Saturday, July 29, 2017
Friday, July 28, 2017
Again..and again...chemical warfare! Another warfare agent for psyco war is Phencyclidine; Some few months ago, my Mother saw on TV that there was a new drug that turned people on cannibals...here it is...(not new anyway...Deschloroketamine=2-Phenyl-2-(methylamino)cyclohexanone) You can purchase it all over the darkweb, on any parallel market, and all sort of internet suplliers. Here my goal is, terrorism.
Dissociative
Thursday, July 27, 2017
Good morning, worldwide! welcome back to war ! "3-Quinuclidinyl benzilate (QNB) — IUPAC name 1-azabicyclo[2.2.2]oct-3-yl 2-hydroxy-2,2-diphenylacetate; US Army code EA-2277; NATO code BZ; Soviet code Substance 78 — is an odorless military incapacitating agent.[1] BZ is a glycolate anticholinergic compound"...BZ is dispersed as an aerosol. It may be micropulverized for dissemination by a disperser (90% dissemination efficiency), or mixed with a pyrotechnic burning mixture for dissemination in burning munitions (70% dissemination efficiency)
Wednesday, July 26, 2017
cholera warfare bateria (to be used on aerosol explosive) preparation
welcome back to war Jihad! You have at least 6 guys on your secret lab, however the cartles and east mafia hv much more. Let's go for cholera preparation:
Thiosulphate Citrate Bile Salts Agar (TCBS)
(Oxoid designation is Cholera Medium TCBS)
Basic ingredients
Peptone 10,0 g
Yeast extract 5,0 g
Sodium citrate 10,0 g
Sodium thiosulfate.5 H2O (Na2S2O3•5 H2O) 10,0 g
Sodium chloride (NaCl) 10,0 g
Ox gall powder 5,0 g
Iron (III) citrate (FeC6H5O7) 1,0 g
Sodium cholate 3,0 g
Sucrose 20,0 g
Thymol Blue solution (0,2%) 20,0 ml
Bromothymol Blue solution (0,2%) 20,0 ml
Agar 15,0 g
Distilled water 1,0 L
pH 8,6 ± 0,2
Preparation
Mix all ingredients and apply heat until all goes into solution. DO NOT STERILIZE USING AUTOCLAVE. Allow to cool to 45-50°C and distribute.
Notes:
from http://www.disknet.com/indiana_biolab/b041.htm:
Peptones are the most widely used source of nitrogen in microbial media. Some are made by cooking milk or meat products in acid, but most are made by incubating milk or meat with trypsin, pepsin, or other proteolytic enzymes to digest the protein to a mixture of amino acids, peptides, and polypeptides. Many microbes, called proteolytic, can digest proteins, but most can't. The choice of peptone is sometimes of importance.
Some water-based inks contain ox gall (bile) as a dispersant. Pure ox gall can be obtained from art supply stores (eg. Winsor & Newton brand).
Sodium cholate, a bile salt, is used as an anionic detergent
http://www.sciencemadness.org/talk/viewthread.php?tid=1485&page=2
Thiosulphate Citrate Bile Salts Agar (TCBS)
(Oxoid designation is Cholera Medium TCBS)
Basic ingredients
Peptone 10,0 g
Yeast extract 5,0 g
Sodium citrate 10,0 g
Sodium thiosulfate.5 H2O (Na2S2O3•5 H2O) 10,0 g
Sodium chloride (NaCl) 10,0 g
Ox gall powder 5,0 g
Iron (III) citrate (FeC6H5O7) 1,0 g
Sodium cholate 3,0 g
Sucrose 20,0 g
Thymol Blue solution (0,2%) 20,0 ml
Bromothymol Blue solution (0,2%) 20,0 ml
Agar 15,0 g
Distilled water 1,0 L
pH 8,6 ± 0,2
Preparation
Mix all ingredients and apply heat until all goes into solution. DO NOT STERILIZE USING AUTOCLAVE. Allow to cool to 45-50°C and distribute.
Notes:
from http://www.disknet.com/indiana_biolab/b041.htm:
Peptones are the most widely used source of nitrogen in microbial media. Some are made by cooking milk or meat products in acid, but most are made by incubating milk or meat with trypsin, pepsin, or other proteolytic enzymes to digest the protein to a mixture of amino acids, peptides, and polypeptides. Many microbes, called proteolytic, can digest proteins, but most can't. The choice of peptone is sometimes of importance.
