Ovchinnikov / Chemistry Journal (2013), Vol. 02, Issue 02, pp.

59-65 ISSN 2049-954X

Research Paper

Thermochemistry of Heteroatomic Compounds: Some

Thermodynamic Aspects of Combustion and Formation
of Carbohydrates of Different Structures
Vitaly Ovchinnikov

Tupolev Kazan National Researching Technical University, St-K, Marks 10, 420111 Kazan, Tatarstan /Russia
E-Mail: chem_vvo@mail.ru

Abstract
The linear equation of a general view Y = i f (N - g), where Y can be a free energy or heat of combustion orformation,
entropy and the heat of capacity, parameters, i and f are correlation factors, describing the interdependence between
thermodynamic functions of sugars and their numbers (N) of valence electrons except the numbers of lone electron pairs (g)
of heteroatoms in them, has been applied for calculation of sugars of a various structure. The obtained results can be used
for an estimation of the energy transfer in living systems by the means of phosphorus containing sugars like adenosine-
triphosphate (ATP).

Keywords: Sugar, Carbohydrate, Combustion, Formation, Free Energy, Heat, Entropy, Heat Capacity

1. Introduction
The interest of biochemists to the definition and analysis of
thermodynamic functions of carbohydrates a various struc-
ture does not weaken during many tens years till this time
(Corbridge, 1980 and Haynie, 2008). It is established, that
metabolism processes of carbohydrates are carried out via
the formation of phosphorus-containing esters. The signif-
icance of phosphorus-containing sugars in biochemical
processes it is possible to explain from the energetic and
structural positions (Stepanenko, 1977). Nucleoside-dipho-
sphosugars (NDFS) are good donors of the sugar rests
from the thermodynamic points of view. According to
Kochetkov and co-authors (Kochetkov et al, 1967) the
hydrogen bonds formation inside NDFS leads to the twist
conformation, which promotes its interaction with enzyme
and help to conduct biochemical reaction. Taking into
account the presented results only it is possible to make
some analysis of the thermochemical properties of sugars
of the different structure.
esponds to Eq. 1 in general (Cox & Pilcher, 1970)
aHbNcOdPVe + nO2 aCO2 + b/2 H2O + d/2 N2+ eH3PO4 + Y..1
Where a, b, c, d, e are stoichiometric coefficients, and Y is a change of
functions: the free energy, enthalpy or entropy at the standard conditions
Earlier it has been shown (Kharasch & Sher, 1925;
Ovchinnikov, 2006; 2011 and 2012) that the magnitudes of
the heats of combustion for organic compounds (co) can
be calculated effectively within the limits of the one-
factorial regression analysis i.e. at the construction of a
various correlation equations between the values obtained
earlier experimentally heats of combustion of compounds
and a number of participating in them bond-forming,
valence electrons (Eq. 2):
co = i f (N - g)...2

Where parameters i and f are a correlation factors. They characterize

2. Results and Discussion structurally-thermal contributions in the heats of combustion and
"sensitivity" of valence electrons N in molecule, from which the number
The combustion process of heteroatomic compounds corr- (g) lone pair electrons of heteroatoms in a various functional groups is

