 4 and Table 1S. Standard specific
energies of combustion Dcu(cr) of myo-inositol are given in
Table 4. They have been used to derive the standard molar
enthalpy of combustion Dc Hm (cr) and the standard molar enthalpy
of formation of compound in the crystalline state Df Hm (cr) (see
Table 5). Values of Dcu and Dc Hm refer to the reaction:

3.2. Thermodynamic functions C6 H12 O6 cr 6O2 g 6CO2 g 6H2 Ol 5

To calculate the standard thermodynamic functions (Table 3) of
myo-inositol, C op values of it were extrapolated from the starting
temperature of the measurement (approximately 9 K) to 0 K by
the Debye function of heat capacity [20]:
 
hD
C op nD ; 4
T
where D is the symbol of Debyes function, n = 3 and hD(C6H12O6)
= 95.1 K are specially selected parameters [20]. Eq. (4) with the
above parameters describes the experimental Cp values of the com-
pound between 9 K and 12 K with the relative standard uncertainty
of 0.52%. In calculating the functions, it was assumed that Eq. (4)
Value of Df Hm
(cr) of the compound under study (see Table 5)
was calculated from the enthalpic balance according to equation
(5) and using standard molar enthalpies of formation of H2O (l)
and CO2 (g) assigned by CODATA [21]. For converting the energy
of the actual bomb process to that of the isothermal process, and
reducing to standard states, the conventional procedure was
applied [22]. Uncertainties related to combustion experiments
were estimated according to the procedure recommended by Olof-
sson [22]: the uncertainties of the standard molar energy of com-
bustion correspond to expanded uncertainties of the mean (0.95
confidence level); the uncertainty of the molar enthalpy of com-
bustion and of the molar enthalpy of formation is twice the overall
standard deviation and includes the uncertainties from calibration,

Table 8
Parameters of unit cells and thermal expansion coefficients versus temperature for myo-inositol; po = 0.1 MPa.

T/K a/nm b/nm c/nm b/ V/nm3 q/gcm
3

150 0.6619 1.2110 1.9657 105.70 1.5168 1.577
175 0.6625 1.2113 1.9669 105.70 1.5196 1.574
200 0.6625 1.2115 1.9653 105.54 1.5197 1.574
225 0.6621 1.2115 1.9651 105.52 1.5187 1.575
250 0.6628 1.2118 1.9674 105.66 1.5216 1.572
275 0.6634 1.2120 1.9688 105.74 1.5237 1.570
300 0.6636 1.2119 1.9684 105.65 1.5244 1.569
325 0.6631 1.2126 1.9704 105.73 1.5250 1.569
350 0.6633 1.2128 1.9718 105.65 1.5273 1.566
375 0.6647 1.2135 1.9727 105.63 1.5324 1.561
400 0.6650 1.2136 1.9738 105.58 1.5343 1.559
425 0.6663 1.2145 1.9746 105.63 1.5389 1.555
450 0.6662 1.2152 1.9747 105.54 1.5403 1.553
T/K aa106/K
1 ab106/K
1 ac106/K
1 ab106/K
1 av106/K
1
150 0.0 0.0 5.2 4.8 2.0
175 2.9 1.8 7.4 3.7 10.2
200 6.5 3.6 9.6 2.6 18.3
225 10.1 5.3 11.8 1.5 26.5
250 13.7 7.1 14.0 0.4 34.6
275 17.4 8.8 16.3
0.7 42.8
300 21.0 10.6 18.5
1.8 50.9
325 24.6 12.3 20.7
2.9 59.0
350 28.2 14.0 22.9
4.0 67.1
375 31.8 15.8 25.0
5.1 75.2
400 35.4 17.5 27.2
6.2 83.3
425 38.9 19.3 29.4
7.3 91.4
450 42.5 21.0 31.6
8.4 99.4