Some water-based inks contain ox gall (bile) as a dispersant. Pure ox gall can be obtained from art supply stores (eg. Winsor & Newton brand).
Sodium cholate, a bile salt, is used as an anionic detergent
http://www.sciencemadness.org/talk/viewthread.php?tid=1485&page=2
Tuesday, July 25, 2017
Hello worldwide! Welcome back to war! To tell you the truth, because I'm a newbie on chemistry, this phosgene warfare chemical agent its a piece of cake!!!!! Its the last phosgene gas, its called Choloropicrin! Here is the recipe : To the 5 liter flask 550 g calcium hypochlorite made into a paste in 1 liter water are placed. A paste of sodium picrate, made by mixing 50 g picric acid with 10 g sodium hydroxide and 250 ml water, is added with continuous stirring. The reaction is very rapid and is completed in about 30 min. To remove chloropicrin the reaction mixture is steam distilled until no more oily droplets come over. The oily distillate is separated from the water, dried over calcium chloride and redistilled. The yield is 70% of the theoretical. Chloropicrin is a slightly oily, colorless or yellow due to impurities liquid with a characteristic odor and with boiling point t 112° C.
Monday, July 24, 2017
PREPARATION OF HYDROGEN CYANIDE FROM POTASSIUM PERMANGANATE, METHANOL, SULFURIC ACID, AQUEOUS AMMONIA, AND POTASSIUM HYDROXIDE
Notes:
-all potassium chemicals can be substituted with their sodium parallel, if mass ratios have been properly adjusted
-it is highly recommended that nbk2000 dismiss all described and inferred safety precautions
PREPARATION OF POTASSIUM FORMATE (HCOOK) AND MANGANESE FORMATE (Mn(HCOO)2):
126.4 grams of potassium permanganate (KMnO4) is added to 32 grams (approximately 40.2mL) of concentrated methanol (CH3OH):
10(CH3OH) + 8(KMnO4) --} 10(HCOOH) + 10(H2O) + 8(MnO) + 4(K2O)
10(HCOOH) + 10(H2O) + 8(MnO) + 4(K2O) --} 10(HCOOH) + 8(KOH) + 8(MnO) + 6(H2O)
10(HCOOH) + 8(KOH) + 8(MnO) + 6(H2O) --} 8(HCOOK) + 2(HCOOH) + 8(MnO) + 14(H2O)
8(HCOOK) + 2(HCOOH) + 8(MnO) + 14(H2O) --} 8(HCOOK) + Mn(HCOO)2 + 7(MnO) + 15(H2O)
Mixture is then filtered to remove the manganese oxide (MnO), and the filtered solution is then allowed to evaporate. What is left is a ratio of eight : one of potassium formate : manganese formate. The remaining crystals should weight approximately 81.77 grams if you acheived a 100% yield.
PREPARATION OF FORMIC ACID (HCOOH):
The mixture of potassium formate and manganese formate is added to concentrated sulfuric acid. That is, all 81.77 grams of the potassium formate and manganese formate crystals are added to 49 grams (26.5mL) of concentrated sulfuric acid. The remaining mixture is heated, and the vapors, which are composed of formic acid, are condensed. WARNING! FORMIC ACID IS TOXIC. PURE FORMIC ACID IS A COLORLESS FUMING LIQUID WITH A PUNGENT ODOUR; IT IRRITATES THE MUCOUS MEMBRANES AND BLISTERS THE SKIN.
8(HCOOK) + Mn(HCOO)2 + 5(H2SO4) --} 10(HCOOH) + 4(K2SO4) + MnSO4
PREPARATION OF AMMONIUM FORMATE ( [HCOO-][NH4+] )
Formic acid is added to an aqueous solution of ammonia ( [NH4+][OH-] ). The remaining solution is evaporated; the crystals left are ammonium formate crystals. Crystals should weight about 64 grams if you have been achieving 100% yields.
