J. Chem.

Thermodynamics 116 (2018) 7684

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J. Chem. Thermodynamics

journal homepage: www.elsevier . com/ locate/ j ct

propiedades termodinmicas de myo-inositol

AV Knyazev un , , VN Emel'yanenko segundo , do , , AS Shipilova un , DH Zaitsau do , MI Lelet un , SS Knyazeva un ,

EV Gusarova un , MA Varfolomeev segundo
un Universidad Lobachevsky, Gagarin Prospekt 23/2, 603950 Nizhny Novgorod, Rusia
segundo Departamento de Qumica Fsica, Universidad Estatal de Kazn, Kremlevskaya Str. 18, 420008 Kazan, Rusia
do Departamento de Qumica Fsica y el Departamento, Ciencia y Tecnologa de la Vida, la Luz y la Materia de la Universidad de Rostock, Dr.-Lorenz-Weg 1, D-18059 Rostock, Alemania

informacin del artculo abstracto

Historia del artculo: In the present work, the temperature dependence of heat capacity of vitamin B 8 ( myo-inositol) has been measured for the rst time over the
Recibido el 2 de de julio de 2.017
range from 8 K to 340 K by precision adiabatic vacuum calorimetry. Based on the experimental data, the thermodynamic functions of the vitamin
Recibida en forma 24 de agosto de 2017 Aceptado revisada 26 de de
B 8, namely, the heat capacity, enthalpy H (T) H ( 0), entropy S (T) S ( 0) and Gibbs function G (T) H ( 0) have been determined for the range from
agosto de 2017 Disponible en Internet el 30 de agosto de 2017
T ? 0 K to 340 K. The value of the fractal dimension D in the function of multifractal generalization of Debyes theory of the heat capacity of solids
was estimated and the character of heterodynamics of structure was detected. The enthalpy of combustion ( 2747.0 2.1) kJ mol 1 of the vitamin
B8
palabras clave:

Vitamina B 8
was measured for the rst time using high-precision combustion calorimeter. The standard molar enthalpy of formation in the crystalline state ( 1329.3
Mioinositol
capacidad calorimetra trmico al vaco
2.3) kJ mol 1 of B 8 at 298.15 K was derived from the combustion experiments. Using combination of the adiabatic and combustion calorimetry
adiabtico results the thermodynamic functions of formation of the myo-inositol at T = 298.15 K and p = 0.1 MPa have been calculated. The low-temperature
calorimetra de combustin funciones X-ray diffraction was used for the determination of coefcients of thermal expansion.
termodinmicas

2017 Elsevier Ltd.

1. Introduction
Myo-inositol (CAS: 87-89-8) is a sugar alcohol (isomer of glucose) 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 structural basis for a number of secondary
messengers in eukaryotic cells, including inositol phosphates (phytic acid), phosphatidylinositol 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 classied as a member of the
vitamin B-complex (often called vitamin B 8).
Patients suffering from clinical depression generally have decreased levels of inositol in their
cerebrospinal uid [2] . This work is a continuation of systematic studies of vitamins B. Earlier in the
articles [36] , we have investigated the thermodynamic properties of vitamins B n ( n = 2, 3, 9, 12). The
goals of this work include calorimetric determination of the standard thermody-
funciones NAMIC del myo-inositol con el propsito de describir los procesos bioqumicos e
industriales con su participacin.
2. Experimental
2.1. Muestra
Myo-inositol fue adquirido de NutriVitaShop. Para la fase de cationes identi fi, un patrn de
difraccin de rayos X de la vitamina B 8 muestra se registraron en un difractmetro de rayos X
Shimadzu XRD-6000 (CuK un
radiacin, geometra marido -2 marido) en el 2 marido variar de 5 a 60 con incremento de barrido de
0,02 . The water content in myo-inositol was determined by Karl Fischer titration. The water content of
the compound 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 certicate led us to
conclude that the myo-inositol sample studied (the content of impurities 0.1 wt%) was an individual
crystalline compound (monoclinic modication, space group P2 1/ c [7] ).

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; 2.2. Apparatus and measurement procedure
fax +7-831434-50-56 (A.V. Knyazev).

