Preparation of nitrogen dioxide
The following synthesis description for the preparation of nitrogen dioxide was submitted by Jared Ledgard from Kings Chem Guide, 3th edition
Preparation of nitrogen dioxide gas generating mixture Into a standard “inexpensive” kitchen style blender utilizing stainless steel blades (make sure it is completely dry; sodium bisulfate is highly corrosive so metal blades will get lightly corroded/tarnished) add in 246 grams (8.67 oz.) of sodium nitrate. Note: most if not all sodium nitrate sold is in the form of small pellets, and hence, these pellets need to be pulverized into a powder first, so once the sodium nitrate has been added, turn on the blender to high speed, and blend dry on moderate speed for about 5 to 10 minutes, stopping every 30 to 60 seconds to “smack” the side of the blender container to make sure all the desired sodium nitrate gets blended properly. Now, once the sodium nitrate pellets have been thoroughly powdered, throw into the blender 400 grams (14.1 oz.) of sodium bisulfate monohydrate, and then carefully blend this combined mixture on moderate speed for 5 to 10 minutes, stopping every 30 to 60 seconds to “smack” or “shake” the side of the blender container to make sure all the desired mixture gets blended properly to form a uniform powdered mixture. Note: Even though the mixture will be dry, some nitrogen oxides will develop inside the blender container, so carry out this blending operation in a well-ventilated area. Second note: The sodium bisulfate monohydrate is readily available from pool supply chemical retailers as it is sold as a pH balancer, and contains 92 to 94% sodium bisulfate and the remainder sodium sulfate (this is the desired sodium bisulfate product to be used in this operation). Also, standard sodium nitrate is readily available from online sellers for a low cost. Now, once the nitrogen dioxide generating mixture has been thoroughly blended, quickly remove the blender lid, blow on the upper surface of the blending container (to blow away any nitrogen oxides), and then either use the nitrogen dioxide generating mixture immediately as discussed in the following, or store it in a HDPE (High Density Polyethylene) container, sealed air tight, and then place this container into a ziplock bag, and seal it air tight for prolonged storage. Note: during storage the mixture may turn yellow due to a small amount of nitrogen oxides being liberated. Step 2: The process Set-up an apparatus similar to the one portrayed in the following.
Then heat the nitrogen dioxide gas generating mixture as illustrated. Continue to heat until no more reddish gas is evolved. Note: Now, some nitric acid of 68 to 70% forms in the reaction flask, but may not pass over, and the nitrogen oxides build up and are passed over under vacuum, and dissolved in water to form dilute nitric acid, or used in other ways.
Kings Chem Guide, 3th edition, by Jared Ledgard, 185, 2014.
Preparation of nitrogen dioxide from sodium nitrite and sulfuric acid
Nitrogen dioxide is very poisonous, all work with it should be performed in a hood. A 500 ml flask containing 40% sodium nitrite solution is fitted with a dropping funnel containing 20% sulfuric acid and an outlet tube that leads first into an empty wash bottle, thence into a U-tube packed with glass wool, finally into a second empty wash bottle, which is immersed in an ice-salt bath at —15° C or lower. By treating 40% sodium nitrite solution with 20% sulfuric acid the evolution of nitrogen oxides occurs. When the evolution of gas has ceased, a gentle air current (2 bubbles/sec) is passed through the liquefied gas until the color has become a pure yellow-brown. The gas may then be distilled into a sealing tube or ampoule by allowing the wash bottle to warm up in the air. The boiling point of nitrogen dioxide is 22 °C.
Inorganic laboratory preparations, by G. G. Schlessinger, 12, 1962
Preparation of nitrogen dioxide from lead nitrate
About 200 g of pure lead nitrate were dried at 110 °C for several hours and then placed in the 500 ml distilling flask. This was heated in a solder-bath to a sufficient temperature to give a moderate flow of deep reddish brown gas, as indicated by the rate of bubbling through the paraffin oil in the U-tube.
The condenser was kept immersed in a bath whose temperature was approximately -15°C. The rate of generation of the nitrogen dioxide was so regulated that a large part of it condensed in the condensing coil and collected in the reservoir at the bottom thereof. As nitrogen dioxide rapidly destroys corks and rubber tubing, it is necessary to make as much as possible of the apparatus of glass. The liquid nitrogen dioxide is collected in the condenser.