HCOOH + [NH4+][OH-] --} [HCOO-][NH4+] + H2O
PREPARATION OF POTASSIUM CYANIDE (KCN):
The ammonium formate crystals are heated by flame in an environment containing as little oxygen gas as possible. The ammonium formate decomposes into formamide (HCONH2) which then decomposes into hydrogen cyanide.
[HCOO-][NH4+] --} HCONH2 + H2O
HCONH2 + H2O --} HCN + 2(H2O)
The gas given off is condensed in in a rubber, plastic, or, preferrably, glass tube that has one end immersed in a beaker containing a solution of potassium hydroxide (KOH). The tube should be positioned so that any liquids forming in it will run off into the beaker of potassium hydroxide. Some of the gas given off may not be condensed; that is why the tube is immersed in the beaker of potassium hydroxide. That will prevent a loss of much cyanide. The hydrogen cyanide will quickly react with the potassium hydroxide to form potassium cyanide. The hydrogen cyanide is reacted with the potassium hydroxide because the hydrogen cyanide will evaporate off quickly, which is both extremely dangerous and will cause the loss of a lot of cyanide. About 56.1 grams of potassium hydroxide should be used if 100% yields are expected. About 65.1 grams of potassium cyanide should result if 100% yields are achieved. The solution in the beaker, once all of the ammonium formate crystals have been converted into various gasses, should be evaporated off. The remaining crystals are potassium cyanide crystals.
HCN + KOH --} KCN + H2O
PREPARATION OF HYDROGEN CYANIDE (HCN) FROM POTASSIUM CYANIDE:
The potassium cyanide is then treated with an acid. This will form the potassium salt of the acid, and hydrogen cyanide. DO NOT ATTEMPT TO STORE HYDROGEN CYANIDE! IT WILL ALMOST CERTAINLY CAUSE THE DEATH OF AN UNINTENDED VICTIM SUCH AS YOURSELF! HYDROGEN CYANIDE SHOULD ALWAYS BE USED IMMEDIATELY AFTER IT IS MADE, OR CONVERTED IMMEDIATELY INTO POTASSIUM CYANIDE! It is recommended to use an acid that can be found concentrated. Concentrated sulfuric acid is believed to be the best acid to use.
KCN + [H+] --} HCN + [K+]
http://www.sciencemadness.org/talk/viewthread.php?tid=23
GET THE POTASSIUM CYANIDE ALREADY LABORATORY GRADE AT AN GOLD MINE EXTRACTION
-all potassium chemicals can be substituted with their sodium parallel, if mass ratios have been properly adjusted
-it is highly recommended that nbk2000 dismiss all described and inferred safety precautions
PREPARATION OF POTASSIUM FORMATE (HCOOK) AND MANGANESE FORMATE (Mn(HCOO)2):
126.4 grams of potassium permanganate (KMnO4) is added to 32 grams (approximately 40.2mL) of concentrated methanol (CH3OH):
10(CH3OH) + 8(KMnO4) --} 10(HCOOH) + 10(H2O) + 8(MnO) + 4(K2O)
10(HCOOH) + 10(H2O) + 8(MnO) + 4(K2O) --} 10(HCOOH) + 8(KOH) + 8(MnO) + 6(H2O)
10(HCOOH) + 8(KOH) + 8(MnO) + 6(H2O) --} 8(HCOOK) + 2(HCOOH) + 8(MnO) + 14(H2O)
8(HCOOK) + 2(HCOOH) + 8(MnO) + 14(H2O) --} 8(HCOOK) + Mn(HCOO)2 + 7(MnO) + 15(H2O)
Mixture is then filtered to remove the manganese oxide (MnO), and the filtered solution is then allowed to evaporate. What is left is a ratio of eight : one of potassium formate : manganese formate. The remaining crystals should weight approximately 81.77 grams if you acheived a 100% yield.
PREPARATION OF FORMIC ACID (HCOOH):
The mixture of potassium formate and manganese formate is added to concentrated sulfuric acid. That is, all 81.77 grams of the potassium formate and manganese formate crystals are added to 49 grams (26.5mL) of concentrated sulfuric acid. The remaining mixture is heated, and the vapors, which are composed of formic acid, are condensed. WARNING! FORMIC ACID IS TOXIC. PURE FORMIC ACID IS A COLORLESS FUMING LIQUID WITH A PUNGENT ODOUR; IT IRRITATES THE MUCOUS MEMBRANES AND BLISTERS THE SKIN.