To measure the heat capacity C op of the tested substance over the range from 8 K to 340 K, a
E-mail addresses: knyazevav@gmail.com (A.V. Knyazev), vladchimic@tut.by
(V.N. Emelyanenko). 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
substance 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, Heidelberg, 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 (J K 1 mol 1) of myo-inositol, M = 180.156 g mol 1. p o = 0.1 MPa.

T/ K C op/ J K 1 mol 1 T/ K C op/ J K 1 mol 1 T/ K C op/ J K 1 mol 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

u r( C p ( T)) = 2% (5 < T h 2 0) K; 0.5% (20 < T h 4 0) K; 0.2% ( T > 40 K), u(T) = 0.01 K, u r( p) = 1% (level of condence = 0.68).
78 A.V. Knyazev et al. / J. Chem. Thermodynamics 116 (2018) 7684

calorimeter e calor = ( 14795.1 1.0) J K 1 was determined with a standard reference sample of benzoic pies, H 298, of the compound were computed with the thermodynamic procedures [12,14] implemented
acid (SRM 39 j, NIST). Correction for nitric acid formation was based on the titration with in the data output.

0.1 mol dm 3 NaOH (aq.). The relative atomic masses used for the elements were calculated as the
mean of the bounds of the interval of the standard atomic weights recommended by the IUPAC 3. Results and discussion
commission in 2011 [10] for each of these elements.

3.1. Heat capacity

The C o p measurements were carried out between 8 K and 340 K (see Table 1 ). The mass of the
2.3. Quartz-crystal microbalance technique
sample loaded in the calorimetric ampoules of the BKT-3.0 device was 0.5418 g. A total of 183

The Quartz Crystal Micrabalance (QCM) technique with the open surface (Langmuir-type) experimental C o p values was obtained in two series of experiments ( Fig. 1 ). The heat capacity of the

sublimation was used for recording of the temperature dependence of the sublimation rate. The sample varied from 20% to 50%
detailed description of the QCM technique can be found elsewhere

[11] .
Table 2
Briey, the solid sample of myo-inositol was dissolved in twicedistilled water and obtained
Coefcients in the tting polynomials for myo-inositol.
solution poured in an open cavity inside of the thermostat block. After heating the solution to 363 K
the water was gently vapourized and the solid lm of studied compound with high thermal contact with T/ K 8.550 40340
polynomials type 2 1
the thermostat block. Water was fully removed from the lm by exposing to vacuum (10 5 Pa) for 1 h at
temperature 393 K. Thus obtained solid lm with good thermal contact with metal thermostat was A 2.75883052 2.74353336
B 1.50843836 7.33676608
used for further investigation. Directly over the solid lm of the sample placed the QCM sensor. When
C 0.387259434 8.38636574
studied sample is heated and exposed to vacuum a certain amount of sample sublimes and deposited
D 3.92957686 10 2 1.88654864
on the surface of the quartz crystal. The mass increase E 0.130532770 0.207067559
F 4.33058693 10 2 1.10546683 10 2
G 0.408506536 2.30121114 10 4
H 1.19473626
I 0.636570563

D m on the QCM surface produces the shift of the vibrational frequency D f. The experimentally
determined with QCM technique temperature dependence of the frequency change rate (d f/ d t)
Deviation from fitting curve / %

was used to evaluate the sublimation enthalpy by using the Clausius-Clapeyron equation. The
frequency shift rates were converted into the absolute vapour pressures according to the procedure
published before [11] . Nevertheless, the ambiguity in the surface area of the sample and calibration
uncertainty gives the nal uncertainty of the absolute vapour pressure is comparable to the absolute
vapour pressure but the level of vapour pressures can be estimated. The initial frequency shift rates
were used to evaluate of the sublimation enthalpy for myo-inositol and, therefore, the uncertainty of
the absolute vapour pressures does not affect the uncertainty of the sublimation enthalpy. T/K

2.4. Calculation

Fig. 2. Temperature dependence of the deviation from tting curve.