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 Ovchinnikov / Chemistry Journal (2013), Vol. 02, Issue 02, pp. 59-65
subtracted. So, for elements of IVA group of Periodic table g is 0, for VA
groups g is 1, for VI group g is 2 (Ovchinnikov, 2012)
Similarly Eq. 3 can be presented for the characteristic of
other thermodynamic functions, such as the free energy of
combustion and formation, entropy and heat capacity
Y = i f (N - g).3
2.1. Free Energies of Combustion and Formation
The values of the free energy of combustion (cGo) and
formation (fGo) in the condensed phase carbohydrates
such as -D-galactose -I, -D-glucose -II, -D-lactose -III,
-D-saccharose -IV, -D-fructose -V for a long time are
known in the literature (Metzler et al, 2001).
The equation (4) has been calculated with the use of all
results in mentioned monography values of the free
energies of non-phosphoric and phosphor-containing carb-
ohydrates (Table 1a, b, column 3, compounds I-V, XIII-
XIX without of brackets).
cGo = (24.715.0)-(121.40.5) (N-g); r 0.999, So 17.0, n 12....4
The dependence (Eq. 4) was used for calculation of the
free energy combustion of non-phosphorus carbohydrates
(D-ribose -VI, D-arabinose -VII, -D-xylofuranose -VIII,
xylose -IX, D-sorbose -X, D-mannose -XI and D-gulose -
XII) and important phosphorylated sugars such as methyl-
-D-glycopyranoside-4,6-cyclophosphate -XX, methyl--
D-ribofuranoside-3,5-cyclo-phosphate[-pXXI,pmethyl--
D-glycopyranoside-2,4-cyclophosphate -XXII, dimethyl-
-D- glycopyranoside -3,5- cyclophosphatep-pXXIII, p1-
adenine-ribofuranoside-3,5-cyclophosphatep-XXIV, p1-
adenine-ribofuranoside-2,3-cyclophosphatep-pXXV, p1-
adenine-ribofuranoside-5-phosphate (AMP) -XXVI, 1-ad-
enine-ribofuranoside-5-diphosphate (ADP) p-pXXVIIpan-
dp1-adenine-ribofuranoside-5-triphosphate (ATP)-XXVIII
(Table 1a, c, the magnitudes in brackets).
It is necessary to add, that in Metzlers monography these
are values of cGo and fGo for six phosphor-containing
carbohydrates. They are erithrose-4-phosphate-XIII, ribose
-5-phosphate-XIV, fructose-6-phosphate-XV, fructose-1,6-
diphosphate-XVI, sedoheptulose-7-phosphate-XVII, sedo-
heptulose-1,7-diphosphate-XVIII and -D-glycose-6-phos-
phate-XIX (Table 1b).
The Eq.5 includes five values for the free energies of
formation (fGo) of sugars (I-V). The essential contributi-
on in general energy of the intramolecular hydrogen bonds
from the acidic phosphorylic groups in carbohydrates
(XIII-XIX) does not allow to include these compounds in
general correlation. They form the separate dependence (6)
with the excellent correlation coefficient:
Available online at www.scientific-journals.co.uk
ISSN 2049-954X
fGo=(-303.920.8)-(25.60.6)(N-g); r 0.999, So 15.3, n5 (I-V)............5
fGo=(-807.36.2)-(39.60.3)(N-g); r 0.999, So 2.5, n5 (XIII-XIX)6
2.2. The Heats of Combustion and Formation
The heats of combustion (co) and formation (fo)
values for compounds (I-XII) are known in the literature
(Karrer & Floroni, 1923; Clarke & Stegeman, 1939;
Skuratov et al, 1957; Ponomarev & Migarskaya, 1960;
Desai & Wilhoit, 1970; Gerasimov et al, 1985; Wu et al,
1987 and Gubareva et al, 1991). Their thermochemical
parameters directly depend on the number of valence
electrons as shown (Eqs. 7 and 8):
co = (23.56.0)-(118.10.2) (N-g); r 0.999, So 7.1, n12 (I-XII)......7
fo = (-264.421.7)-(40.90.8) (N-g); r 0.998, So 25.7, n12 (I-XII)..8
The heats of combustion of all phosphorus-containing
carbohydrates (XIII-XXVIII) have been calculated with
the use of dependence (Eq. 7). The contribution acidic
groups (-75.3 kJmol-1) has been considered at
calculation of values co.
The heats of formation of phosphorus carbohydrates have
been calculated with the combination of equations (1, 8,
and 9). The values of fH for gaseous CO2, liquid H2O
and solid H3PO4 (-393.5, 285.8, -1279.0 kJ mol-1 correspo-
ndingly) were taken from the higher mentioned Cox &
Pilchers (1970) monography.
co = foproducts - foreagents..9
It is necessary to add, that the heats of combustion and
formation for the carbohydrates, containing the phosphate
cycles and adenine fragments (XX-XXVIII), were calcula-
ted previously (Ovchinnikov & Lapteva, 2011). The values
for the same parameters calculated in this work good
correspond to the mentioned earlier in the frames of
uncertainties (0.5 %) for calculations.
2.3. Entropy and Heat of Capacity
It was assumed that all thermodynamic data on entropy
(So) and heat capacity (Cp) of carbohydrates, (Miller,
1935; Jack & Stegeman, 1941; Kawaizumi et al, 1981;
Domalski & Hearing, 1990; Boerio-Goates, 1991 and
Putnam & Boerio-Goates, 1993). These data could be exa-
mined in the frame work the given above approach: the
interrelation of the chosen thermodynamic function with
the number of valence electrons in heteroatomic molecule
Eq. 3).
The equations (10 and 11) reflect the dependences of
entropy and heat capacity from number valence electrons;
they have been calculated similarly:
60
 Ovchinnikov / Chemistry Journal (2013), Vol. 02, Issue 02, pp. 59-65 ISSN 2049-954X

