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\title{Combustion Calorimetry and Thermodynamic Functions of Cyanocobalamin}
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             \author[1]{Alexander V.  Knyazev}

             \affil[1]{  Lobachevsky University}

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\date{\small \em Received: 15 December 2015 Accepted: 31 December 2015 Published: 15 January 2016}

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\begin{abstract}
        


In a calorimeter with a static bomb and an isothermal shield, the energy of combustion of the cyanocobalamin has been measured at 298.15 K. Physico-chemical methods established the products of combustion of cyanocobalamin in the conditions of calorimetric experiment. The enthalpy of combustion Î?"cH° and the thermodynamic parameters Î?"fH°, Î?"fG° of the cyanocobalamin at T = 298.15 K and p = 0.1 MPa have been calculated. Thermodynamic parameters Î?"fH°, Î?"fS° were determined and used to calculate the enthalpy of formation of cyanocobalamin.

\end{abstract}


\keywords{vitamin B12; cyanocobalamin; combustion calorimetry; thermodynamic functions.}

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\let\tabcellsep& 	 	 		 
\section[{Introduction}]{Introduction}\par
yanocobalamin, also called vitamin B 12 (PubChem CID: 5479203), is a water-soluble vitamin with a key role in the normal functioning of the brain and nervous system, and for the formation of blood. Vitamin B 12 is a cobalt-containing compound synthesized by bacteria and an essential nutrient in mammals, which take it up from diet \hyperref[b0]{[1]}. The significance of vitamin B 12 adequate nutritional status throughout life span is established and the adverse effects of vitamin B 12 deficiency in human health are currently recognized \hyperref[b1]{[2]}\hyperref[b2]{[3]}\hyperref[b3]{[4]}. In addition to the welldescribed reversible hematological and often irreversible neurological changes of severe vitamin B 12 deficiency, epidemiological studies revealed a more common condition, the low vitamin B 12 status particularly in elder and pregnant women \hyperref[b4]{[5]}\hyperref[b5]{[6]}. Because vitamin B 12 is essential for DNA synthesis and cellular energy production, a low vitamin B 12 status may be a risk factor for altered cellular metabolism and age-related diseases including cognitive decline and cardio-vascular disease \hyperref[b6]{[7]}.\par
This work is a continuation of systematic studies of vitamins B. Earlier in the articles \hyperref[b7]{[8]}\hyperref[b8]{[9]}\hyperref[b9]{[10]}, we have investigated the thermodynamic properties of vitamins B 2 , B 3 and the temperature dependence of the heat capacity of cyanocobalamin. The goals of this work include calorimetric determination of the standard thermodynamic functions of the cyanocobalamin. II. 
\section[{Experimental i. Sample}]{Experimental i. Sample}\par
Cyanocobalamin was purchased from Fluka. For phase identification, an X-ray diffraction pattern of the vitamin B 12 sample was recorded on a Shimadzu Xray diffractometer XRD-6000 (CuK ? radiation, geometry ?-2?) in the 2? range from 5º to 60º with scan increment of 0.02º. The X-ray data and estimated impurity content (0.1 wt \%) in the substance led us to conclude that the cyanocobalamin sample studied was an individual crystalline compound. Cyanocobalamin can crystallize in three modifications \hyperref[b3]{[4]}: 1) "as-purchased"; 2). "wet"; 3) "dry". According to X-ray diffraction and solid-state NMR spectroscopy, we investigated the "as-purchased" sample cyanocobalamin. This sample is usually obtained by rapid crystallization from water at 343 K. 