Quantum chemical calculations were performed with the Gaussian 09 series software [12] .
Energies of molecules involved in this study were calculated using the G3MP2 method [13] . The
enthal-
C p / J K- 1 mol- 1

C p / J K- 1 mol- 1

T/K

T/K

Fig. 3. Comparison of the low-temperature heat capacity between myo-inositol (circles) and a- D-glucose (squares).
Fig. 1. Temperature dependence of heat capacity of myo-inositol.
 A.V. Knyazev et al. / J. Chem. Thermodynamics 116 (2018) 7684 79

Table 3
Thermodynamic functions of crystalline myo-inositol, M = 180.156 g mol 1, p o = 0.1 MPa.

T/ K C op T /( J K 1 mol 1) H T H 0 /( kJ mol 1) S T /( J K 1 mol 1) [ G T H 0 ]/( kJ mol 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

u r( C p ( T)) = 2% (5 < T h 2 0) K; 0.5% (20 < T h 4 0) K; 0.2% ( T > 40 K). u r( function values) = 2% ( T < 40 K); 0.5% (40 < T h 8 0) K; 0.2% (80 < T h 3 4 0) K., u r( p) = 1% (level of condence = 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

m 0( cotton)/g 0.001275 0.001206 0.001093 0.001102 0.001040 0.001015 0.001110
m 00( polyethylene)/g 0.404867 0.346619 0.453702 0.352508 0.424407 0.516725 0.321436
D T c/ K 1.60840 1.44839 1.61524 1.44829 1.64209 1.80212 1.75084
( e calor) ( D T c)/ J 23796.4 21437.4 23897.7 21427.7 24294.9 26662.6 25903.8
( e cont) ( D T c)/ J 26.73 24.14 26.67 23.69 27.16 30.45 30.18
D U decomp HNO 3/ J 36.43 33.45 37.03 36.43 34.04 39.42 38.82
D U corr/ J 9.88 9.24 8.70 9.04 9.82 9.61 12.23
m 0 D c u 0/ J 21.60 20.44 18.52 18.67 17.62 17.20 18.81
m 00 D c u 00/ J 18768.54 16068.22 21032.40 16341.32 19674.36 23953.82 14900.91
D c u ( cr)/(J g 1) 15249.9 15245.8 15241.0 15253.0 15244.9 15241.1 15249.2
D c u ( cr)/(J g 1) 15246.4
u( D c u )/ J g 1 1.7 b

a The denition of the symbols assigned according to ref [22] as follows: m( substance), m 0( cotton) and m 00( 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 dm 3 is the internal volume of the calorimetric bomb; p i( gas) = 3.04 MPa is the initial oxygen pressure in the bomb; m i( H 2 O) = 1.00 g is the mass of water added to the bomb for

dissolution of combustion gases;

D Tc= Tf T i + D T corr is the corrected temperature rise from initial temperature T i to nal temperature T f, with the correction D T corr for heat exchange during the experiment;
e cont is the energy equivalents of the bomb contents in their initial e icont and nal states e fcont, the contribution for the bomb content is calculated with ( e cont) ( D T c) = ( e icont)
( Ti 298.15) + ( e fcont) ( 298.15 T f + D T corr.). D U decomp HNO 3 is the energy correction for the nitric acid formation. D U corr 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.

D f H m( cr)/ D f H m( cr)/ D f S m( cr)/ D f G m( cr)/ D gcr H m/ D f H m( g)/ D f H m( g) calc c /

kJ mol 1 kJ mol 1 J K 1 mol 1 kJ mol 1 kJ mol 1 kJ mol 1 kJ mol 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 condence 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% condence level was evaluated accounting the uncertainties of the enthalpy of combustion D c H 0m and the uncertainty of the enthalpies of formation for resulting H 2 O (liq) and CO 2 ( g).

c G3MP2 calculation with procedure from atomization reaction.

