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    Purification of Nitromethane by Crystallization

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    This document describes a method for purifying nitromethane through crystallization. Commercial nitromethane contains impurities like higher nitroalkanes and cyanoalkanes. Conventional purification methods were found to be inadequate. Crystallizing commercial nitromethane from diethyl ether at temperatures below -60°C effectively removes all impurities, as shown through NMR spectroscopy. The purified nitromethane yields are 60-80% with a purity greater than 99.9%.

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    Purification of Nitromethane by Crystallization

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    de palo
    108 views1 page
    This document describes a method for purifying nitromethane through crystallization. Commercial nitromethane contains impurities like higher nitroalkanes and cyanoalkanes. Conventional purification methods were found to be inadequate. Crystallizing commercial nitromethane from diethyl ether at temperatures below -60°C effectively removes all impurities, as shown through NMR spectroscopy. The purified nitromethane yields are 60-80% with a purity greater than 99.9%.

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    This document describes a method for purifying nitromethane through crystallization. Commercial nitromethane contains impurities like higher nitroalkanes and cyanoalkanes. Conventional purification methods were found to be inadequate. Crystallizing commercial nitromethane from diethyl ether at temperatures below -60°C effectively removes all impurities, as shown through NMR spectroscopy. The purified nitromethane yields are 60-80% with a purity greater than 99.9%.

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    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    108 views1 page

    Purification of Nitromethane by Crystallization

    Uploaded by

    de palo
    This document describes a method for purifying nitromethane through crystallization. Commercial nitromethane contains impurities like higher nitroalkanes and cyanoalkanes. Conventional purification methods were found to be inadequate. Crystallizing commercial nitromethane from diethyl ether at temperatures below -60°C effectively removes all impurities, as shown through NMR spectroscopy. The purified nitromethane yields are 60-80% with a purity greater than 99.9%.

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    of 1

    Purification of Nitromethane by Crystallization

    There is no purified nitromethane an the market, and to obtain pure nitromethane for research purposes seems to be
    a problem. It has been said1 that conventional methods of purification were inadequate for the removal of impurities in
    commercial grade nitromethane. The impurities are usually higher nitroalkanes plus trace cyanoalkanes and are distin-
    guishable from nitromethane by nmr spectroscopy (Fig. 1).We have tried the reported methods of purifying nitromethane,
    such as the chemical treatmentsz and the szeotropic distillation^,^,^ but the results were unsatisfactory. Now we find that
    a treatment of crystallization from ether a t -60-78OC eliminates all the impurities which appear in the nmr spectrum of
    the commercial product (Fig. 2).

    Fbve 1. Nm s m m of commercial MeN02, neat (Varian T-60A Figure 2. Nmr spectrum of purified MeNOs, neat (Varian T-BOA at
    at 35%). 3S°C).

    This is an excellent example of liquid purification by the crystallization method. The physical constants (m.p. 'C, h.p.
    OC) of nitramethane (-28.5. . 101). and the oossihle imourities.. e.e.. ~ ~. .
    " . nitroethane~.(-90. 115). 2-nitrooraoane (-93.
    . . .. 1-
    120).
    nihopropane I-106,131), propionitrile (-$1.9,97.2l,andacetonitrile (-45.7.60.1) cliarlyikdicate that alow temperature
    crystnllirar~onshould be more efficient. The solid nitromethane is only slightly soluble indiethylether (m.p. -1 1 6 W below
    -60°C. and Dry Ice is therefore a perfect cooling agent for this purpose. There is no need to build a vacuum system. The
    condensed moisture from the atmosphere can be removed easily via an ordinary fractional distillation as nitromethane and
    water form an azeotrope a t 83%
    A simple procedure of this method for laboratory operation is outlined as follows: To a stirred 1:l (vlv) mixture of
    commercial nitromethane and diethyl ether in a Dewar flask, add Dry Ice powder slowly until the temperature is well below
    -60°C. Stir for five more minutes and transfer the mixture to a deep Bnehner type funnel (with coarse fritted disc) jacketed
    with Dry Ice. Apply the water pump for several seconds to remove most of the ether. Stop pumping and pack the crystals
    tight in the funnel with a glass rod. Spread some Dry Ice powder over the surface and suck for 20 sec. Wash twice with ether
    precooled at -78°C each of half the amount in the original mixture. Pack the crystals and add more Dry Ice as above during
    each washing. Remove the Dry Ice jacket and allow the solid in the funnel tomelt and filter through into adistilling flask.
    Distill the liquid through a packed column to the boiling point of nitromethane, discarding the distillate. Clean and dry
    the condenser thoroughly and continue distillating. Discard a small amount of forerun and collect the rest of the distillate.
    This would recover 60-80% of the commercial nitromethane in a nure state.
    The purity of the nitromethane after treatment should be b e k r than 99.9%as the nrnrpeaks of the impurities are no
    longer drtectahlr compared with the intensities of the ':'C satellites (Fig. 2) which is 0.5590 of the intensity of the nitro-
    methane.
    This work was supported by the Defence Researeh Board of Canada (Grant No. 9530-102).

    Bardin, J. C., Analusis, 1(2), 140 (1972); C.A., 78,8516f (1973).


    Thomoson. C. J.. Coleman. H . J.. and Helm. R. V.. J. Arner. Chem. Soc.. 76.3445 (1954).

    Royal Military College of Canada Frederick William Parrett


    Kingston. Ontario. Canada K7L 2W3 Mian Shin S u n

    448 1 Journal of Chemical Education

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