Table 1a. Thermodynamic Functions (kJ mol-1, J mol-1 K-1) of Carbohydrates at 298.15 K; all Compounds are in The Condensed Phase

No Compound, -cGo (calc. -fGo (calc. -co (calc. -fo (calc. So (calc.
Cp (calc. 0.5%)
Comp. Formula, (N-g) 0.5%) 0.5%) 0.5%) 0.5%) 0.5%)
1 2 3 4 5 6 7 8
Sugars

I 2865.9 923.5 2804.5 1271.5 205.4 217.0

6126 , 24

II 2872.2 917.2 2803.3 1272.8 209.2 219.2

6126, 24

(395.7
III 5826.5 1515.2 5652.1 2214.2 417.6
2.0)
122211, 48

5643.4 2221.2
IV 5789.9 1551.8 392.4 424.3

122211, 48

(201.3
V 2874.1 915.4 2810.4 1265.6 208.0
1.0)
6126, 24

(2403.3 (168.9
VI (815.9 4.1) 2347.6 1049.1 187.0
12.0) 0.8)
C5H10O5, 20

(2403.3 (168.9
VII (815.9 4.1) 2338.8 1057.9 184.0
12.0) 0.8)
C5H10O5, 20

(2403.3 (168.9
VIII (815.9 4.1) 2340.0 1057.8 -
12.0) 0.8)
C5H10O5, 20

So = (6.925.4)+(8.10.8) (N-g); r 0.984, So 19.3, n5 (I,II,IV,IX,X).10
Cp = (15.25.1)+(8.40.2) (N-g); r 0.998, So 5.7, n10 (I-VII, IX-XI)....11
The interdependence between entropy and heat capacity
values is available too as shown in Eq. 12.
So = (14.14.2) + (0.90.1) Cp; r 0.999, So 2.6, n 4 (I, II, IV, X)..12
heat capacity for sugars (III, VI, XI, XII) and not
applicable for calculation for sugars including phosphorus
-atom.
The other way for definition of the same function is known
as Gibbss equation (13). Last dependence can be used for
phosphorus carbohydrates (XIII-XXVIII).

The equations (10 and 11) allow to calculate entropy and cGo = co-* So.......13

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 Ovchinnikov / Chemistry Journal (2013), Vol. 02, Issue 02, pp. 59-65 ISSN 2049-954X

Table 1b. Thermodynamic Functions (kJ mol-1, J mol-1 K-1) of Carbohydrates at 298.15 K; all Compounds are in The Condensed Phase