Standard uncertainties u are u(T) = 1 K, u(a) = 0.0008 nm, u(b) = 0.0010 nm, u(c) = 0.0017 nm, u(b) = 0.13, u(V) = 0.0020 nm3, u(q) = 0.003 gcm
3, ur(p) = 1% (level of
confidence = 0.68).
 A.V. Knyazev et al. / J. Chem. Thermodynamics 116 (2018) 7684 83

from the combustion energies of the auxiliary materials (the ratio the thermal expansion coefficient in given direction corresponds
between the mass of compound and the mass of the auxiliary to length of radius-vector, which is traced from origin of coordi-
material was taken into account for each combustion experiment nates to edge of figure of expansion [34]. The thermal expansion
[22]), the uncertainties of the enthalpies of formation of the reac- of the myo-inositol is anisotropic; the greatest thermal deforma-
tion products H2O and CO2 [21]. tions are observed along the crystallographic axis a, which is due
It should be noted that the enthalpy of combustion of myo- to the weakest hydrogen bonds along this direction (Fig. 6).
inositol inositol is less by 58 kJmol
1 compared with a-D-
glucose, which is due to structural effects [23].
From the absolute value of the entropy of the myo-inositol
(Table 2), carbon in the form of graphite, gaseous hydrogen and
oxygen [24,25] the standard entropy of formation Df Sm of myo-
inositol at T = 298.15 K was calculated by methods described ear-
lier [26]. The Gibbs function of formation Df Gm of the myo-
inositol was evaluated from Df Hm and Df Sm values (Table 5). The
values conform to the following process:
6  Cgr 6  H2 g 3  O2 g ! C6 H12 O6 cr
The standard molar thermodynamic functions in the crystalline
state collected in Table 5 can be used for optimization of methods
of synthesis, as well as for validation of theoretical and empirical
methods for prediction of thermodynamic properties. As an exam-
ple, we analysed the reactions of myo-inositol synthesis from car-
bohydrates (Fig. 4). It turns out that the reactions are
thermodynamically allowed regardless of natural carbohydrate
structure; therefore this is one of the most probable ways of syn-
thesis of this vitamin-like compound in living organisms.

3.4. QCM study of myo-inositol. Enthalpy of sublimation

Primary experimental results of the QCM studies can be found

in Table 6. The heat capacity difference between crystal and gas
phases Dgcr C p =
33.5 JK
1 mol
1 have been evaluated according
to the empirical procedure suggested by Chickos and Acree [33]
based on the experimental isobaric heat capacity value C p (cr) =
222.1 JK
1 mol
1 at 298.15 K determined in the present work.
The sublimations of myo-inositol was previously studied by
calorimetry [28], as well as by torsion-effusion and mass effusion
Knudsen methods [3032]. The all adjusted to the reference tem-
perature values of Dgcr Hom are listed in Table 7. The comparison of
the experimental enthalpies of sublimation obviously indicates
that enthalpy of sublimation for the studied compound determined
in the present work and in works [29,31] agrees within the deter-
mination uncertainty (see Table 7). In order to establish more con-
fidence, we calculated the mean average value Dgcr Hom (298.15 K) =
(173.9 1.2) kJmol
1 for myo-inositol using the uncertainties of
the individual sublimation enthalpy results from this work and
[29,31] as the weighting factor. This weighted mean value (see
Table 7) was recommended for further thermochemical
calculations.

3.5. Low-temperature and high-temperature X-ray diffraction

The next task of the work was the X-ray diffraction investiga-
tion of compound with the purpose of definition of the thermal
expansion coefficients. The temperature dependence of the unit
cell parameters is plotted in Fig. 5 and Table 8 lists these parame-
ters together with thermal expansion coefficients and densities.
The density values obtained are slightly smaller than those pre-
sented in the work [7], in which the calculated density (q =
1.61 gcm
3) from X-ray diffraction data is given. It should be
noted that the density of X-ray diffraction data is the maximum
and corresponds to the density of an ideal single crystal.
Thermal expansion coefficient is the quantitative characteristic
of thermal expansion. We used the formula aL 1L  DDLT , where aL
coefficient of thermal expansion, L unit cell parameter. Value of Fig. 6. 2D thermal expansion diagrams for myo-inositol.
84 A.V. Knyazev et al. / J. Chem. Thermodynamics 116 (2018) 7684
4. Conclusions
The general aim of these investigations was to report the results
of the thermodynamic study of the myo-inositol. The heat capacity
of this vitamin B8 was measured over the temperature range from
(8 to 340) K, the thermodynamic functions were calculated and the
fractal dimension D evaluated. Thermochemical parameters of for-
mation are determined by combining the data obtained by using
combustion calorimetry and heat capacity measurements.
Acknowledgements
The work was performed with the financial support of the Rus-
sian Foundation of Basic Research (Project Number 16-03-00288).
This work has been partly supported by the Russian Government
Program of Competitive Growth of Kazan Federal University.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jct.2017.08.028.
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JCT 17-569