bottle, but they add to the cost of the finished package and that brings up the question of economics in the highly competitive toiletry goods market. How far will the manufacturers be willing to go in absorbing the cost of extra protection, or how much extra will the consumer be willing t o pay? There is a question, too, of safety regulations, for if manufacturers do not provide a n absolutely safe package, state or federal agencies, such as the Federal Trade Commission, may step into the picture and set up standards. Plastic Containers. Plastic containers are a n even newer development. Although they have not yet been tested on the consumer market, many think they provide the answer t o some of the fears of breakage in the glass container. Plastic and glass containers find greatest application in packages of 2 to 6 ounces. Polyethylene materials, such as those used in squeeze-type plastic dispenser packages, would be ideal, but present indications are t h a t they are permeable to fluorinated hydrocarbon propellents and, therefore, would not be satisfactory for retaining these under pressure. Valves. Valves constitute another part of the aerosol industry’s problems, and much work remains t o be done on improving the spray pattern and freedom from clogging. A fine spray requires a fine valve orifice and places a limit on particle
size of the active ingredient. The first commercially produced valves cost more than double the present prices. The presentday valve is a more accurately made product and almost any desired spray pattern may be obtained. Some of the many valves available today for use in aerosol containers are pictured in Figure 6. Research is going ahead in both the container and valve fields t o develop more corrosion-resistant containers, safer containers, and better and more efficient valves with a wider range of usefulness. Problems are being solved every day and members of the aerosol industry are confident that, given time, no problem is insurmountable. ACKNOWLEDGMENT
The assistance of Frank Zumbro, Kinetic Chemicals Division, E. I. du Pont de Kemours & Co., Inc., John D . Conner, CSRfA counsel, and many others in the Aerosol Division of the Chemical Specialties Manufacturers Association, who contributed photographs and material for this presentation, is gratefully acknowledged. RECEIVED for review October 15, 1954.
ACCEPTEDMarch 25, 1955.
precautionary Labeling of
Hazardous Chemicals Active work is continuing, with Government and industry cooperating, to develop and make effective and uniform labeling of hazardous chemicals.
R. D. MINTEER Monsanto Chemical Co., St. Louis, M o .
P
OSSIBLY the least understood part of the business of pro-
ducing, transporting, and handling of chemicals is the part played by precautionary labeling. The need for warning labels was recognized many years ago. Introduction in Congress of the Bingham Act, in 1932, caused a vigorous awakening on the part of the chemical industry. As a result, a permanent committee was organized to work out with the Surgeon General of the United States a series of agreements between the manufacturers of some 8 or 10 chemical products and the Surgeon General’s office, whereby the manufacturers voluntarily agreed to affix a warning label on all shipments of these products from the manufacturer’s plant. The texts of the various labels were worked out by the committee and representatives of the Surgeon General’s office. These agreements, entered into early in 1934, were kept until 1952, when they mere discontinued as a result of the introduction of a large number of new, and in many cases hazardous, products not covered by the agreements, and the existence of the Manufacturing Chemists’ Association labeling principles (on which study was begun in 1944 by MCh’s Labeling and Precautionary Information Committee), which were considered to provide for more appropriate warning labels. The U. S. Public Health Service has recently reactivated the Chemical Products Agreement Committee to work with the Manufacturing Chemists’ Association in a continual evaluation of labeling requirements. The objectives of the labeling committee were largely attained with the development of the warning label program and the pub-
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lishing of the first manual. The manual has been through three revisions, the latest published in 1953. Industry voluntarily adopted the program to a remarkable degree, and it was felt t h a t this would forestall state and federal ordinances requiring warning labels. However, this has not been the case. STATE REGULATIONS
The California Division of Industrial Safety determined t o publish a regulation setting forth labels which must be placed on every container of hazardous chemicals to be used in t h a t state. A great deal of correspondence was carried on between t h e Manufacturing Chemists’ Association and the state of California in a n endeavor to have this California regulation correspond t o LAPI principles. An agreement was reached, and LAPI labels were accepted by California. Oregon soon followed suit, but, instead of publishing a list of required labels, simply stated t h a t labels as set forth in the M C S manual mould be acceptable. I n 1948 the Federal Insecticide, Fungicide, and Rodenticide Act was passed, which required, among other things, t h a t labels for economic poisons should contain warning statements to protect the users of these substances. The LAPI Committee worked closely with the U. S. Department of Agriculture, with the result that regulations published under the above law required warning labels which correspond closely with LAPI principles. After the Federal Insecticide, Fungicide, and Rodenticide Act was passed, msny states revised old laws or passed new ones which closely followed the federal pattern, with the result
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 47, NO. 6
’
.,
I
Handling of Chemicals that warning labels for agricultural pesticides are uniform throughout the United States. Although the Manufacturing Chemists’ Sssociation program is directed primarily t o the labeling of industrial chemicals, the principles are generally applicable t o small package labeling and experimental samples. However, as the repackaging of chemicals into smaller units was beyond the control of the manufacturing industry and because accidents occurred from the misuse of chemicals in these small packages, state agencies became somewhat alarmed and began to consider regulations which would require labels on packages of all sizes. Accidents arising from the handling of paint removers led Illinois t o follow in the footsteps of California and Oregon. I n June 1961, Illinois passed a regulation requiring warning labeling on all containers of hazardous chemicals. Members of the LAPI Committee met with representatives from the state of Illinois. with the result t h a t LAPI principles were adopted. The Illinois regulation copies P a r t I of the %IC4 manual. I n the past 2 years several states have expressed the desire to draft a similar regulation controlling labeling of hazardous chemicals. It became apparent t h a t industry’s voluntary use of precautionary labeling of industrial chemicals would not be sufficient t o forestall state legislation. It m,s felt t h a t the next best thing would be t o lend LAPI Committee efforts t o help the states draft uniform regulations. The International Association of Governmental Labor Officials formed a labeling conmittee, and in conjunction with the MCA group, worked out a set of model regulations to be presented at the next association meeting for use by states considering labeling regulations.
