Info Jbj
The induction period for pure trinitrotoluene at 275 C is 12 min and at 328 C-50 sec. As T. Urbanski and Pillich 93 found, the addition of sulphur to TNT causes the initiation temperature to fall. This can be seen from the following data Sulphur content, Initiation temperature, C The explosion caused by heating TNT to which 5-10 of sulphur has been added is more violent than the explosion of pure TNT. Investigations on the influence of metals on TNT are of special importance. Extensive studies...
Nitro Derivatives Of Cresols
Of the three isomeric cresols ortho-, meta-, and para-, only m- cresol can be used as the starting material for introducing three nitro groups, viz. in the 2,4,6-positions. Ortho and p- cresols are able to form stable nitro group systems only when no more than two nitro groups are introduced. Under the conditions of the nitration of m- cresol to its trinitro derivative the o- and p- isomers are oxidized to oxalic acid. Cresol for nitration should contain a high proportion of the m- isomer....
Threestage preparation of TNXf
Mononitration. For 100 parts of m- xylene, separated from its isomers by sulpho-nation, 220 parts of a nitrating mixture of the composition The nitrating mixture is prepared from spent acids from di- and tri-nitration, by fortifying them with fresh concentrated acids. The nitration temperature should not exceed 35 C. From 100 parts of m- xylene, 130-135 parts of MNX are obtained, i.e. the yield is 90-94 of the theoretical. Further procedure separation of the nitro compound from the spent acid...
CHEMICAL PROPERTIES Jbq
An outstanding feature of picric acid is its acidic character. It readily forms picrates they are dealt with in a special chapter, p. 525 and esters, which are phenol ethers, e.g. trinitroanisole p. 545 , trinitrophinetole p. 548 . Like other polynitroaromatic compounds, picric acid readily forms addition products with aromatic hydrocarbons. This behaviour is especially pronounced in picric acid. Addition compounds with phenols, aromatic ketones, acids and even with nitro compounds are also...
Purification of dinitrophenol
The product prepared by the above methods usually contains 2,4-dinitiophenol 88-89 2,6-dinitrophenol 3 4 Since liquid impurities may produce exudates in explosive compositions, to avoid this the crude product should be purified. For a preliminary washing, a dilute 2 solution of sodium carbonate may be used. Picric acid reacts with the carbonate which then goes into solutions as sodium picrate. Instead of sodium carbonate milk of lime or calcium hydrogen carbonate may be used. Desvergnes...
CHEMICAL PROPERTIES Lia
Although tetranitromethane does not contain active hydrogen it readily enters certain reactions. With water it reacts slowly to form trinitromethane, i.e. nitro-form C NO2 4 HOH - gt CH NO2 3 HNO3 20 With potassium hydroxide, tetranitromethane readily yields its potassium salt of nitroform C NO2 4 2KOH CK NO2 3 KNO3 H2O 21 It react with sodium sulphite to yield sodium trinitromethanesulphonate C NO2 4 NO2SO3 - gt O2N 3CSO3Na NaNO2 22 With copper or nickel in the presence of ammonia it forms...
Chemical Properties Of Trinitronaphthalene Isomers
1,3,5- a - and 1,3,8- b - trinitronaphthalenes form the following molecular compounds a3.p, a.p, a.p3 Pascal 20 . Trinitronaphthalenes can be oxidized relatively easily to form corresponding nitrophthalic acids. Some of the nitro groups can be relatively readily substituted by a methoxy or ethoxy group when heated with the corresponding sodium alcoholate. The oxidation of such a compound leads in the first place to rupture of the ring with the alkoxy group. Oxidation reactions have been...
Infrared Absorption Spectra
In the infra-red region the nitro group produces two bands of high intensity one near 6.4 1563 cm-1 , which characterizes asymmetric vibrations of the bonds of the nitro group I , and another near 7.4 1351cm-1 , which characterizes symmetric vibrations of the bonds of the nitro group II . In addition to this, vibrations of the nitro group ranging from 4.0-4.17 2500-2398 cm-1 exist Kornblum, Ungnade and Smiley 19 , but they are of little significance for identification according to the authors....