1 2 3 4 5 6 7 8

(2403.3 (815.9
IX 2345.3 1051.4 143.5 184.0
12.0) 4.1)
C5H10O5, 20

(2889.5 (918.3
X 2799.1 1276.9 220.9 228.6
14.4) 4.6)
6126, 24

(2889.5 (918.3 (201.3

XI 2812.7 1263.4 214.2
14.4) 4.6) 1.0)
6126, 24

(2888.9 (918.3 (201.3

XII 2820.4 1255.7 -
14.4) 4.6) 1.0)
6126, 24
O|P
O|

|
|
H
O

O
H
2

( ) (1940.9 (1769.6 (10.7

XIII 1944.1 1439.1 -
9.7) 8.8) 0.05)
C4H9O7P, 16
Phosphor-Containing Sugars
O|

O|
H
|

O|
|P
H

O
O
H
|O
|

(2413.2 (1976.7 (5.7

2

( )
H
H
O

XIV 2414.9 1599.9 -

12.0) 9.9) 0.03)
5118P, 20
O|

O|
H
|

O|
H
O

|P
O
O
H
|O

(2885.5 (2183.7 (8.7

|

( )
H
H
O

XV 2888.1 1758.3 -
14.4) 10.9) 0.04)
6139P, 24
O|P2

O|

O|
H
|O

O|
H
O

|P

( )
(2960.8 (3530.4 (-195.5
O
O
H
|O
|

( )
XVI 2902.5 2600.8 -
H
H
O

14.8) 17.6) 1.0)

61412P2, 24
O|
O|

|P
|-
H
O

O
O
H
- H
C|O
H

( ) ( )
4

(3357.8 (2390.8 (22.8

XVII 3364.6 1913.3 -
16.8) 11.9) 0.1)
C7H15O10P, 28
O|P2

O|
O|
|O

|P
|-
H
O

O
O
H
- H
C|O
H

( ) ( ) ( )
4

(3433.1 (3308.7 (-181.4

XVIII 3379.0 2755.8 -
17.2) 16.5) 0.9)
C7H16O13P2, 28
O| P O
|
O H
H
O

_ ( )
2
O

_
H
O

_ _ (2885.5 (2183.7 (1.7

XIX 2886.0 1760.3 -
14.4) 14.4) 0.01)
C
H
H
O

6139P, 24
O OMe
O
O P OH
(3617.3 (1995.1 (3594.0 (1868.8 (78.1
XX O -
HO 18.1) 10.0) 18.0) 9.3) 0.4)
OH
7138P, 30

The analysis of entropic data for phosphor-containing unds there is a relatively big number of internal freedom
carbohydrates allows tomake some conclusion. A small degrees. The greater negative So values for compounds
positive magnitude of So values (compounds XIII-XVII, (XVIII and XXVIII) correspond to the presence of strong
XIX-XXVII) can characterize the fact that in these compo- hydrogen bonds, as shown by work of Kochetkov and co-

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 Ovchinnikov / Chemistry Journal (2013), Vol. 02, Issue 02, pp. 59-65 ISSN 2049-954X

Table 1c. Thermodynamic Functions (kJ mol-1, J mol-1 K-1) of Carbohydrates at 298.15 K; all Compounds are in The Condensed Phase

HO

O
M
e
O
O
(3617.3 (1995.1 (3594.0 (1868.8 (78.1
XXI -
/

O P
O OH
18.1) 10.0) 18.0) 9.3) 0.4)
HO
7138P, 30
OH
O OH
OMe
(3617.3 (1995.1 (3594.0 (1868.8 (78.1
O O -
XXII 18.1) 10.0) 18.0) 9.3) 0.4)
P
HO O
C7H13O8P, 30
HO
O
O
P
O (4831.3 (2391.3 (4774.7 (1760.9 (189.8
HO O -
XXIII O
Me2 24.1) 11.9) 23.9) 8.8) 0.9)
O
C9H15O8P, 40

O O Ade
O (5955.4 (544.9
P (6045.3 (2787.3 (301.5
XXIV HO O 29.8) 2.7) -
OH 30.2) 13.9) 1.5)
1012N56P, 50
HO O Ade

(5930.3 (570.0
O O (6045.3 (2787.3 (385.7
XXV 29.6) 2.8) -
P 30.2) 13.9) 1.9)
O OH
1012N56P, 50
O
( HO)2P O O Ade (5955.4 (544.9
(6045.3 (2787.3 (301.5
XXVI 29.8) 2.7) -
30.2) 13.9) 1.5)
HO OH
1014N57P, 50
O|
|P

|
| |
[

O
H
O

_
(6030.7 (1748.7
1

( ) O O Ade
P
2 n= (6045.3 (2787.3 (49.0
XXVII HO 30.1) 8.7) -
HO OH
30.2) 13.9) 0.2)
1015N510P2, 50
O|
|[

|
| |
]