8(HCOOK) + Mn(HCOO)2 + 5(H2SO4) --} 10(HCOOH) + 4(K2SO4) + MnSO4
PREPARATION OF AMMONIUM FORMATE ( [HCOO-][NH4+] )
Formic acid is added to an aqueous solution of ammonia ( [NH4+][OH-] ). The remaining solution is evaporated; the crystals left are ammonium formate crystals. Crystals should weight about 64 grams if you have been achieving 100% yields.
HCOOH + [NH4+][OH-] --} [HCOO-][NH4+] + H2O
PREPARATION OF POTASSIUM CYANIDE (KCN):
The ammonium formate crystals are heated by flame in an environment containing as little oxygen gas as possible. The ammonium formate decomposes into formamide (HCONH2) which then decomposes into hydrogen cyanide.
[HCOO-][NH4+] --} HCONH2 + H2O
HCONH2 + H2O --} HCN + 2(H2O)
The gas given off is condensed in in a rubber, plastic, or, preferrably, glass tube that has one end immersed in a beaker containing a solution of potassium hydroxide (KOH). The tube should be positioned so that any liquids forming in it will run off into the beaker of potassium hydroxide. Some of the gas given off may not be condensed; that is why the tube is immersed in the beaker of potassium hydroxide. That will prevent a loss of much cyanide. The hydrogen cyanide will quickly react with the potassium hydroxide to form potassium cyanide. The hydrogen cyanide is reacted with the potassium hydroxide because the hydrogen cyanide will evaporate off quickly, which is both extremely dangerous and will cause the loss of a lot of cyanide. About 56.1 grams of potassium hydroxide should be used if 100% yields are expected. About 65.1 grams of potassium cyanide should result if 100% yields are achieved. The solution in the beaker, once all of the ammonium formate crystals have been converted into various gasses, should be evaporated off. The remaining crystals are potassium cyanide crystals.
HCN + KOH --} KCN + H2O
PREPARATION OF HYDROGEN CYANIDE (HCN) FROM POTASSIUM CYANIDE:
The potassium cyanide is then treated with an acid. This will form the potassium salt of the acid, and hydrogen cyanide. DO NOT ATTEMPT TO STORE HYDROGEN CYANIDE! IT WILL ALMOST CERTAINLY CAUSE THE DEATH OF AN UNINTENDED VICTIM SUCH AS YOURSELF! HYDROGEN CYANIDE SHOULD ALWAYS BE USED IMMEDIATELY AFTER IT IS MADE, OR CONVERTED IMMEDIATELY INTO POTASSIUM CYANIDE! It is recommended to use an acid that can be found concentrated. Concentrated sulfuric acid is believed to be the best acid to use.
KCN + [H+] --} HCN + [K+]
http://www.sciencemadness.org/talk/viewthread.php?tid=23
GET THE POTASSIUM CYANIDE ALREADY LABORATORY GRADE AT AN GOLD MINE EXTRACTION
WELCOME BACK TO WAR! good morning worldwide! Another chemical gas warfare agent : Hydrogen Cyanide ! Preparation: All work MUST be done in a ventilated hood! To the round bottom, flask fitted with dropping funnel and gas outlet tube 100 g carbonate-free potassium cyanide are placed. The gas outlet tube leads to two U tubes in series which are filled with a mixture of fused and granular calcium chloride, and immersed in a water-bath at 35° C. The second of these U tubes may be connected to two more U tubes, the first of which is maintained at about — 10° C in a freezing mixture and the second at + 20° C. Each of these tubes, which are designed to receive the condensate of hydrogen cyanide formed in the reaction, is fitted at the bottom with a glass lead-off tube. This is connected through a glass cock to a cooled flask in which the liquid hydrogen cyanide collects. Before the synthesis a current of dry air is passed through the whole of the apparatus. Cooled aqueous sulfuric acid (1 : 1) is allowed to drop slowly through the dropping-funnel on to the potassium cyanide, regulating the rate of addition so that 1 drop of hydrogen cyanide condenses in the first receiver every second minute. Towards the end of the reaction it may be necessary to gently heat the contents of the flask. The greater part of the hydrogen cyanide produced in the reaction condenses in the first U tube and is collected in the corresponding flask. Pure anhydrous hydrogen cyanide is a clear colorless liquid with a peculiar odor of bitter almonds. It boils at 26.5° C, and solidifies on cooling at — 13.4° C, forming a crystalline mass which melts at — 15° C.