Perchloric acid from ammonium perchlorate and oxides of nitrogen, by Alfred W. Knight, 12-14, 1922
Preparation of nitrogen dioxide from arsenic trioxide and nitric acid
A 500 ml flask is fitted with a dropping funnel and an outlet tube that leads first into an empty wash bottle, thence into a U-tube packed with glass wool, finally into a second empty wash bottle, which is immersed in an ice-salt bath at —15°C or lower. Forty grams of arsenic trioxide are placed in the flask and 50 ml of concentrated nitric acid (d=1.4) slowly dropped in while warming gently. When evolution of gas has ceased, a gentle air current (2 bubbles/sec) is passed through the liquefied gas until the color has become a pure yellow-brown. The gas may then be distilled into a sealing tube or ampule by allowing the wash bottle to warm up in the air. The boiling point of nitrogen (IV) oxide is 22 °C.
The nitrogen dioxide gas exists as a colorless or very pale yellow dimer below 17°C and deepens in color as the temperature is raised, until at 64° C both forms exist at equilibrium in equal amounts.
Above 130°C nitrogen dioxide slowly decomposes to nitrogen (II) oxide and oxygen. The process is complete above 154°C.
Inorganic laboratory preparations, by G. G. Schlessinger, 11, 1962
Preparation of nitrogen dioxide by the action of tin on concentrated nitric acid
Metallic tin and nitric acid react vigorously, nitrogen dioxide being evolved. The bottom of a 250-500 ml Erlenmeyer flask is covered with granulated metallic tin, and conc. nitric acid is introduced through a thistle-tube reaching to the bottom of the flask. A glass elbow thrust through the cork in the neck of the flask is connected to a gas washing-bottle, which is in turn connected with a U-tube immersed in a freezing-mixture of salt and ice. As soon as the nitric acid is added, the reaction begins and great heat is developed. Most of the steam formed is condensed in the gas washing-bottle. The nitrogen dioxide is condensed in the U-tube. By disconnecting the U-tube and connecting a glass tube to the gas washing-bottle, the gas may be collected by displacement.
Chemical lecture experiments, by F. G. Benedict, 220, 1916.
Preparation of nitrogen dioxide by decomposition of nitric acid by heat
At a high temperature nitric acid undergoes decomposition, with the formation of nitrogen dioxide and oxygen. A very simple and efficient method for showing this decomposition consists in allowing the nitric acid in vapor form to pass over pumice stone heated in a piece of combustion tubing 40 cm. long and 15 mm. in diameter.
A thick piece of rubber tubing is slipped over one arm of a large glass elbow 10 mm. in diameter which is then crowded into one end of the combustion-tube, thereby. making a tight joint. In the other end of the glass elbow a dropping-funnel containing strong nitric acid is fitted by thrusting the stem of the funnel through a piece of rubber tube slipped over the end of the elbow. A roll of previously ignited asbestos paper 6 cm. long is inserted in the combustion-tube and so arranged that the glass elbow is pushed a short distance into its core. The rest of the tube is filled with broken bits of pumice-stone and the end closed with a cork carrying a small glass elbow, the other end of which is thrust some distance through a two-holed rubber stopper. The rubber stopper is inserted in the mouth of a large test-tube, kept cool by being immersed in water, and a delivery-tube connects the test-tube with the pneumatic trough. The combustion-tube is first strongly heated over a four-tube burner and concentrated nitric acid then allowed to drop slowly (10 to 15 drops per minute) into the glass elbow. If the tip of the dropping funnel is below the rubber connection, the rate of dropping may be easily determined. The nitric acid flows down the glass elbow and comes in contact with the asbestos coil. This, acting as a wick, conducts the liquid toward the warmer portion of the tube, where it is gradually vaporized. The vapor then passes over the heated pumice-stone and there undergoes decomposition. The water and nitrogen dioxide condense in the test-tube and the oxygen may be collected at the pneumatic trough. If the burners are so arranged that the asbestos roll is heated only at one end, i.e., that nearest the pumice-stone, by placing a burner directly under this end of the asbestos, a regular gradation of temperature is secured along the asbestos roll, which is very hot at the inner end and cool at the end nearer the cork. A roll of wire gauze may be wound around the outside of that portion of the combustion-tube which is occupied by the pumice-stone and consequently requires the highest heat. By use of the asbestos roll the contact of the liquid with hot glass is avoided, and the glass tube is therefore seldom broken. By allowing the acid to drop continually at a very slow rate the dropping-funnel acts as a safety-tube; for should the pressure inside the tube be materially increased, the dropping of the acid would cease.
Chemical lecture experiments, by F. G. Benedict, 225-227, 1916.
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NITROGEN DIOXIDE, Dinitrogen tetroxide, Dioxide, Nitrogen, dioxide, Nitrogen, NITROGEN TETROXIDE, Nitrogen oxide (NO2), CID3032552, D009585, 10102-44-0