C o p= J K 1 mol 1 A B T= K = 30 C f T= K = 30 g 2

D f T= K = 30 g 3 E f T= K = 30 g 4

F f T= K = 30 g 5 G f T= K = 30 g 6 1

ln f C o p= J K 1 mol 1 g A B ln f T= K = 30 g C ln 2 f T= K = 30 g

D ln 3 f T= K = 30 g E ln 4 f T= K = 30 g F ln 5 f T= K = 30 g

G ln 6 f T= K = 30 g H ln 7 f T= K = 30 g I ln 8 f T= K = 30 g

Partitioning into 2 intervals of the temperature dependence of the heat capacity contributes to the
best smoothing of the experimental curve. Their root mean square deviation from the averaging

C o p = 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
Fig. 4. Scheme of myo-inositol synthesis.
myo-inositol over the range from 8 K to 340 K and the averaging

of the total heat capacity of calorimetric (ampoule + substance) over the range between 8 K and 340
C o p = f(T) plot are presented in Fig. 1 . The heat capacity C o p of this substance gradually increases with
K. The experimental points of C o p within the temperature interval (8.5340) K were tted by means of
rising temperature and does not show any peculiarities. It should be noted that the temperature
the least-squares method and polynomial equations (Eqs. (1) and (2) ) of the C o p versus temperature
dependences of the heat capacity of myo-inositol and a- D-glucose
have been obtained. The corresponding coefcients (A, B, C, etc.) are given in Table 2

[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 df dt 1 of the QCM and corresponding product of condensation coefcient, sample surface roughness and vapor pressure ( ac p sat) for myo-inositol, as well as, sublimation enthalpy D g

cr H m ( T) determination. a

Run T/ K df dt 1/ Hz s 1 10 6 ac p sat/ Pa T 1/ K 1 R ln( ac p sat/ p o) D gcr H m/ kJ mol 1

T0 T 0 = 376.8 K
In ac p sat= p o 72325 RT 0
172771
R1T
1
T0
33:5
R T
1 In T T0

D gcr H m( 298.15 K) = 175.4 1.8 kJ mol 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, U r( df dt 1) = 0.01, U r( ac p* sat) = 1 for condence 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, D g cr H m, of myo-inositol.

Method a T range/ K ( D crg H m/ T av)/ kJ mol 1 K_ 1 D gcr H m( 298.15)/kJ mol 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 condence 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 From the experimental C o p values within the range (2550) K, the value of the fractal dimension D
are due to the difference in the structure of the compounds and the number of hydrogen bonds in the of the myo-inositol was evaluated. According to the fractal theory of the heat capacity [16] , D is the
crystals. It should be noted that the difference between the heat capacity of myo-inositol and a- D-glucose most important parameter that species the character of heterodynamics of the substance structure.
reaches 15% in the temperature interval 25160 K [15] . For solids of a chain structure the relation C o p versus T at lower temperatures is propor-
 A.V. Knyazev et al. / J. Chem. Thermodynamics 116 (2018) 7684

tional to T 1, of a layer structure to T 2 and of steric one to T 3 [ 17] . In the fractal theory of the heat reproduces the C op values of myo-inositol at T < 9 K with the same relative standard uncertainty.
capacity, an exponent on T is the heat capacity function is denoted by D and is called the fractal
dimension. This follows specically from Eq. (3) [16] : The calculations of H (T) H ( 0) and S (T) S ( 0) were made by the numerical integration of C p = f(T)
and C p = f( ln T) curves, respectively, and the Gibbs function G (T) H ( 0) was estimated from the
D enthalpies and entropies at the corresponding temperatures [17] . It was suggested that the relative
T
Cv 3 D D 1 k N cD1nD1 ; 3 standard uncertainty of the function values was 2% at T < 40 K, 0.5% between 40 K and 80 K and
h max
0.2% in the range from 80 K to 340 K.

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 h max is the characteristic temperature. As follows from inferences [16]
, D can be evaluated from the experimental data on the temperature-dependent heat capacities from
a slope of the corresponding rectilinear sections of the plot ln C v versus ln T. Without a substantial 3.3. Combustion calorimetry. Thermodynamic characteristics of myoinositol formation
uncertainty it may be assumed that at T < 50 K C o p = C v. From the ln C v versus ln T plot and Eq. (3) it
was found that in the range (2550) K, D = 1.5, h max = 271.5 K for myo-inositol. With these values of D and
h max Eq. (3) reproduces the experimental C o p values over the temperature range mentioned with an Experimental results from combustion experiments with the myo-inositol are given in Table 4 and
uncertainty of 0.34%. The D- value points to the chain structure of myo-inositol Table 1S. Standard specic energies of combustion D c u ( cr) of myo-inositol are given in