Sunday, July 23, 2017
Preparation of Hydrazine Sulfate (Rosco Bodine)
A. Reagents
355 mL of 10wt% NaOCl solution (0.55 mole)
47.8g of NaOH (1.20 mole)
34.1g of urea (0.57 mole)
0.47g gelatine
122 mL of 31% HCl (1.18 mole)
37.5mL of conc (92%) H2SO4 (0.64 mole)
30mL of 70% isopropyl alcohol
15mL of anhydrous isopropyl alcohol
water
B. Equipment
fume hood
1 quart jar with threaded lid
1-liter mL Erlenmeyer flask
250 mL pressure-equalizing (P-E) dropping funnel
24/40 to 19/22 reducing adaptor
24/40 Keck clamp
#9 rubber stopper with ½” dia hole
2 quart plastic funnel
plastic plate to cover mouth of funnel
magnetic stirrer/hotplate
3” magnetic stir bar
15cm Buchner funnel with filter paper
fridge for cooling to at least 8ºC (46ºF)
freezer
thermometer
small watch glass for the 1-liter E. flask
small watch glass for P-E dropping funnel fill port
bowl for use as a cooling pan for the 1-liter E. flask
ceramic dinner plate
ringstand with clamp for P-E dropping funnel
25mL beaker
250mL beaker
stirring rod
125mL Erlenmeyer flask w/stopper
250mL Erlenmeyer flask w/stopper
C. Cautions
1. Hydrazine is highly toxic.
2. Hydrazine is an environmental hazard.
3. Hydrazine is flammable.
4. Hydrazine is destroyed by air.
D. Procedure
a. Prepare the Cold NaOCl/NaOH Solution
1. Place 355mL of 10% NaOCl solution in a 1-quart jar with screw cap and cool to at least 8°C (46°F) in a fridge (or freezer).
2. Using a magnetic stirrer mix in NaOH to the cooled NaOCl solution in two 23.9g portions, cooling in between to 8°C. Try not to let the temperature rise above 20°C. Then chill in the fridge to 5-8°C.
b. Prepare the Urea/Gelatine Solution
1. Place 3mL of water in a 25mL beaker. Sprinkle in the 0.47g of gelatine, breaking it up and dispersing it with a stirring rod. Add 15mL of boiling water and stir the gelatine until dissolved.
2. Add 20mL of hot water to a 250mL beaker. Then add 34.1g of urea and stir until dissolved.
3. Pour the gelatine solution into the urea solution and stir until mixed.
c. Form the Hydrazine Solution
This is to be done in the hood as hydrazine is toxic.
(H2N)2C=O + NaOCl + 2 NaOH → N2H4 + H2O + NaCl + Na2CO3
(Hofmann degradation)
Note: A viscous, voluminous foam will be quickly formed in the following reaction. Vigorous action by the large magnetic stir bar will help keep it beaten down.
1. Place the 3” stir bar in the 1-liter E. flask and place on the magnetic stirrer/hotplate.
Insert the plastic funnel in the one-hole stopper.
Note: The following reaction should be allowed to take place for a few minutes before supplemental heating is applied. As the foam begins to dissipate heat is to be applied to steadily drive the reaction to completion at boiling.
2. Retrieve the hypochlorite solution from the freezer.
3. When the hypochlorite solution has warmed to 5-8°C, set the stir bar at speed 3 and pour the hypochlorite solution into the E. flask. Install the plastic funnel w/stopper in the E. flask. Then quickly pour in the urea/gelatine solution through the funnel into the vortex. Immediately raise the stir bar speed as required.
4. Cover the funnel with a plastic plate. The reaction initiates immediately and a snow white foam will rise to fill the flask to about the 900mL level, but possibly may even overflow into the funnel. After a few minutes the foam will begin to subside and the solution will turn translucent orange, and heat up. Turn down the stir rate to prevent foam generation. Apply heat steadily to drive the solution to boiling. The color will fade to a pale yellow then to almost clear. The clear color indicates the endpoint of the reaction. At this point heating is stopped.
