Liquid Oxygen

Most of what appears below was taken from the Air Products’ website with its permission.

Information Specific to Liquid Oxygen

General

Oxygen is the second largest component of the atmosphere, comprising 20.8% by volume. Liquid oxygen is pale blue and extremely cold. Although nonflammable, oxygen is a strong oxidizer. Oxygen is necessary to support life. Oxygen will react with nearly all organic materials and metals usually forming an oxide. Materials that burn in air will burn more vigorously in oxygen. Equipment used in oxygen service must meet stringent cleaning requirements and systems must be constructed of materials that have high ignition temperatures and that are non-reactive with oxygen under the service conditions. Vessels should be manufactured to American Society of Mechanical Engineers (ASME) codes and designed to withstand the process temperatures and pressures.

Liquid oxygen is a cryogenic liquid. Cryogenic liquids are liquefied gases that have a normal boiling point below -238°F (-150°C). Liquid oxygen has a boiling point of -297.3°F (-183.0°C). Because the temperature difference between the product and the surrounding environment is substantial—even in the winter—keeping liquid oxygen insulated from the surrounding heat is essential. The product also requires special equipment for handling and storage. Oxygen is often stored as a liquid, although it is used primarily as a gas. Liquid storage is less bulky and less costly than the equivalent capacity of high-pressure gaseous storage.

A typical storage system consists of a cryogenic storage tank, one or more vaporizers, a pressure control system, and all piping necessary for the fill, vaporization, and supply functions. The cryogenic tank is constructed, in principle, like a thermos bottle. There is an inner vessel surrounded by an outer vessel. Between the vessels is an annular space that contains an insulating medium, from which all the air has been removed. This space keeps heat away from the liquid oxygen held in the inner vessel. Vaporizers convert the liquid oxygen into a gaseous state. A pressure control manifold then controls the gas pressure that is fed to the process or application. Vessels used in liquid oxygen service should be designed according to ASME codes for the pressure and temperatures involved. Piping design should follow similar codes, as issued by the American National Standards Institute (ANSI).

Health Effects

Normally air contains 21% oxygen and oxygen is essentially nontoxic. No health effects have been observed in people exposed to concentrations up to 50% at 1 atmosphere for 24 hours or longer. The inhalation at 1 atmosphere of 80% oxygen for more than 12 hours can cause irritation of the respiratory tract, progressive decrease in vital capacity, coughing, nasal stuffiness, sore throat, and chest pain, followed by tracheobronchitis and later by pulmonary congestion and/or edema. Inhalation of pure oxygen at atmospheric pressure or less can cause pulmonary irritation and edema after 24 hours. Respiratory symptoms can occur in two to six hours at pressures above 1 atmosphere. One of the earliest responses of the lung is accumulation of water in its interstitial spaces and within the pulmonary cells. This can cause reduced lung function, which is the earliest measurable sign of toxicity.

Other symptoms include fever, and sinus and eye irritation. When pure oxygen is inhaled at pressures greater than 2 or 3 atmospheres, a characteristic neurological syndrome can be observed. Signs and symptoms include nausea, dizziness, vomiting, tiredness, light-headedness, mood changes, euphoria, confusion, incoordination, muscular twitching, burning/ tingling sensations particularly of the fingers and toes, and loss of consciousness. Characteristic epileptic-like convulsions, which may be preceded by visual disturbances, such as loss of peripheral vision, also occur. Continued exposure can cause severe convulsions that can lead to death. The effects are reversible after reduction of oxygen pressure.

Premature infants placed in incubators to breathe oxygen in concentrations greater than in air can develop irreversible eye damage. Within six hours after an infant is placed in a high-oxygen atmosphere, vasoconstriction of the immature vessels of the retina occurs, which is reversible if the child is immediately returned to air, but irreversible if oxygen-rich therapy is continued. Fully developed blood vessels are not sensitive to oxygen toxicity. Extensive tissue damage or cryogenic burns can result from exposure to liquid oxygen or cold oxygen vapors.

Physical Properties

  • Molecular Formula: O2
  • Molecular Weight: 31.999
  • Boiling Point @ 1 atm: -297.4°F (-183.0°C, 90oK)
  • Freezing Point @ 1 atm: -361.9°F (-218.8°C, 54oK)
  • Critical Temperature: -181.8°F (-118.4°C)
  • Critical Pressure: 729.1 psia (49.6 atm)
  • Density, Liquid @ BP, 1 atm: 71.23 lb/scf
  • Density, Gas @ 68°F (20°C), 1 atm: 0.0831 lb/scf
  • Specific Gravity, Gas (air=1) @ 68°F (20°C), 1 atm: 1.11
  • Specific Gravity, Liquid (water=1) @ 68°F (20°C), 1 atm: 1.14
  • Specific Volume @ 68°F (20°C), 1 atm: 12.08 scf/lb
  • Latent Heat of Vaporization: 2934 BTU/lb mole
  • Expansion Ratio, Liquid to Gas, BP to 68°F (20°C): 1 to 860
  • Solubility in Water @ 77°F (25°C), 1 atm: 3.16% by volume