O
H
O
P
O

_ O
( ) P O Ade (6106.0 (2666.6
2 n= 2 (6045.3 (2787.3 (-203.6
XXVIII HO 30.5) 13.3) -
HO OH
30.2) 13.9) 1.0)
1016N513P3, 50

workers (Kochetkov et al, 1967). glucose-6-phospate (XIX) and 1-adenine-ribofuranoside-5-

2.4. The Application of P-Sugars for Energy Transmissi-
on
The obtained thermodynamic data can be possible use for
the calculation of the heat of reaction (ro) between the
compressed glucose (II) and 1-adenine-ribofuranoside-5-
triphosphate (XXVII, ATP) (Eq. 14) for reception D-
diphophate (XXVII, ADP) in standard conditions (White
et al, 1981).
(II) +ATP(XXVIII) (XIX)+ADP(XXVII) + ro ...14
Let this reaction takes place in the absence of catalysis by
hexokinase-enzyme as it is known for alive organisms. The
free energy of this process it is possible to calculate by the

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 Ovchinnikov / Chemistry Journal (2013), Vol. 02, Issue 02, pp. 59-65
Eq. 15. The heat of this reaction it is possible to calculate
by the Eq. 16. The entropy of this interaction it is possible
to calculate with the use of Eq. 17.
rGo = = fGoproducts - fGoreagents.15
ro = foproducts - foreagents ...16 Standard heats of formation of intermediates in the synthe-
rSo = Soproducts - Soreagents ......17 Khim. Tekhnol., 28, pp. 54-56.
The calculated values obtained are rGo = -843, ro = +7,
rSo = +45 kJ mol-1 and J mol-1 K-1 correspondingly. Reac-
tion can be carried out under the control of free energy.
However it is necessary to remember, that the values used
at calculation have been calculated approximately and
have the significant uncertainty.
3. Conclusion
We have shown the application of the equation Y = i f
(N - g) for the calculation of the free energy, of the heat of
combustion and formation, of entropy and heat capacity
for the big row of known sugars with a numbers valence
electrons N, from which the numbers of lone electron pair
g are excluded. The calculated equations give a possibility
to calculate the same thermodynamic parameters for phos-
phor-containing carbohydrates with the important bioche-
mical function. The presented results can be used for an
estimation of the energy transfer in living systems by the
means of P-sugars like adenosine-triphosphate (ATP) too.
Acknowledgement
References
Boerio-Goates, J. (1991) Heat-capacity measurements and
thermodynamic functions of crystalline -D-glucose at
temperatures from 10K to 340K. J. Chem. Thermodyn-
am., 23, pp. 403-409.
Clarke, T.H., and Stegeman, G. (1939) Heats of combusti-
on of some mono- and disaccharides. J. Am. Chem. Soc.,
61(7), pp. 1726-1730.
Corbridge, D.E.C. (1980) Phosphorus. An Outline of its
Chemistry, Biochemistry and Technology. 2nd ed.
Amsterdam-Oxford-New York, Elsevier Scientific Publis-
hing Company.
Cox, J.D., and Pilcher, G. (1970) Thermochemistry of
Organic and Organometallic Compounds. London-New
York, Academic Press.
Desai, P., and Wilhoit, R.C. (1970) Heats of combustion
and enthalpies of formation of D-ribose, D-arabinose, and
L-ascorbic acid. Thermochim. Acta, 1, pp. 61-64.
Available online at www.scientific-journals.co.uk
ISSN 2049-954X
Domalski, E.S., and Hearing, E.D. (1990) Heat Capacities
and Entropies of Organic Compounds in the Condensed
Phase. Volume II. J. Phys. Chem. Ref. Data, 19(4), pp.
881-1047.
Gerasimov, P.A., Blokh, E.L., and Gubareva, A.I. (1985)
sis of vitamin C. Izv. Vyssh. Uchebn. Zaved., Khim.
Gubareva, A., Kunderenko, V.M., and Gerasimov, P.A.
(1991) Enthalpy of combustion and formation of d-ribose
and d-ribono--lactone. Izv. Vyssh. Uchebn. Zaved.,
Khim. Khim. Tekhnol., 34, pp. 41-45.
Haynie, D.T. (2008) Biological Thermodynamics. 2nd ed.
Cambridge University Press.
Jack, G.W., and Stegeman, G. (1941) The heat capacities
and entropies of two monosaccharides. J. Am. Chem.
Soc., 63(8), pp. 2121-2123.
Karrer, P., and Floroni, W. (1923) Polysaccharide XIX.
Die Verbrennungswarmen de kohlenhydrate. Helv. Chim.
Acta, 6, pp. 396-401.
Kawaizumi, F., Nishio, N., Nomura, H., and Miyahara, Y.
(1981) Heat-capacity measurements of aqueous solutions
of mono-, di-, and tri-saccharides using an isoperibol twin
calorimeter. J. Chem. Thermodynam., 13, pp. 89-98.
Kharasch, M.S., and Sher, B. (1925) The electronic conce-
ption of valence and heats of combustion of organic comp-
ounds. J. Phys. Chem., 29(6), pp. 625-658.
Kochetkov, N.K., Bochrov, A.F., Dmitriev, B.A., Usov,
A.I., Chilsov, O.S., and Schibaev, V.N. (1967) Chemistry
of Carbohydrates. Moskow, Chemistry.
Metzler, D.E., Metzler, C.M., and Sauke, D.J. (2001)
Biochemistry: The Chemical Reactions of Living Cells.
2nd ed. Academic Press.
Miller, P. (1935) The free energy of furfural and some of
its derivatives. Iowa State Coll. J. Sci., 10, pp. 91-93.
Ovchinnikov, V.V. (2006) Thermochemistry of Heteroato-
mic Compounds: Enthalpies of Combustion and Formation
of Organic Derivatives of P, As, Sb and Bi. Doklady
Phys. Chem., 411(2), pp. 328-330.
Ovchinnikov, V.V. (2011) Thermochemistry of Heteroato-
mic Compounds: Calculation of Combustion and Formati-
on Enthalpies of some Bioorganic Molecules of different
Phenanthrenes Rows. Open J. Phys. Chem., 1, pp. 1-5.
Ovchinnikov, V.V. (2012) Thermochemistry of Heteroato-
64
 Ovchinnikov / Chemistry Journal (2013), Vol. 02, Issue 02, pp. 59-65 ISSN 2049-954X