The state of New Jersey, Department of Labor and Industry, has just issued a new regulation relating to the labeling of harmful substances, which has been patterned after this proposed model bill. Future state regulations relating t o labeling of hazardous substances will probably follow this IAGLO model. The state of New York passed a labeling code which took effect August 27, 1954. The New York regulations were worked out by the manufacturers of t h e MCA committee and the New York State Department of Public Health. A committee of the Chemical Specialties Manufacturers Association is working on the labeling of household products and ways of applying the MCA principles. Directions for use are usually a n important addition for small packages. The Chemical Specialties Manufacturers Association committee released its first paper early in July. This association has also lent its assistance to the state of Kew York in the preparation of the labeling code and t o the International Association of Governmental Labor Officials in the preparation of its model regulations. Much work remains to be done, and this will be a continuing task of this committee. EDUCATIKG THE PUBLIC
There still remains a n important task, t h a t of educating the public to understand the significance of warning labels and teaching them t o read the label. I n this task of education, help is needed. The Manufacturing Chemists’ Association appeals t o all members of the chemical industry and their trade associations for suggestions as to how this might best be accomplished. RECEIVED for review October 1.3, 1954.
-4CCEPTED
March 25, 1956.
END OF SYMPOSIUM
I
TO IMPROVE YllELDS
1
in the Raschig synthesis of hydrazine
II
. . , gelatin three substitutes for as a metal deactivator are proposed
1I
Metal Deactivators in Synthesis of Hydrazine R.
F.SkVFTNER, 33. AI. JONES,
T
I
HE development of new potential markets requiring substantial quantities of hydrazine and hydrazine derivatives has been accompanied by intensive research designed not only t o explore new synthetic approaches t o this most versatile chemical commodity, but al-o to develop and improve the Raschig synthesis ( 2 , $0) making use of ammonia, chlorine, and caustic as raw materials. Chloramine is, however, the important reactant since it is produced as the intermediate from hypochlorite and ammonia, Equation 1, and then reacts under proper conditions to give hydrazine, Equation 2 . However, a side reaction, represented by Equation 3, may also take place t o reduce the yield of hydrazine.
+ SaOCl + KaOH + NH, 2NH2Cl + N2Ha
XH3 SH&1
+
+ NH&1 + NaCl + + 2XH4Cl
XaOH
+ S2H4 -+
A-2
(1) H20
(2)
(3)
It has been shown t h a t the hydrazine-chloramine reaction, Equation 3, is catalyzed by trace quantities of certain metal ions (IO),most markedly, however, by dissolved copper. To obtain satisfactory yields of hydrazine it is necessary t o add t o the makeu p solution a small quantity of gelatin or glue which serves as a metal deactivator. June 1955
AND L.
F. AUDRIETH
Uniuersity of Illinois, Urbana, I l l .
Earlier work designed t o develop, somewhat empirically, substitutes for gelatin is widely scattered in the literature; published information is summarized in Table I. This classification is based on the claimed effectiveness of these substances as inhibitors and represents a personal evaluation of the published data by the authors. The present investigation was undertaken with two major objectives in mind: 1. To develop possible substitutes for gelatin since the use of gelatin causes excessive foaming e~peciallyin the distillation of hydrazine from t h e salt solution which constitutes t h e product synthesis liquor 2 . T o arrive a t a more precise understanding of t h e role t h a t gelatin and other inhibitors play in the Raschig synthesis
A standard procedure was developed t o test the efficiency of a wide variety of possible metal deactivators. Complexing agents, coprecipitants, and polysaccharide derivatives were evaluated. High molecular weight proteins were in general the most effective, although a number of simple amino acids and polypeptides approached the natural products in their usefulness as metal deactivators. Experimental data indicate that those amino acids, that contain a multiplicity of sites for coordination
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