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    Ammonium Carbamate

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    Michely Carvalho

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    Ammonium Carbamate

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    ammonium-carbamate

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    Ammonium Carbamate

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    of 2

    Inorganic Syntheses, VolumeI1

    Edited by W Conard Fernelius


    Copyright © 1946 by McGraw-Hill Book Company, Inc.

    A.I1S l O N I GAIICARB A N A TE 85

    inhaled, it combines with the hemoglobin of the blood,


    rendering it incapable of acting as an oxygen carrier..
    23. AMMONIUM CARBAMATE
    2kH3(liquid) GOz(solid) + H2NCOONH4
    SWAUTTEr- A . A. BROOKS*A V D L. F. AUDRIETA*
    BY Ei. B L U E ~ T OAND
    CHECSED N E WARREN
    ~ C. J O F I N S O X ~

    Ammonium carbamate has been prepared by the direct


    combination of ammonia and carbon dioxide in the gas
    phase and also in cooled inert solvents such as alxolute
    alcohol and petroleum ether.l The direct laboratory
    preparation from readily available Dry Ice and liquid
    ammonia offers a convenient source of ammonium car-
    bamate. It is interesting to note that under other condi-
    tions these same reactants produce urea.
    Ammonium carbamate may be used as an ammonating
    agent where a reagent less vigorous than ammonia is
    desired.
    Procedure
    About 400 ml. of anhydrous liquid ammonia is placed in
    a 1-liter pyrex Dewar flask,$ preferably unsilvered for
    visual observation. Dry Ice is powdered and added
    slowly, yet as rapidly as feasible, to the liquid ammonia.§
    Addition of solid carbon dioxide is continued until the
    mixture attains a slushy consistency. The excess of
    ammonia is then allowed to evaporate, leaving the car-
    * University of Illinois, Urbana, Ill.
    t University of Chicago, Chicago, Lll.
    $ These vacuum flasks are obtainable from the American Thermos Bottle
    Co., Norwich, C o w . Unsilvered flasks of ordinary glass may also be used,
    but these do not n-ithstand the repeated temperature changes as well as
    those made of pyres.
    0 Care should be taken both in the powdering of the dry ice and in its
    addition to ammonia to prevent absorption of moisture. This is best
    accomplished by keeping the Dry Ice in a suitable container and powdering
    it in small portions as it is needed. Condensation of moisture at the surfacc
    of the liquid ammonia can be prevented by closing the flask with a stopper
    fitted with a bent capillary tube, which serves as a n ammonia vapcr trap.
    86 INORGANIC SYXTHESEB

    bamate as a lumpy residue. This material is transferred


    to a desiccator and kept under slight,ly reduced pressure
    for 24 hours. It is transformed, through loss of excess
    ammonia and dissociation of some ammonium carbamate,
    into a powdery product. When the quantities of ammonia
    specified above are used, 200 to 300 g. of ammonium car-
    bamate can be prepared. And. Calcd. for HzNCOzNH4:
    N, 35.9. Found: N, 35.3, 35.2.
    Properties
    Ammonium carbamate is obtained as a fine crystalline
    powder, slightly volatile at room temperature and com-
    pletely dissociated a t 59”. It is very soluble in water
    but, in solution or on standing in moist air, it undergoes
    hydration to ammonium carbonate :
    HzNCOONH, + HzO -+ (NH,)zC03
    A solution of ammonium carbamate may be distinguished
    from one of ammonium carbonate by adding a drop or
    two of a soluble calcium salt. No immediate precipitate
    is observed; but, after standing or heating, hydration occurs,
    resulting in the precipitation of calcium carbonate.
    Reference
    I . For a complete review, with bibliography, of the properties and reactions
    of ammonium carbamate see Gmelin, ‘‘Randbuch der anorganischen
    Chem‘e,” 8th ed., KO.23, pp, 348-362, Verlag Chemie G.m.b.H.,
    Berlin, 1936.

    24. ALKALI METAL CYANATES


    RIzC03 + 2HzNCONHz-t 2MNCO + COz + 2NH3 + H20
    SWMITTEDB Y ALLEN SCATTERGOOD*
    B Y DONR. MCADAMS~
    CHECKED P. M C R E Y N O L D s t j
    P.XD JAMES

    Potassium cyanate has been prepared by the oxidation


    of potassium cyanide by many reagents,* by fusion of
    * Union Junior College, Roselle, N.J.
    t The Ohio State University, Columbus, Ohio.
    Deceased.

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