Hydrogen Peroxide and Its Analogues: Iv. Some Thermal Properties of Hydrogen Peroxide

Foley, William T.; Giguère, Paul A.

doi:10.1139/v51-104

Cited by 21 publications

(11 citation statements)

References 7 publications

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“…T h e present results for the heat of fusion and the triple point of hydrogen peroxide lie outside the limits of error assigned by Foley and Gig~16re for their determinations (4,5). Because the experimental method ~ised this time was nl~ich more accurate there is no q~lestion that the new values are to be preferred.…”

Section: The Ileat Of Fusionsupporting

confidence: 45%

“…Knowledge of the thermal properties of solid hydrogen peroxide has hitherto been fragmentary and uncertain (15,5). The accurate determination of the heat capacity of the compound in the solid state down to low temperatures was considered to be of special interest, primarily because it would make possible a calculation of the third law entropy.…”

Section: Introductionmentioning

confidence: 99%

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Hydrogen Peroxide: The Low Temperature Heat Capacity of the Solid and the Third Law Entropy

Giguère¹,

Liu²,

Dugdale³

et al. 1954

Can. J. Chem.

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The heat capacity of crystalline hydrogen peroxide between 12" I<. and the melting point has been determined with a low temperature adiabatic calorimeter. T h e heat of fusion was also measured and found to be 2987 f 3 cal./mole.The two samples of hydrogen peroxide used were 99.97 mole % pure as deduced from behavior on melting and from premelting heat capacities; the triple point was estimated to be 272.74" I<.The only anomaly observed it1 the heat capacity measuren~ents was the absorption of 1.3 cal./mole a t 216.8 f 0.15" K., the lower eutectic temperature of H20-Hg02 solutions. Such an effect is to be expected if the only significant impurity is water. The entropy of hydrogen peroxide as an ideal gas a t 1 atm. pressure and 25" C. computed from the thermal measurements is 55.76 f 0.12 cal./mole deg. Comparison of this datum with the recalculated statistical entropy leads to a value of 3.5 kcal./mole for the height of a hypothetical single barrier hindering internal rotation in the molecule. From these results it is concl~~ded that hydrogen peroxide does not consist of two tauton~eric modifications.

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Section: The Ileat Of Fusionsupporting

confidence: 45%

Section: Introductionmentioning

confidence: 99%

Hydrogen Peroxide: The Low Temperature Heat Capacity of the Solid and the Third Law Entropy

Giguère¹,

Liu²,

Dugdale³

et al. 1954

Can. J. Chem.

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“…The properties of H 2 O 2 have been extensively studied because of its importance. Available experimental data include crystal structures, ,− vibrational spectra, − vapor pressure, density and viscosity, , heat of vaporization, , and heat capacity . Aqueous H 2 O 2 solutions also have been investigated experimentally, and crystal structure, vapor pressure, density, ,, and freezing point measurements have been reported but these have been limited to temperatures below 100 °C due to the dangers associated with explosions above 150 °C …”

Section: Introductionmentioning

confidence: 99%

A Simple Additive Potential Model for Simulating Hydrogen Peroxide in Chemical and Biological Systems