Containers

A typical cryogenic liquid cylinder is depicted below. This is an insulated, vacuum-jacketed, pressure vessel. They are equipped with pressure-relief valves and rupture disks to protect the cylinders from pressure build-up. Liquid containers operate at pressures up to 350 psig and have capacities between 80 and 450 liters of liquid. Oxygen may be withdrawn as a gas by passing liquid through an internal vaporizer or as a liquid under its own vapor pressure.

Cryo_LN2

Safety Considerations

The hazards associated with liquid oxygen are exposure to cold temperatures that can cause severe burns; over-pressurization due to expansion of small amounts of liquid into large volumes of gas in inadequately vented equipment; oxygen enrichment of the surrounding atmosphere; and the possibility of a combustion reaction if the oxygen is permitted to contact a non-compatible material. The low temperature of liquid oxygen and the vapors it releases not only pose a serious burn hazard to human tissue, but can also cause many materials of construction to lose their strength and become brittle enough to shatter. The large expansion ratio of liquid-to-gas can rapidly build pressure in systems where liquid can be trapped. This necessitates that these areas be identified and protected with pressure relief. This expansion ratio also allows atmospheres of oxygen-enriched air to form in the area surrounding a release.

It is important to note that fire chemistry starts to change when the concentration of oxygen increases to as little as 23%. Materials easily ignited in air not only become more susceptible to ignition, but also burn with added violence in the presence of oxygen. These materials include clothing and hair, which have air spaces that readily trap the oxygen. Oxygen levels of 23% can be reached very quickly and all personnel must be aware of the hazard. Any clothing that has been splashed or soaked with liquid oxygen or exposed to high oxygen concentrations should be removed immediately and aired for at least an hour. Personnel should stay in a well-ventilated area and avoid any source of ignition until their clothing is completely free of any excess oxygen. Clothing saturated with oxygen is readily ignitable and will burn vigorously.

Do not permit smoking or open flames in any areas where liquid oxygen is stored or handled. Do not permit liquid oxygen or oxygen-enriched air to come in contact with organic materials or flammable or combustible substances of any kind. Some of the organic materials that can react violently with oxygen when ignited by a spark or even a mechanical shock are oil, grease, asphalt, kerosene, cloth, tar, and dirt that may contain oil or grease. If liquid oxygen spills on asphalt or other surfaces contaminated with combustibles, do not walk on or roll equipment over the area of the spill. Keep sources of ignition away for 30 minutes after all frost or fog has disappeared.

Systems used in oxygen service must meet stringent cleaning requirements to eliminate any incompatible contaminants. The Compressed Gas Association’s (CGA’s) Pamphlet G-4.1, “Cleaning Equipment for Oxygen Service,” describes cleaning methods for equipment used in oxygen service. CGA’s Pamphlet O2-DIR, “Directory of Cleaning Agents for Oxygen Service,” provides comparative information on cleaning agents used to clean oxygen equipment. Also, review the Material Safety Data Sheet (MSDS) and follow all recommendations.

Handling and Storage

Store and use liquid oxygen with adequate ventilation. Do not store in a confined space.

Cryogenic containers are equipped with pressure-relief devices to control internal pressure. Under normal conditions these containers will periodically vent product. Do not plug, remove, or tamper with any pressure-relief device.

Where outside storage is used, provide for protection against the extremes of weather.

Oxygen must be separated from flammables and combustibles by 20 feet or a half-hour fire wall. Post “No Smoking” and “No Open Flames” signs.

Customer storage sites having a capacity of more than 20,000 scf must be installed in accordance with the National Fire Protection Association (NFPA) Standard 50.

Use only oxygen compatible lubricants.

Personal Protective Equipment (PPE)

One must be thoroughly familiar with the properties and safety considerations before handling a cryogenic liquid and its associated equipment. The eyes are the most sensitive body part to the extreme cold of the liquid and vapors of cryogenic liquids. The recommended personal protective equipment for handling cryogens includes a full face shield over safety glasses, loose-fitting thermal insulated or leather gloves, long sleeve shirts, and trousers without cuffs. In addition, safety shoes are recommended for people involved in the handling of containers. Depending on the application, special clothing suitable for that application may be advisable.

A special note on insulated gloves: Gloves should be loose-fitting so they are able to be quickly removed if cryogenic liquid is spilled on them. Insulated gloves are not made to permit the hands to be put into a cryogenic liquid. They will only provide short-term protection from accidental contact with the liquid. In emergency situations, self-contained breathing apparatus (SCBA) may be required.