International Journal of Organic Chemistry, 2011, 1, 67-70
doi:10.4236/ijoc.2011.13011 Published Online September 2011 (http://www.SciRP.org/journal/ijoc)
Thermochemistry of Heteroatomic Compounds:
the Heats of Combustion and Formation of Glyc oside
and Adenosine Phosphates
Vitaly Ovchinnikov, Ludmila Lapteva
National Researching University, Tupolev Kazan State Technical University, Kazan, Russian Federation
Received April 22, 2011; revised June 2, 2011; accepted July 13, 2011
Abstract
The heats of combustion of 4-th glycoside in the condensed state with the use of the equation

15.7 117.2
comb

H
Ng , in which N is a number bond-forming (valence) electrons less the number (g) of
lone electron pairs of nitrogen (g = 1) and oxygen (g = 2), have been determined. Such dependence is de-
duced previously joint for the description of the combustion enthalpies of 17 simple ethers of a cyclic struc-
ture and different sugars. The heats of formation (f
H

) of the mentioned above glycosides were calculated
according to the Hess law via two ways: 1) through the use their heats of hydrolysis (hydr
H
), which have
been investigated earlier experimentally, 2) with the use the calculated the heats of combustion. The last pro-
cedure has been used also for the calculation of the heats of formation of the adenosine tri(ATP)-, di(ADP)-
and mono(AMP)phosphates because of such thermochemical parameter is often hard achieved experimen-
tally. The heats of hydrolysis () of ATP into ADP and ADP into AMP were calculated on the basis of
their heats of formation in water (
hydr
fH

faq
H
). The free energies of the same process (hy
ere known in lit-
erature. Last circumstance give us a possibility to calculate the hydrolysis entropies (hydrSg the Gibbs
equation. The entropy values are a large negative, that pointed on the preliminary complex formation be-
tween adenosine phosphates and water before the breaking of P-O bonds or P-O-C fragments in its.
dr G) w
) usin
Keywords: Glycoside Phosphates, Adenosine Phosphates, Heat of Combustion, Heat of Formation
1. Introduction
Molecules, which contain cyclic phosphoric fragments,
represent the big interest within many decades as a bio-
chemical objects [1,2]. Nucleosides and phosphates of
sugars are representative of the important classes of es-
ters of a phosphorous acid. However their thermochem-
istry, having essential value for the much deeper, de-
tailed understanding of their important biochemical func-
tion, is poorly investigated. For this reason we have un-
dertaken the theoretical calculation of the heats of com-
bustion (comb
H
) and then on this basis the heats of
formation (f
H

2. Results and Dicussions
The heats of hydrolysis (hydr
H

) of methyl-α-D-glyco-
pyranoside-4’,6’-cyclophosphate (1), methyl-β-D-ribofu-
ranoside-3’,5’-cyclo-phosphate (2), adenosine(Ade)-3’,5’-
mono-cyclophosphate(3), adenosine-2’,3’-mono- cyc-lo-
phosphate (4) were founded previously (Table 1) [3].
The products of these interactions with water are methyl-
ά-D-glucopyranoside (5,aq), methyl-β-D-ribofuranoside
(6,aq) and 1-adenosine ribofuranoside (7,aq) are pre-
sented in Equation (1)


 
2
34
-, 2
-, hydr
liqH Oliq
aqH POaqH

 
14
57 (1)

) in the condensed state of organic
phosphor-nucleotides of a cyclic structure, kinetics and
thermochemistry of hydrolysis of which has been inves-
tigated earlier experimentally [3].
To calculate the heats of formation (f
H
) of the
molecules (1-4) and glycosides (5-7) in condensed state

V. OVCHINNIKOV ET AL.
68
and in water environment (aq
f
o
H
), necessary to calcu-
late at first their heats of combustion (comb
H
). The sum
of lasts with the heats in the water shells (ws
H
), which
were calculated via the molecular mechanics method
(MMM, column 7 in Table 1), gives the magnitudes of
f
aq
H in Equation (2)

-
aq
ffws
H
H
57 H (2)
In the previous communication us it has been estab-
lished, that the heats of formation (f
H
) of some
phosphorylated sugars can be calculated effectively from
their heats of of combustion (comb
H
), which generally
depends on the number of bond-forming (valent) elec-
trons N in a molecule minus the number (g) of lone elec-
tron pairs of nitrogen (g = 1) and oxygen (g = 2) in Equa-
tions (3) and (4) [5]