Chapter Ix Tnt Manufacture
Nitration of toluene to TNT 347 General Three stage process for manufacture of TNT 347 Old French Old British Old U. S. S. R. method according to Gorst 354 German Two-stage manufacture of TNT old Italian method 363 Material Continuous methods of Earlier Modern Purificalion of Purification by Sulphitation and drying of TNT 379 Schematic diagram of a plant for continuous TNT manufacture 386 Utilization and neutralizing sulphitation liquors 389 Waste Safety in TNT
Dinitroresorcinol
They are yellow substances, readily soluble in hot water, which dye animal fibres and leather. Only the 2,4-isomer is of practical importance as the one most easily available. The 4,6-isomer cannot be obtained directly, though it may be prepared by the nitration of diacetylresorcinol. Since the nitration of resorcinol by the conventional method for phenols i.e. sulphonation followed by the action of nitric acid yields a trinitro derivative, two other methods for the preparation of...
O
According to Schaarschmidt 18 the mechanism of nitration with a mixture of nitric and sulphuric acids consists in the formation of nitric anhydride which becomes attached to the aromatic compound. The addition compound is unstable and decomposes, giving a nitro compound and nitric acid. The mechanism of nitration suggested by Schaarschmidt is 2HNO3 H2SO4 lt - gt N2O5 H2SO4.H2O 2HNO3 H2SO4 lt - gt N2O5 H2SO4.H2O Hetherington and Masson 19 suggested that nitrobenzene can form complexes with H2SO4...
Separation Of Isomers
The composition of the mononitrotoluenes prepared at Griesheim is Distillation of crude nitrotoluene. The still kettle is of 60 m3 capacity, heated with 18.5 atm steam. The column has 40 plates, 8 m height, 2 m diameter. 55,000 1. of the crude, steam distilled and dried nitrotoluene are sucked into the still while heating up. Distillation begins under reduced pressure 15 mm Hg on the receiver and 120 mm Hg in the kettle at a still temperature of 160 C. First runnings ca. 200 1. have a setting...
Picrylhydroxylamine
Picrylhydroxylamine is oxidized in a yield of about 60 of theory. Holleman 58 obtained tetranitrobenzene in another way, starting from picr-amide Picrylhydroxylamine is oxidized in a yield of about 60 of theory. Holleman 58 obtained tetranitrobenzene in another way, starting from picr-amide Tetranitrobenzene is a crystalline substance, melting at 129-130 C. In the presence of moisture it is readily decomposed to form picric acid. When boiled with water it is fully converted to picric acid. It...
CI Mdu
MONONITRO DERIVATIVES OF CHLOROBENZENE There are three chloronitrobenzene isomers known ortho, meta and para The o- and p- isomers can be obtained during the nitration of chlorobenzene. The higher the nitration temperature, the more o- isomer is formed. As Holleman and de Bruyn 8 reported At 0 C 30.1 of the ortho- and 69.9 of the para- isomer is formed, at 30 C 26.9 of the ortho-, and 73.1 of the para-isomer is formed. Besides, higher temperatures favour the formation of some small quantities...
Conductometric studies
Further conductometric studies of nitric acid by Medard 48 and later Dalmon 49 have shown that on adding water to the anhydrous acid, conductivity falls to a minimum at concentrations of 96-97 HNO3, and then on further dilution it rises again. This is explained by the fact that anhydrous nitric acid is dissociated, but in the presence of small quantities of water is converted into an undissociated hydrate HNO3.H2O. It is only on further dilution that the hydrate dissociates. In conductometric...
Mixing Of Reagents During Nitration
There are three methods of mixing organic substances to be nitrated with nitrating mixtures 1 adding the substance to the acid, 2 adding the acid to the substance, 3 simultaneous introduction of both acid and organic substance into the nitrator. The first method is the one most frequently applied. It has, however, certain drawbacks. The first portions of the nitrated substance are introduced into an excess of nitrating mixture and may be converted to a higher degree of nitration than required...