\section[{ii. Apparatus and measurement procedure}]{ii. Apparatus and measurement procedure}\par
The energy of combustion, Î?" c U, of cyanocobalamin was measured in a calorimeter (V-08) with a static bomb and an isothermal shield. The calorimeter design, the procedure of measuring the energies of combustion and the results of calibration and testing are given elsewhere \hyperref[b10]{[11]}. It should be noted that while checking the calorimeter by burning succinic acid, prepared at D.I. Mendeleev Research Institute of Metrology (the value of the standard enthalpy of combustion of the acid coincided with the certificate value within ±0.017\%). For complete combustion of cyanocobalamin we used paraffin as an auxiliary substance.\par
Physico-chemical methods established the products of combustion of cyanocobalamin in the conditions of calorimetric experiment. Firstly, the solid products of combustion were identified by X-ray diffraction (Shimadzu X-ray diffractometer XRD-6000). Secondly, the formed liquid droplets were analyzed for phosphorus content using atomic absorption spectrophotometry (Shimadzu atomic absorption spectrophotometer AA-6300). Thirdly, the liquid droplets were titrated for total inorganic acids (Mettler Toledo pH meter Five Easy FE-20). Fourthly, the analysis of the gas phase was carried out by gas chromatography ( Shimadzu G? 2010 Plus).\par
iii. 
\section[{Results and Discussion}]{Results and Discussion}\par
The experimental data on burning of cyanocobalamin are presented in Table \hyperref[tab_0]{1}. As a result, the energies and enthalpies of combustion of riboflavin at T = 298.15K and standard pressure were determined. The values are for the reaction:C 63 H 88 ??N 14 ? 14 ?(cr)+79.75?O 2 (g)?63??O 2 (g)+42.875?? 2 ?(l) + 0.75?CoO(cr) + +0.125?Co 2 P 2 O 7 (cr)+0.75?H 3 PO 4 (sl-n,700? 2 ?)+7?N 2 (g)\par
In brackets are given the physical states of reagents: (cr), crystalline; (g), gaseous; (l), liquid; (sl-n), solution. It should be noted that we have used a significant amount of physico-chemical methods (see section 2.2) in the study of combustion products of cyanocobalamin which is an organometallic compound. The data on the enthalpy of combustion of the crystalline cyanocobalamin was used to estimate enthalpy of combustion and formation at T = 298.15K and p = 0.1MPa (Table \hyperref[tab_1]{2}). Due to the fact that the standard enthalpy of formation of dicobalt diphosphate absent in the literature, we calculated the standard enthalpy and entropy of formation of Co 2 P 2 O 7 at 298.15 K (Table \hyperref[tab_1]{2}). In works \hyperref[b11]{[12,}\hyperref[b12]{13]}, the absolute entropy and the standard Gibbs function of formation of dicobalt diphosphate were determined.\par
The Gibbs function of formation Î?" f G° of the cyanocobalamin was evaluated from the Î?" f H° and Î?" f S° \hyperref[b9]{[10]} values (Table \hyperref[tab_1]{2}). The values conform to the following process:63?C(gr) + 44?H 2 (g) + 7?N 2 (g) + 7?O 2 (g) + Co(cr) + P(cr) ? C 63 H 88 ??N 14 ? 14 ?(cr)\par
where in the brackets are indicated the physical states of reagents: (gr), graphite; (g), gaseous; (cr), crystalline.\par
IV. 
\section[{Conclusions}]{Conclusions}\par