15.7 117.2
comb

H
Ng

  (3)
Table 1. Thermochemical parameters (kJ·mol–1) of glycoside and adenosine phosphate s. P : 101kP a ; T: 298. 15; all compounds
are in condensed state.
–f
H

cond
No Formula of compound,
(N-g) –hydr
H
expa–comb
H
b
calc.c calc.d –ws
H
e –aq
f
H

f
1
O
PO
OOMe
HO OH
OH
O
(30)
28.7 ± 0.5 3500.1 ± 17.61962.7 ±
3.0 1952.6 ± 9.8
2
O
HO
OH
HO
O
PO
O
(26)
49.1 ± 0.8 3447.5 ± 17.81731.9
± 5.7
2015.2
± 8.7
3
OAd
e
HO P
OH
O
O
O
(50)
48.1 ± 1.5 5844.0 ± 29.3663.2 ± 3.3656.4 ± 3.2
4
O
HO Ad
e
OH
PO
O
O
(50)
39.3 ± 1.5 5866.4 ± 29.3671.9 ± 5.9656.4 ± 3.2
5
OOMe HOCH
HO
HO
OH
2
(30)
3518.0
g ± 0.4 1233.4 g ± 0.8 29.7 ±1.5 1263.5 ±2.5
6
HO
HO
OH
HO O
(26)
3552.6
g ± 0.8 1202.7 g ± 0.8 18.0 ± 1.5 1220.7 ± 2.3
7
O
OAd
e
HO OH
H
(50)
5844.0 ± 29.2 –51.1 ± 0.2 43.9 ± 1.5 –7.2 ± 1.7
8
O
HO )( OP
O
PAd
e
HO OH
O
O
[]
n
=2 2
(50)
6061.5 ± 30.3 2711.1 ± 13.5 115.5 ± 1.5 2826.6 ± 15.0
9
O
HO )( OP
O
PAd
e
HO OH
O
O
[]
n
=2 1
(50)
6007.1 ± 30.0 1772.3 ± 8.8 97.1 ± .5 1869.3 ± 10.3
10
O
HO
)
( O
O
PAd
e
HO OH
2
(50)
5952.7 ± 29.8 833.5 ± 4.2 77.0 ± 1.5 910.5 ± 4.5
aData of the Ref. [3]; bCalculated by Equation (3); cCalculated by Equations (1) and (5); dCalculated by Equations (3) and (5); eCalculated by MMM-method;
lculated by Equation (2); gData of the Reference [6].
fCa

69 V. OVCHINNIKOV ET AL.

  
 
2
22
234
pqrst
comb
CHONPcondensO
uNgasxCO gas
y HOliqz HPOsolH


 
(4)
where p, q, r, s, t, u, x, y, z are stoichiometric factors.
This approach was applied to all biomolecules (1-7) and
the calculated comb
H
, f
H
and aq
f
H

magnitudes
through combination of the Equations (1-5) presented in
Table 1.

/() hydr combffreag
prod
HH H

(5)
Necessary values f
H
 (kJ·mol–1) for СО2(gas):
–395.5, H2O(liq): –285.8 and Н3РО4(aq, sol): –1289.9,
–1279.0 are taken from the monograph [4].
If it can be seen from the data of Table 1, the calcu-
lated the heats of formation in the condensed state with
the use of the experimental heats of hydrolysis [3] and
the same values obtained via Equations (3)-(5) [5] are
good correspond each other in the range of the assumed
in Table 1 (columns 5, 6) indefinites 2% - 3%, which
expressed in Equation (6)




1
1
kJ mol90.9159.3
0.91.1kJmol
hydr
calc
H
H




r = 0.985, so = 143.2, n = 4 (6)
It gives a real basis for the application of the men-
tioned above approach to the calculation of the thermo-
chemical parameters of such important bioorganic sub-
stances as adenosine tri(ATP, 8)-, di(ADP, 9)- and
mono(AMP, 10) phosphates.
It is known [1,2], that at each step of the hydrolysis
reaction of adenosine phosphates in the water shell, as it
shown on Equations (7)-(9), the essential quantity of
energy due to the breaking of P-O bonds in P-O-P frag-
ments is allocated accordingly to Hess law in Equation
(5).
 