Utilization And Neutralizing Of Sulphitation Liquors
The sulphitation liquors contain dinitrotoluenesulphonic acids in a quantity amounting to about 4 of the TNT produced. In a period of intensive manufacture of TNT this may be of considerable importance from an economic point of view. This is why the problem has arisen of how to utilize the organic compounds contained in sulphitation liquors. Batik 27 found that the acidification of sulphitation liquors with an inorganic acid resulted in the formation of NaHSO3, which reduced the nitro- to the...
Metal nitrates in the presence of FriedelCrafts catalysts
Apart from the investigations on nitration with the nitrates of some metals in the presence of sulphuric or nitric acid Topchiyev 115 has carried out extensive studies on nitration with metal nitrates in the presence of AlCl3, FeCl3, SiCl4, and BF3. He showed that all the nitrates had nitrating properties, and he ordered the nitrates he studied according to their increasing nitration activity in the presence of AlCl3 With KNO3 and NaNO3 the yield of nitrobenzene was 70 and 73 respectively,...
no
It has been found by the same authors that heating 2,3-dinitrophenol with sulphuric acid leads to partial isomerization to 2,5-dinitrophenol. Other dinitro compounds, viz. those substituted in the 2,5- and 3,4-positions, do not undergo such rearrangement. This fact is evidence that only that group can migrate which meets with steric hindrance i.e. the nitro group in the ortho position to the adjacent group or groups . No evidence of reversibility of aromatic C-nitration has so far been found....
Info Mcr
Such a mechanism accounts for the first-order dependence of the rate on reaction the nitric acid concentration in presence of sulphuric acid. A higher-order dependence on nitric acid concentration in the absence of added strong acid H2SO4 was also observed. This, according to Paul, is a consequence of the dual role assumed by nitric acid itself providing the proton acquired in step a . The nitric acid-acetic anhydride reaction is not a simple one, and requires more study. Nitration with...
Classification Of Explosives
explosives may be classified both from the chemical point of view and according to their uses. From the chemical viewpoint we distinguish between chemical individual substances and mixtures. 4 derivatives of chloric and perchloric acids 6 various compounds capable of producing an explosion, for example fulminates, acetylides, nitrogen rich compounds such as tetrazene, peroxides and ozonides, etc. Individual substances are explosive if their molecules contain groups which confer upon them...
Info Yge
According to T. Urbanski and Pawelec 35 , the rate of detonation of nitro-methane can be expressed by the following figures Table 125 . Rate of detonation average values m sec
Info Psk
For charges 21 mm in diameter. initiated by a 2 g detonator, in the open. In a metal pipe 10-15 mm in diameter. Charges in bakelite pipes of 4.5-8.2 mm internal diameter. in a steel pipe 31.7 mm in diameter. For charges 21 mm in diameter. initiated by a 2 g detonator, in the open. In a metal pipe 10-15 mm in diameter. Charges in bakelite pipes of 4.5-8.2 mm internal diameter. in a steel pipe 31.7 mm in diameter. Values ranging from 6900 to 7000 m sec are usually accepted as the maximum rate of...
Info Lbo
According to the same author Jefremov and Frolova 32 , with l-chloro-2,4-dinitrobenzene picryl chloride forms an addition compound mol. ratio 1 1 m. p. 31.2 C. Formerly Frankland and P. H. Garner 27 and Desvergnes 18 reported only the formation of a simple eutectic containing 44-45 picryl chloride with m. p. 25.0-25.6 C. Recently T. Urbanski, Semenczuk and Gorski 32a confirmed the statement of Jefremov and Frolova. Picryl chloride reacts with pyridine to form picrylpyridinium chloride IV This...
Photonitration With Nitrogen Dioxide
Gorislavets 93 claimed that the nitration of benzene or nitrobenzene with nitrogen dioxide readily occurred on irradiation with rays of certain definite wavelengths, which activate nitrogen dioxide. Thus, benzene was nitrated quantitatively at the wavelengths 4000 - 7000 A at a temperature of 55-60 C. The highest yield of dinitrobenzene was obtained at wavelengths 1800 - 2900 A. The experiments of other workers did not confirm his results Hastings and Matsen 94 . On the other hand Lippert and...
