Part of the Hydrogen Peroxide Propulsion Guide
The storability (or storage stability) of hydrogen peroxide is usually described in terms of decomposition rate and/or concentration change of the H2O2 over a period of time. Because storability is directly related to decomposition, it becomes a function of the considerations involved in the decomposition mechanisms. In a simplification of these mechanisms, which are described in detail in Section 7, the basic factors controlling decomposition rate in a storage system are H2O2 concentration; temperature; impurity types and concentrations in the H2O2; and the composition, area, and condition of the surface in contact with the H2O2. Although many of these factors are discussed in other sections of this handbook as a result of studies of materials compatibility, passivation techniques, decomposition mechanisms, etc., they are interrelated and presented in this section in terms of storability.
Until the early 1960's, the generally accepted decomposition rate AOL* of commercial, unstabilized, propellant-grade hydrogen peroxide under normal storage conditions (e.g., in a 30-gallon storage drum at an S/V of 0.38 in.-1) was ~1 percent/year at ambient temperatures of 77 to 86 F (Ref. 1). This rate is theoretically equivalent to a propellant-grade hydrogen peroxide concentration loss of ~0.5 w/o H2O2/year. Some examples of decomposition rates actually experienced during drum storage (under field handling conditions) of various types of peroxide between 1945 and 1963 are shown in Table 4.1 in terms of concentration changes and actual oxygen loss. These results, which are essentially representative of propellant manufactured before 1960 and of storage at the S/V (0.38 in.-1) typically found in 30-gallon storage drums, were reported in Ref. 2.
*.AOL (active oxygen loss) is defined in Section 126.96.36.199.4.
There are some discrepancies noted in Table 4.1 between the reported oxygen losses and the H2O2 concentration changes. It would appear that if the magnitudes of the reported H2O2 concentration charges were entirely attributable to H2O2 decomposition, the oxygen losses would be much higher. Although it is possible that some of the H2O2 concentration change during the storage period was due to moisture absorption from the air (during drum "breathing"), the discrepancies do cause some doubt in the validity of the oxygen losses reported. Because the technique for determination of oxygen loss is not reported, and it is assumed that such a measurement would be difficult under the uncontrolled conditions of drum storage, the concentration change appears to be the most indicative factor of decomposition rate during these tests.
From the H2O2 concentration changes reported in Table 4.1, the decomposition rate of the unstabilized 90 w/o H2O2 can be estimated as approximately 1-percent AOL/year which corresponds to that rate generally accepted by the industry during this period. The data presented in the table also indicate smaller decomposition rates for both the 98 w/o H2O2 propulsion grade and the stabilized torpedo grades (90 and 70 w/o 1202) under essentially the same storage conditions. These effects are discussed further in Sections 188.8.131.52 and 184.108.40.206.
Recently, improvements have been reported in the storage stability of hydrogen peroxide, particularly, in the 90 w/o grade. The gross result of this improvement is illustrated in Table 4.2 with data from studies conducted in 1947 (Ref. 3) and in 1965 (Ref. 1 and Ref. 4) on 90 w/o H2O2 and studies on 99+ w/o H2O2 in 1953 (Ref. 5). In this table the rate of decomposition of the hydrogen peroxide has been reported as a function of temperature and as a function of contamination for the three different time periods. Although the reasons for the improvement in hydrogen peroxide stability are not defined in Table 4.2, the data are indicative of the progress that has been made in the storability of hydrogen peroxide.
Shell Development Company, Emeryville, California, Concentrated Storable Hydrogen Peroxide, Report No. S-13974, Report period: May 1964 - August 1965, Contract DA-04-200-AMC-569(Z).
McCormick, James C., F.M.C. Corporation, Buffalo, New York, Hydrogen Peroxide Rocket Manual, 1965.
Shanley, E. S. and F. P. Greenspan, “Highly Concentrated Hydrogen Peroxide - Physical and Chemical Properties,” Ind. Eng. Chem., 39 1536-43(1947).
LTV Astronautics Division, Dallas, Texas, Peroxide Contamination Study, Final Summary Report, Report No. ER 23.210, 30 April 1965.
- Roth, E. M., Jr., and E. S. Shanley, “Stability of Pure Hydrogen Peroxide,” Ind. Eng. Chem., 45, 2343-9 (1953).