mic Compounds: Enthalpy of Combustion and Formation

of Organic Compounds of Groups I-VII Elements.
Doklady Phys. Chem., 443, pp. 69-72.

Ovchinnikov, V.V., and Lapteva, L.I. (2011) Thermoche-

mistry of Heteroatomic Compounds: the Heats of Combus-
tion and Formation of Clycoside and Adenosine Phosphat-
es. Intern. J. Org. Chem., 1, pp. 67-70.

Ponomarev, V.V., and Migarskaya, L.B. (1960) Heat of

combustion of some amino-acids. Russ. J. Phys. Chem.
(Engl. Transl.), 34, pp. 1182-1183.

Putnam, R.L., and Boerio-Goates, J. (1993) Heat capacity

measurements and thermodynamic functions of crystalline
sucrose at temepratures from 5 to 342 K. Revised values
for _fGm(sucrose, cr, 298.15 K), _fGm (sucrose, aq,
298.15 K), Sm(sucrose, aq, 298.15 K); and _rGm(298.15
K) for the hydrolysis of aqueous sucrose. J. Chem.
Thermodynam., 25(5), pp. 607-613.

Skuratov, S.M., Strepikheev, A.A., and Kozina, M.P.

(1957) About the reaction activity of five and six-member-
ed heterocyclic compounds. Dokl. Akad. Nauk SSSR,
117, pp. 452-454.

Stepanenko, B.N. (1977) Chemistry and Biochemistry of

Carbohydrates (monosugars). Moskow, Chemistry, pp.
181-192.

White, A., Handler, Ph., Smith, E.L., Hill, R.L., and Lehm-
an, I.R. (1981) Principles of Biochemistry. Moskow,
Chemistry, pp. 617-623.

Wu, D., Finch, A., and Gardner, P.J. (1987) Standard

energy of combustion and enthalpy of formation of -D-
mannose. Wuhan Daxue Zuebao, Ziran Kexueban, pp.
59-63.

Available online at www.scientific-journals.co.uk 65