Preparation Of Unsymmetrical Isomers Of Trinitrobenzene
1,2,4-Trinitrobenzene may be obtained only in moderate yield by nitration of o- or p- dinitrobenzene. A product of high purity may be obtained from 2,4-di-nitroaniline Korner and Contardi 56 This isomer dissolves less easily in alcohol or ether than sym-trinitrobenzene. The nitro group in position 1 can readily be substituted by a hydroxyl or amino group. 1,2,3-Trinitrobenzene cannot be obtained by the nitration of o- dinitrobenzene. Kamer and Contardi have prepared this isomer from...
LITERATURE Ygi
1. K. Smolenski, S. Turowicz and R. Dobrowolski, Przemysl Chem. 5, 201, 237 1921 6, 250, 281 1924 . 2. R. C. George and J. B. Patberg, Ind. Eng. Chem. Anal. Ed. 13, 768 1941 . 3. G. Desseigne, Y. Glalel, A. Guillemin and Y. Sousselier, Chimie et Zndustrie 20, No. spec. 290 1954 . 4. A. G. Gorst, Porokha i vzryvchatyye veshchestva, Oborongiz, Moskva, 1957. 5. P. Pascal, Poudres, explosifs, gaz de combat, Hermann, Paris, 1925. 6. Technical Records of Explosives Supply 1914-1918, No. 2....
Nitric acid and acetic acid or anhydride
Acetic anhydride creates dehydrating conditions, therefore a mixture of nitric acid with acetic anhydride has strong nitrating properties. Moreover in esterifi-cation with nitric acid, the acetic acid present in the mixture or formed in the reaction does not hydrolyse the nitric acid ester formed. Nitric and acetic acids. According to A. Pictet and Genequand 100 , acetic acid combines with nitric acid d 1.52 to give a kind of mixed orthonitric and acetic anhydride, the so-called...
Addition Compounds Of Aromatic Polynitro Compounds
The ability to form addition compounds, especially with aromatic hydrocarbons composed of condensed rings, is one of the specific properties of aromatic poly-nitro compounds. For example, compounds of trinitrobenzene or picric acid with naphthalene, as well as with other hydrocarbons with condensed rings, are very characteristic. Generally they are intensely coloured. The nature of the bonds forming molecular addition compounds has been investigated by several workers, but up to now it has not...
Applications of TNX
Trinitroxylene is used as an additive for fusible explosive compositions mixed with TNT, with TNT and picric acid, or with ammonium nitrate Vol. III . For the compositions of various eutectics with trinitroxylene see p. 400. MONONITRO DERIVATIVES OF o- AND p- XYLENES Ortho- and p- xylene nitrate more readily than m- xylene. They are also more readily oxidized especially during mononitration as well as during vigorous nitration to trinitro derivatives. For this reason the yields obtained in the...
Swedish BoforsNorell method
The Bofors-Norell process 21 was tried out in 1940-41 and has now been in full-scale operation for nearly two decades. The process includes both continuous nitration of toluene or mononitrotoluene to trinitrotoluene and continuous crystallization of the product from dilute nitric acid. The nitration is carried out continuously in a series of nitrators through which the nitrating acids and toluene or nitrotoluenes pass in counter-current. Each nitrator is joined with a separator. According to A....
More Recent Studies
Hantzsch's work and his conclusions have lately been revised and criticized. In his extensive work published in 1941, Titov 35 drew attention to the fact that none of the existing view about the action of sulphuric acid on nitric acid explained Hantzsch's observation that the value of the van't Hoff i-factor for nitric acid dissolved in sulphuric acid may be close to 4. Titov quotes the following equations, based on different existing views HNO3 2H2SO4 HO3S ONO2 H2SO4.H2O 12 equation based on...
Reactivity Of The Nitro Group
Aromatic nitro compounds which are of course tertiary, form a separate group of compounds, differing from the aliphatic nitro derivatives in many respects. For this reason they deserve special attention. The attachment of nitro groups to the aromatic ring affects their reactivity. For example, nitro groups in ortho or para position in relation to each other are rather reactive, and one of them can be substituted relatively easily. Only the nitro groups in the meta position to each other are...