Table 4 . They have been used to derive the standard molar enthalpy of combustion D c H m ( cr) and the
standard molar enthalpy of formation of compound in the crystalline state D f H m ( cr) (see

[1719] . Table 5 ). Values of D c u and D c H m refer to the reaction: C 6 H 12 O 6 cr 6O 2 g

3.2. Thermodynamic functions

6CO 2 g 6H 2 O l 5

Value of D f H m ( cr) of the compound under study (see Table 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] :
C op n D h D
T;
where D is the symbol of Debyes function, n = 3 and h D( C 6 H 12 O 6)
= 95.1 K are specially selected parameters [20] . Eq. (4) with the above parameters describes the
experimental C p values of the compound between 9 K and 12 K with the relative standard uncertainty
of 0.52%. In calculating the functions, it was assumed that Eq. (4)
was calculated from the enthalpic balance according to equation
(5) and using standard molar enthalpies of formation of H 2 O (l) and CO 2 ( 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 Olofsson [22] : the
4 uncertainties of the standard molar energy of combustion correspond to expanded uncertainties of the
mean (0.95 condence level); the uncertainty of the molar enthalpy of combustion 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 coefcients versus temperature for myo-inositol; p o = 0.1 MPa.

T/ K a/ nm b/ nm c/ nm b/ V/ nm 3 q/ g cm 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 a a 10 6/ K 1 a b 10 6/ K 1 a c 10 6/ K 1 a b 10 6/ K 1 a v 10 6/ 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 nm 3, u( q) = 0.003 g cm 3, u r( p) = 1% (level of condence = 0.68). 82
 A.V. Knyazev et al. / J. Chem. Thermodynamics 116 (2018) 7684 83

from the combustion energies of the auxiliary materials (the ratio between the mass of compound and the thermal expansion coefcient in given direction corresponds to length of radius-vector, which is
the mass of the auxiliary material was taken into account for each combustion experiment traced from origin of coordinates to edge of gure of expansion [34] . The thermal expansion of the
myo-inositol is anisotropic; the greatest thermal deformations are observed along the crystallographic
[22] ), the uncertainties of the enthalpies of formation of the reaction products H 2 O and CO 2 [ 21] . axis a, which is due to the weakest hydrogen bonds along this direction ( Fig. 6 ).

It should be noted that the enthalpy of combustion of myoinositol inositol is less by 58 kJ mol 1 compared
with a- Dglucose, 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 D f S m of

myoinositol at T = 298.15 K was calculated by methods described earlier [26] . The Gibbs function of

formation D f G m of the myoinositol was evaluated from D f H m and D f S m values ( Table 5 ). The values

conform to the following process: 6 C gr 6 H 2 g 3 O 2 g ! C 6 H 12 O 6 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 example, we analysed the reactions of
myo-inositol synthesis from carbohydrates ( 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 synthesis 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 D gcr C p = 33.5 J K 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 J K 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
temperature values of D gcr H om 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 determination uncertainty (see Table 7 ). In
order to establish more condence, we calculated the mean average value D gcr H om ( 298.15 K) =
(173.9 1.2) kJ mol 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 investigation of compound with the purpose of
denition of the thermal expansion coefcients. The temperature dependence of the unit cell
parameters is plotted in Fig. 5 and Table 8 lists these parameters together with thermal expansion
coefcients and densities. The density values obtained are slightly smaller than those presented in
the work [7] , in which the calculated density ( q=

1.61 g cm 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 coefcient is the quantitative characteristic of thermal expansion. We used

the formula a L 1 L D L
D T, where a L

coefcient 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 B 8 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 formation are determined by combining the data obtained by using
combustion calorimetry and heat capacity measurements.
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The work was performed with the nancial support of the Russian Foundation of Basic Research [18] N.V. Karyakin, N.G. Chernorukov, E.V. Suleimanov, M.I. Alimzhanov, V.L. Trostin, A.V. Knyazev, The
(Project Number 16-03-00288). This work has been partly supported by the Russian Government thermodynamic properties of uranyl pyrovanadate and uranovanadic acid, Russ. J. Phys. Chem. 74 (2000)

Program of Competitive Growth of Kazan Federal University. 12261231 .

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JCT 17-569