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Phase Properties of Hydrogen Peroxide

hydrogen peroxide Propulsion

Part of the Hydrogen Peroxide Propulsion Guide

Those properties of hydrogen peroxide,which are associated with one particular phase (either solid, liquid, or gas) have been grouped as phase properties.


A density of 1.70 gm/cc (106.76 lb/cu ft) was computed for solid 100-percent H2O2 from X-ray diffraction measurements (Ref. 5) at -20 C (-4 F). Density measurements on H2O2-H2O solutions during cooling and freezing (Ref. 6) indicated that true solid solutions of H2O2 and H2O were not formed; this was later verified in Ref. 1. Since the occlusion of the mother liquor occurred in freezing, the measured densities were a function of the freezing technique. However, it was noted (Ref. 6) that solutions containing < 45 w/o H2O2 expand during freezing and solutions > 65 w/o H2O2 contract during freezing.

Experimental determinations of the liquid densities of various H2O2-H2O solutions were reported as a function of composition in Ref. 2.6 (at 0 and 18 C), Ref. 6 (at 0 C), Ref. 7 (at 20 c), and Ref. 2.17 (at 0, 10, 25, 50, and 96 C). In addition, experimental studies have determined the density of 90 w/o H2O2 from 76 to 193 C (Ref. 8), and the density of 98 w/o H2O2 from 27 to 105 C (Ref. 9). The data from these six studies were simultaneously curve fitted by a least-squares computer program, and the following equation was found to adequately (actual deviation for each experimental point was < 0.002 gm/cc) describe the data from 0 to 193 C (32 to 379 F) over a concentration range of 60 to 100 w/o H2O2.

Ρ(gm/cc) = 1.0479 + 2.455 x 10-3W + 1.781 x 10-5W2 - 6.76 x 10-4 T(C) - 2.4 x 10-7T(C) 2 -3.98 x 10-6WT(C)

where W is weight percent H2O2.

Converting to English units, this equation becomes:

Ρ(lb/cu ft) = 66.166 + 1.577 x 10-1W + 1.112 x 10-3W2 - 2.31 x  10-2 T(F) - 4.7 x 10-6T(F)2 -1.38 x 10-4WT(F)

The curves described by these equations are graphically illustrated for propellant-grade H2O2 solutions in Fig. 2.4 and 2.4a, respectively.

Experimental vapor density measurements (Ref. 2) at 92 C (165.6 F) show that H2O2 is not associated in the vapor state. If it is assumed that no decomposition occurs, the vapor density may be calculated through use of the perfect gas law.

Coefficient of Thermal Expansion

Using the curve fits of the density data, the coefficients (cubicle) of thermal expansion were calculated for propellant-grade H2O2-H2O solutions from 0 to 100 C (32 to 212 F) through the following relationship.

ɑ = l/V (δV/δt)Ρ

Curve fits of these calculations are presented in Fig. 2.5 and 2.5a.


The adiabatic compressibilities of H2O2 solutions were calculated (Ref. 7) from experimental density and sonic velocity data covering a temperature range of 3.5 to to 33.5 C (38.3 to 92.3 F) and a concentration range of 0 to 93.4 m/o (0 to 96.5 w/o). These data were used to plot the adiabatic compressibilities of propellant-grade H2O2 solutions shown in Fig. 2.6 and 2.6a.

Although no experimental data have been reported on the isothermal compressibility of H2O2, the adiabatic compressibility density, and heat capacity data were used to calculate (Ref. 7) an isothermal compressibility of 26.514 x 10-12 cm2/dyne

(26.865 x 10-6 atm-1 , 18.281 x 10-5 psia-1) for 100 w/o H2O2 at 20 C (68 F).

Vapor Pressure

The vapor pressure data resulting from four different experimental measurements (Ref. 3, 4, Ref. 9, and Ref. 11) on various aqueous solutions of H2O2 over temperature ranges of 0 to 90 C (32 to 194 F) have been correlated. Using a least squares curve-fit computer program, these data were curve-fitted with the following equations (in the metric system):

100 w/o H2O2 log P (mm Hg)= 8.92536-282.60/T(K) -24675/T(K)2

98 w/o H2O2 log P(mm Hg)= 7.89728-1797.84/T(K) -134089/T(K)2

95 w/o H2O2 log P(mm Hg)= 7.68235- 1647.17/T(K) -154665/T(K)2

90 w/o H2O2 log P(mm Hg)= 7.67297- 1606.47/T(K) -157563/T(K)2

75 w/o H2O2 log P(mm Hg)= 7.39108- 1351.86/T(K) -185863/T(K)2

70 w/o H2O2 log P(mm Hg) -7.42560- 1354.10/T(K) -181798/T(K)2

Converting these equations to English units resulted in the following:

100 w/o H2O2 log P(psia) = 7.21175 - 4468.68/T(R) -79947/T(R)2

98 w/o H2O2 log P(psia) = 6.18367 - 3236.11/T(R) -434448/T(R)2

 95 w/o H2O2 log P(psia) = 5.96874 - 2964.91/T(R) -501115/T(R)2

90 w/o H2O2 log P(psia) = 5.95936 - 2891.65/T(R) -510504/T(R)2

75 w/o H2O2 log P(psia) = 5.67747 - 2433.35/T(R) -602196/T(R)2

70 w/o H2O2 log P(psia) = 5.71199 - 2437.38/T(R) -589026/T(R)2

The equations are illustrated graphically in Fig. 2.7 and 2.7a, where the data are extrapolated to temperatures above 90 C (194 F) by assuming a linear relationship between the temperatures for which H2O2 solutions and water have the same vapor pressures. These extrapolations were used to determine the pseudo-boiling points (the temperatures where the pressures are equivalent to 760 mm Hg) of the propellant-grade H2O2 mixtures.

Vapor-Liquid Equilibrium

Vapor-liquid equilibrium compositions of H2O2-H2O solutions were determined experimentally in two different studies (Ref. 4 and Ref. 11). Although comparable, there are slight differences in the data at some of the temperatures. The data of Ref 4 were used in Ref. 12 to plot vapor composition and vapor-liquid equilibrium, and to calculate and plot activity coefficients for the system. These plots are shown in Fig. 2.8 through 2.10.

Calculations (Ref. 13) of saturation pressure, activity coefficients, and vapor compositions have been made for three different H2O2-H2O solutions (90, 81.5, and 65.4 w/o) at high temperatures and pressures. The computation of these data, which are shown in Table 2.2, are described in detail in Ref. 13. Although these computations were based on assumptions of H2O2 critical constants that are different (critical temperature = 457 C, critical pressure = 215 atmosphere) from the values recommended in this handbook, corrections to Table 2.2 are slight.

Surface Tension

The surface tensions of H2O2-H2O solutions have been experimentally determined (Ref. 14) as a function of composition at 0 C (32 F) and 20 C (68 F). Graphical representations of the data are shown in Fig. 2.11 and 2.11a.



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  4. Scatchard, G., G. M. Kavanagh, and L. B. Tickner, “Vapor-Liquid Equilibrium. VIII. Hydrogen Peroxide-Water Mixtures,” J. Am. Chem. Soc., 74, 3715-20 (1952).

  5. Abrahams, S. C., R. L. Collin, and W. N. Lipscomb, The Crystal Structure of Hydrogen Peroxide,” Acta Cryst., 4, 15-20 (1951).

  6. Giguere, P. A. and Pierre Geoffrion, “Changes of Density of Hydrogen Peroxide Solutions on Cooling and Freezing,” Can. J. Research, 28B, 599-607 (1950).

  7. Papousek, D., “intermolecular Interaction in Liquids. I. Adiabatic Compressibility and Structure in the System Hydrogen Peroxide,” Chem. Listy, 59 1781-6 (1957).

  8. R-2094P, Summary Report, Research Program on H2O2  , Rocketdyne, a Division of North American Aviation, Inc., Canoga Park, California, March 1, 1960, CONFIDENTIAL.

  9. AFRPL-TR-66-6, Final Report, Advanced Propellant Staged Combustion Feasibility Program, Phase I, Part 2, Aerojet-General Corporation, Sacramento, California, April 1966, CONFIDENTIAL.

  10. Egerton, A. C., W. Emte, and G. J. Minkoff, “Some Properties of Organic Peroxides,” Discussions Faraday Society, 1951 (10), 278-82 (1951).

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  12. Bulletin No. 67, Hydrogen Peroxide Physical Properties Data Book, FMC Corporation, Buffalo, New York, 1955.

  13. 290-63, Hydrogen Peroxide Decomposition. I, Shell Development Company, Emeryville, California, January 1964.

  14. Phibbs, M. K. and P. A. Giguere, “Hydrogen Peroxide and Its Analogues. I. Density, Refractive Index, Viscosity, and Surface Tension of Deuterium Oxide Solutions,” Can. J. Chem., 29, 173-31 (1951).

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