Nitro Derivatives Of Xylenes
m- Xylene is the most important of the three xylene isomers ortho-, meta- and para- as a starting material for the preparation of nitro derivatives, as it enables three nitro groups to be introduced into the 2-, 4, and 6- positions. Ortho- and para- xylenes can give a stable system when only two nitro groups are introduced, for when three groups are introduced one of them is compelled to occupy an inappropriate position and may easily undergo substitution reactions. Xylene for nitration should...
noh 1
Tetranitrophenol forms by the action of 50 nitric acid followed by a 63 acid on diquinoyltrioxime at a temperature lower than the room temperature. By neutralizing the solution a sparingly soluble potassium salt is precipitated, which in turn may be converted by double decomposition into a still less soluble barium salt. From the latter, by the action of a calculated quantity of sulphuric acid, free tetranitrophenol may be obtained. A product of higher purity than that obtained by Nietzki was...
Picric Acid Salts
Metal salts of picric acid may be formed by the action of picric acid on metals, their oxides or carbonates and in certain cases also on their other salts. They are crystalline substances, mostly more sensitive to friction, impact and heat, than picric acid itself. Due to their high sensitivity to stimuli, the explosive properties of picrates were known long before those of picric acid. Picrates formed by precipitation from aqueous solutions contain water of crystallization which may...
Nitric acid salts in mixtures with other acids
In the days when anhydrous nitric acid was not easily available, nitric acid salts NaNO3, KNO3 mixed with sulphuric acid were widely used for nitration. Such mixtures acted similarly to the mixture of nitric and sulphuric acids. Later, as synthetic nitric acid became one of the most readily available chemical products, and the production of nitric acid salts from nitric acid had started, nitrating mixtures with sodium or potassium nitrates were abandoned. This is the principal explanation for...
Design Of Nitrators
The nitrators used in the manufacture of aromatic nitro compounds consist of iron vessels Fig. 29 , equipped with a stirrer I and a jacket 2 for cooling or heating the contents, as well as with a lid 3 , connected with a ventilation pipe 4 . Gaseous products from the nitration process NO, NO2, HNO3, SO3, SO2, CO, CO2 are conducted away through it. The ventilation duct is equipped with a sight glass 5 , which permits the observation of waste gases - mainly their colour. In addition to the...
Stirrers
The influence of stirring on the nitration rate and the safety of the operation has already been emphasized. It is evident that special attention must be paid to the stirring equipment provided in a nitrator. Various types of stirrers are used. Horseshoe stirrers, the shape of which fits well into the inside of a nitrator, are the simplest type Fig. 29 . Fig. 30. Diagram of a nitrator with a spiral screw stirrer. Fig. 30. Diagram of a nitrator with a spiral screw stirrer. Another type of simple...
Product Separation And Discharge Of The Nitrator
When the reaction has been completed the nitrator contents must remain at rest for some time to allow the product to separate from the spent acid. This may be done in the nitrator itself or the mixture may be transferred into a special settler-separator. The latter is more advantageous if the next nitration is to be carried out in the nitrator immediately after the first reaction. The nitrator is discharged either through an outlet located in the bottom Fig. 34 or by forcing the contents out by...
B 1
Fig. 19. Heat evolved on mixing nitric acid with sulphuric acid in relation to the water content A in these acids. Quantity of heat Q A B Gelfman 5 . In this diagram the heat of interaction between the anhydrous acids, H2SO4, and HNO3, calculated on 100 g of mixture, has been presented, where Q is the heat of mixing in calories and x is the H2SO4 content in the mixtures wt. . The heat maximum corresponds to x ca. 67 of H2SO4. Gelfman points out that the heat of interaction between sulphuric and...
Physical Properties 1
The boiling points of the ortho-, meta-, and para- isomers are 319 C, 303 C, and 299 C respectively. The corresponding melting points are 118 C, 91 C and 172 C. They are all crystalline, pale yellow products, highly toxic, the ortho- and para-isomers even more than m- dinitrobenzene, according to existing data. Commercial dinitrobenzene is a mixture of the m-dinitro compound, as a principal component, with some 8.0 the ortho- and para-isomers. It melts at 80-82 C. The melting point of...