 
34
2
,,
,,
hydr ff
ff
H
Haq HHPOaq
H
aqHHO liq

 


  

8
9

(7)
 
 
34
2
,,
,,
hydr ff
ff
H
Haq HHPOaq
H
aqHHOliq

 


  

9
10 (8)
 
 
34
2
,,
,,
hydr ff
ff
H
Haq HHPOaq
HaqHHOliq

 


  

10
7 (9)
In last Equation (9) the dissociation to the same bond
in AMP leads to formation of a water 1-adenosine ribo-
furanoside (7) and a water phosphorus acid. It is neces-
sary to note, that into the structure of a listed adenosine
phosphates enter the some hydroxyl groups at phospho-
rus, the energy of each is estimated as –54.4 kJ·mol–1;
this factor is considered at calculations of comb
H

for
compounds (8-10).
Despite of the approached calculations of the last
thermochemical parameter, it is possible to note, that the
hydrolysis of ATP and ADP is carried out with identical
(about –45, –46 kJ·mol–1) energy while the hydrolysis
AMP up to adenosine furanoside (7) and a phosphorus
acid is characterized noticeably by more greater the heats
of about –86 kJ mol-1, which presented in Table 2. Tak-
ing into account the published in the monograph [1] the
free energies of hydrolysis (hydr ) for ATP, ADP and
AMP and obtained in this work hydr
G
H

S
magnitudes, the
values of the entropies (hydr

) according to the Gibbs
Equation (10) were calculated and shown in Table 2.
hydr hydrhydr
GHTS

 (10)
Necessary to note, that the calculated the entropy
magnitudes are a large negative, especially for the hy-
drolysis process of AMP, that can pointed on the pre-
liminary complex formation between AMP and a water
molecules before the breaking of P-O bond in P-O-C
fragment.
3. Conclusions
Thus, as it has been shown during this work the Equation
(3), worked up to the correlation between of the heats of
combustion of 17 sugars of the different space structure
and the number of the valent electrons in its, excluding
of the lone electron pairs of heteroatoms, can be useful
applied to the calculation of the same thermochemical
parameters of the different bioorganic molecules, in
partly glycosides and adenosine phosphates.
Table 2. Thermodynamic parameters (J·mol–1 and
J·mol–1·K–1) of the hydrolysis reaction of adenosine phos-
phates at 298.15 K.
Hydrolysis reaction –hydrG a –hydrH –hydrS
Equation (7) 30543.2 46800 54.5
Equation (8) 27196.0 45300 60.7
Equation (9) 9204.8 86400 259.0
aData of the Reference [1].

V. OVCHINNIKOV ET AL.
70
4. References
[1] D. E. C. Corbribge, “Phosphorus: An Outline of Its
Chemistry, Biochemistry, and Technology,” 2nd Edition,
Elsevier, Amsterdam-Oxford-New York, 1980.
[2] А. White, Ph. Handler, E. Smith, R. Hill and I. R. Leman,
“Principles of Biochemistry,” McGraw-Hill, New York,
1978.
[3] J. A. Gerlt, F. H. Westheimer and J. M. Sturtevant, “The
Enthalpies of Hydrolysis of Acyclic, Monocyclic, and
Glycoside Cyclic Phosphate Diesters,” The Journal of
Biological Chemistry, Vol. 250, 1975, pp. 5059-5067.
[4] J. D. Cox and G. Pilcher, “Thermochemistry of Organic
and Organometallic Compounds,” Academic Press, New
York, 1970.
[5] V. V. Ovchinnikov and N. R. Muzafarov, “Thermo-
Chemistry of Heteroatomic Compounds. Calculation of
the Formation Enthalpy for Methyl-α-D-4’,6’-Cyclophos-
Phate on the Basis of His Enthalpy of Combustion,” Rus-
sian Journal of Organic Chemistry, Vol. 45, No. 1, 2009,
pp. 318-319.
[6] S. M. Skuratov, A. A. Strepikheev and M. P. Kozina,
“About the Combustion of Five and Six-Membered Het-
erocyclic Compounds,” Dokl. Acad. Sci. SSSR, Vol. 117,
1957, pp. 452-454.