The general aim of these investigations was to report the results of the thermodynamic study of the cyanocobalamin. The standard enthalpy of formation is determined by using combustion calorimetry. Much of the work is devoted to the study of the mechanism of combustion of cyanocobalamin and determination of thermodynamic functions of the combustion products.\par
V. \begin{figure}[htbp]
\noindent\textbf{1} \par 
\begin{longtable}{P{0.3997357992073976\textwidth}P{0.07298546895640687\textwidth}P{0.07410832232496697\textwidth}P{0.08533685601056804\textwidth}P{0.07073976221928666\textwidth}P{0.07298546895640687\textwidth}P{0.07410832232496697\textwidth}}
Value\tabcellsep \tabcellsep \tabcellsep \multicolumn{2}{l}{Experiment}\tabcellsep \tabcellsep \\
\tabcellsep 1\tabcellsep 2\tabcellsep 3\tabcellsep 4\tabcellsep 5\tabcellsep 6\\
m sam (g) a\tabcellsep 0.15345\tabcellsep 0.1600\tabcellsep 0.1466\tabcellsep 0.1580\tabcellsep 0.1595\tabcellsep 0.1607\\
m par (g) a\tabcellsep 0.6920\tabcellsep 0.6989\tabcellsep 0.7024\tabcellsep 0.7021\tabcellsep 0.7050\tabcellsep 0.7059\\
m thread (g) a\tabcellsep 0.0025\tabcellsep 0.0022\tabcellsep 0.00235\tabcellsep 0.00215\tabcellsep 0.0021\tabcellsep 0.0019\\
W (J?K -1 ) b\tabcellsep 14805\tabcellsep 14805\tabcellsep 14805\tabcellsep 14805\tabcellsep 14805\tabcellsep 14805\\
?t (K) c\tabcellsep 2.443105\tabcellsep 2.475455\tabcellsep 2.463935\tabcellsep 2.483210\tabcellsep 2.493200\tabcellsep 2.497915\\
?? ? U ? (J) d\tabcellsep 36170.4\tabcellsep 36649.1\tabcellsep 36478.6\tabcellsep 36763.9\tabcellsep 36911.8\tabcellsep 36981.6\\
?? ? U par (J) e\tabcellsep 32347.1\tabcellsep 32668.2\tabcellsep 32831.8\tabcellsep 32818.7\tabcellsep 32954.3\tabcellsep 32997.3\\
?? ? U thread (J) e\tabcellsep 42.0\tabcellsep 36.5\tabcellsep 39.3\tabcellsep 36.0\tabcellsep 35.6\tabcellsep 32.1\\
?? ? U HNO3 (J) f ?? ? U ? (J) g\tabcellsep 5.9 9.8\tabcellsep 10.5 16.4\tabcellsep 8.2 16.4\tabcellsep 8.8 -\tabcellsep 9.4 26.2\tabcellsep 11.7 26.2\\
?? ? U (J?g -1 ) h\tabcellsep 24666.0\tabcellsep 24689.4\tabcellsep 24663.7\tabcellsep 24686.1\tabcellsep 24694.0\tabcellsep 24683.9\\
\multicolumn{3}{l}{?? ? U = 24681 ± 10 J?g -1 = 33452 ± 14 kJ?mol -1 , the}\tabcellsep \tabcellsep \tabcellsep \tabcellsep \\
\multicolumn{3}{l}{mean energy of combustion of cyanocobalamin, ?? ?}\tabcellsep \tabcellsep \tabcellsep \tabcellsep \\
\multicolumn{3}{l}{°U = 33435 ± 14 kJ?mol -1 , the energy of combustion}\tabcellsep \tabcellsep \tabcellsep \tabcellsep \\
\multicolumn{2}{l}{of cyanocobalamin at standard pressure.}\tabcellsep \tabcellsep \tabcellsep \tabcellsep \tabcellsep \end{longtable} \par
  {\small\itshape [Note: a b W, the energy equivalent of the calorimeter. c ?t, the temperature increase in the experience, adjusted for heat transfer.d h ? ?]} 
\caption{\label{tab_0}Table 1 :}\end{figure}
 \begin{figure}[htbp]
\noindent\textbf{2} \par 
\begin{longtable}{}
\end{longtable} \par
 
\caption{\label{tab_1}Table 2 :}\end{figure}
 		 		\backmatter   			 
\subsection[{Acknowledgements}]{Acknowledgements}\par
The work was performed with the financial support of the Russian Foundation of Basic Research (Project Number 16-03-00288). 			  			  				\begin{bibitemlist}{1}
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\bibitem[Lebedev and Kiparisova ()]{b10}\label{b10} 	 		\textit{},  		 			B V Lebedev 		,  		 			E G Kiparisova 		,  		 			Russ 		.  	 	 		\textit{J. Phys. Chem}  		1996. 70 p. .  	 
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\end{bibitemlist}
 			 		 	 
\end{document}