Kinetics Of The Nitration Of Dinitrotoluene To Trinitrotoluene
From the results of their studies on the kinetics of the nitration of 2,4-dinitroto-luene to 2,4,6-trinitrotoluene Bennett and his co-workers 109, 110 inferred that the reaction is of the third order, represented as follows DNT NO2 HSO4- - gt TNT H2SO4 17 DNT NO2 H2SO4 - gt TNT H2SO4 18 In the presence of oleum the reaction DNT NO2 HS2O7- - gt TNT H2S2O7 19 The rate of the nitration reaction in the presence of sulphuric acid can be re presented by k DNT NO2 HSO4- k' DNT NO2 H2SO4 20 The...
NO Lvl
The reaction of nitric acid with phenols including resorcinol has been fully investigated by K. H. Meyer and Elbers 36 . They isolated a reddish-brown product to which they assigned the indophenol N-oxide structure III . The compound can be, formed directly from phenol and nitric acid, according to the scheme The direct formation of styphnic acid from resorcinol and nitric acid may also be explained by this series of reactions. Earlier, Auwers 37 expressed the opinion that phenols when reacted...
Info Wvf
Phenoltrisulphonic acid is formed only when using an excess of 20 oleum. The second stage in the preparation of picric acid is the nitration of the phenol-sulphonic acid obtained in the first stage of the process. Sulphophenol, which is the name of the starting material for the second stage, is a mixture of 1,4-phenolsulphonic and 1,2,4-phenoldisulphonic acids. For the nitration the following nitrating agents may be used a dilute 44-65 nitric acid b mixture of dilute nitric acid and sodium...
Chapter Xi Nitro Derivatives Of Naphthalene
General Mononitro derivatives of Dinitro derivatives of Physical Composition of the commercial product 429 Chemical Trinitro derivatives of Chemical properties of trinitronaphthalene isomers 432 Structure of a- and g somers 433 Explosive properties and application of trinitronaphthalene 434 Tetranitro derivatives of Structure of Thermochemical properties of Side reactions in the nitration of naphthalene 437 Manufacture of nitro derivatives of naphthalene 438 Nitration of naphthalene to...
Washing picric acid
The contents of 4-5 nitrators 200-300 kg of picric acid are transferred by means of wooden ladles to a wooden washing vat Fig. 114 , where picric acid is washed several mostly five times with 150-200 1. portions of water. For 100 kg of picric acid 400 1. of water is used. The product is tested for purity by determining the SO42 ions in a solution of the picric acid in distilled water. After washing, picric acid is separated from water in a centrifuge usually made of copper, the water content...
Nitropolystyrene
Investigations on the nitration of polystyrene go back to 1845, to the experiments of Blyth and Hofmann 39 , who reacted boiling nitric acid with glassy polystyrene, which was obtained from styrene of natural origin, namely from Styrax resin. The product prepared contained 10.6 of N. During World War II several authors resumed the investigations. G. B. Bachman and his co-workers 40 nitrated polystyrene with nitric acid sp. gr. 1.50 and obtained products of various degrees of nitration depending...
K
A nitro group ortho to the phenol group can form a chelate through an internal hydrogen bond p. 177, see also p. 171 . This structure accounts for certain properties of o- nitrophenol, and namely those by which it differs from its m- and p- isomers. For example, o- nitrophenol is volatile in steam. This may be explained by the fact that owing to the presence of an internal hydrogen bond, the intermolecular links which are responsible for molecular association are either weakened or...
Electrolytic Nitration
Electrolytic nitration was first proposed by Triller 22 in 1897. This author pointed out that with nitric acid of concentration 52 HNO3 at 80 C a- nitro-naphthalene free from dinitronaphthalene can be obtained at the anode. With nitric acid of concentration 65 HNO3 dinitronaphthalene is obtained. Fichter and Pluss 23 checked the Triller's patent in 1931 by carrying out simultaneous experiments with ordinary and electrolytic nitration. They found that the electrolytic method did indeed provide...