Orabi

English

2018

J. Chem. Theory Comput.

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Hydrogen peroxide (HO) has numerous industrial, environmental, medical, cosmetic, and biological applications. Given its importance, we provide a simple model as an alternative to experiment for studying the properties of pure liquid HO and its concentrated aqueous solutions, which are hazardous, and for understanding the biological roles of HO at the molecular level. A four-site additive model is calibrated for HO based on the ab initio and experimental properties of the gaseous monomer and the density and heat of vaporization of liquid HO at 0 °C. Our model together with the TIP3P water model reproduce the ab initio binding energies of (HO) , HO· nHO, and nHO·HO clusters ( m = 2, 3 and n = 1, 2) calculated at the MP2 level using the 6-311++G(d,p) or the 6-311++G(3df,3pd) basis set. It yields structure, the self-diffusion coefficient, heat capacity, and densities at temperatures up to 200 °C of the pure liquid in good agreement with experiment. The model correctly predicts the hydration free energy of HO and reproduces the experimental density of aqueous HO solutions at 0-96 °C. Investigation of the solvation of HO and HO in aqueous HO solutions reveals that, as in the gas phase, HO is a better H-bond donor but poorer acceptor than HO and the bonding stability follows the order O-H···O > O-H···O ≥ O-H···O > O-H···O. Stronger H-bonding in HO/HO mixtures than in the pure liquids is consistent with exothermic heats of mixing and explains why the observed density and vapor pressure of the aqueous solutions are higher and lower, respectively, than expected from ideal mixing. Results also show that HO adopts a skewed equilibrium geometry in gas and liquid phases but more polar cis and nonpolar trans conformations also are accessible and will stabilize HO in environments of different polarity. In sum, our simple model presents a reliable tool for simulating HO in chemistry and biology.

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“…For the saturated H 2 O 2 amount, we calculate the vapor pressure using the Clausius-Clapeyron equation. Then, we use the thermal properties of H 2 O 2 (Foley & Giguére 1951a) and its saturation vapor pressure of 4.69 × 10 −4 bar at the melting point (272.69 K) as a reference pressure (Manatt & Manatt 2004). In the other cases, the molar fraction of H 2 O 2 is assumed to be vertically constant and its value was in the range from 10 ppb to 10 ppm.…”

Section: Atmospheric Modelmentioning

confidence: 99%

H₂O₂-induced Greenhouse Warming on Oxidized Early Mars

Itō

Hashimoto

Takahashi

et al. 2020

ApJ

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The existence of liquid water within an oxidized environment on early Mars has been inferred by the Mn-rich rocks found during recent explorations on Mars. The oxidized atmosphere implied by the Mn-rich rocks would basically be comprised of CO 2 and H 2 O without any reduced greenhouse gases such as H 2 and CH 4. So far, however, it has been thought that early Mars could not have been warm enough to sustain water in liquid form without the presence of reduced greenhouse gases. Here, we propose that H 2 O 2 could have been the gas responsible for warming the surface of the oxidized early Mars. Our one-dimensional atmospheric model shows that only 1 ppm of H 2 O 2 is enough to warm the planetary surface because of its strong absorption at far-infrared wavelengths, in which the surface temperature could have reached over 273K for a CO 2 atmosphere with a pressure of 3bar. A wet and oxidized atmosphere is expected to maintain sufficient quantities of H 2 O 2 gas in its upper atmosphere due to its rapid photochemical production in slow condensation conditions. Our results demonstrate that a warm and wet environment could have been maintained on an oxidized early Mars, thereby suggesting that there may be connections between its ancient atmospheric redox state and possible aqueous environment.

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Hydrogen Peroxide and Its Analogues: Iv. Some Thermal Properties of Hydrogen Peroxide

Cited by 21 publications

References 7 publications

Hydrogen Peroxide: The Low Temperature Heat Capacity of the Solid and the Third Law Entropy

Hydrogen Peroxide: The Low Temperature Heat Capacity of the Solid and the Third Law Entropy

A Simple Additive Potential Model for Simulating Hydrogen Peroxide in Chemical and Biological Systems

H₂O₂-induced Greenhouse Warming on Oxidized Early Mars

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Hydrogen Peroxide and Its Analogues: Iv. Some Thermal Properties of Hydrogen Peroxide

Cited by 21 publications

References 7 publications

Hydrogen Peroxide: The Low Temperature Heat Capacity of the Solid and the Third Law Entropy

Hydrogen Peroxide: The Low Temperature Heat Capacity of the Solid and the Third Law Entropy

A Simple Additive Potential Model for Simulating Hydrogen Peroxide in Chemical and Biological Systems

H2O2-induced Greenhouse Warming on Oxidized Early Mars

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Product

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H₂O₂-induced Greenhouse Warming on Oxidized Early Mars