5. Remove the overflow funnel and place a small watch glass over the mouth of the flask to exclude air. The watch glass will allow any CO2 to escape and also prevent a vacuum from forming. Cool the flask well in an ice bath. This is in preparation for the neutralization, during which an exotherm will be generated.
d. Neutralization with HCl
This should be done in the hood as considerable CO2 is released.
2HCl + Na2CO3 --> 2NaCl + CO2 + H2O + heat
1. While the reaction mixture is cooling measure out 122 mL of 31% HCl into a 250 mL E. flask, stopper, and place in the freezer to cool.
2. Prepare a diluted sulfuric acid solution of 38mLs of conc sulfuric acid diluted with 33 mLs of water in a 125mL E. flask. Stopper and place in the freezer to prepare for the formation of the hydrazine sulfate.
3. Attach a 24/40 to 19/22 adaptor to a 250 mL pressure-equalizing dropping funnel using a Keck clamp. Insert the outlet of the adaptor into the #9 one-holed stopper. Support the addition funnel with a ringstand and clamp and insert the stopper in the 1-liter E. flask. Add the cooled HCl from the freezer to the P-E dropping funnel (valve closed!). Place a small watch glass over the fill port of the P-E dropping funnel. This excludes air, which destroys hydrazine, yet allows the CO2 to escape as the HCl is being added. Add the HCl at 1 drop/sec to the hydrazine solution stirred on the stirrer/hotplate. The mixture will warm up.
e. Formation of Hydrazine Sulfate
NH2-NH2 + H2SO4 --> [N2H5]HSO4
1. Close the valve on the P-E dropping funnel and add the cooled/diluted sulfuric acid.
2. To the rapidly stirring mixture add the dilute sulfuric acid at 2 drops/sec. Reduce the drip rate to control foaming if necessary.
3. Continue stirring and slow the drip rate to about 1 drop/sec as crystals of hydrazine sulfate begin to appear. Stir for one hour past the addition point.
4. Place a small watch glass on the mouth of the E. flask and set aside in a cool place overnight. CO2 may continue to vent.
5. Just prior to filtering the crystals cool the flask in an ice bath for at least an hour.
f. Filtering the Crystals
1. Set up the 15cm Buchner funnel with filter paper for vacuum filtration.
2. Stir the E. flask to loosen any CO2 bubbles and clumps of crystals.
3. Remove the stir bar from the flask.
4. Decant the supernate and save it for washing crystals out of the flask.
5. Pour the crystal slurry onto the Buchner funnel and suck the supernate from the crystals.
6. Flood the wet but drained crystals with 30 mL of 70% isopropyl alcohol, stirring with a stirring rod.
7. Use a final rinse of 15 mL of anhydrous isopropyl alcohol
8. Remove the filter paper with crystals and wick away any excess liquid on a blotter paper or paper towels.
9. Air dry the crystals on a dinner plate.
E. Expected Yield
The expected yield for Mr. A’s full scale batch is about 60% based on the amount of hypochlorite used. For this reduced scale that would be 41 to 44g (0.33 mole). MP of hydrazine sulfate is 254 °C per the Baker MSDS.
F. References
1. Improved procedure of Mr. Anonymous, posted on SM 6/7/2003.
2. SM post of garage chemist on 5/19/07 providing an improvement and a reduced scale.
3. Merck patent GB392845, upon which Mr. A’s procedure is based.
4. Wikipedia entries for “hydrazine” and “Hofmann degradation.”
http://www.sciencemadness.org/talk/viewthread.php?tid=15091
355 mL of 10wt% NaOCl solution (0.55 mole)
47.8g of NaOH (1.20 mole)
34.1g of urea (0.57 mole)
0.47g gelatine
122 mL of 31% HCl (1.18 mole)
37.5mL of conc (92%) H2SO4 (0.64 mole)
30mL of 70% isopropyl alcohol
15mL of anhydrous isopropyl alcohol
water
B. Equipment
fume hood
1 quart jar with threaded lid
1-liter mL Erlenmeyer flask
250 mL pressure-equalizing (P-E) dropping funnel
24/40 to 19/22 reducing adaptor
24/40 Keck clamp
#9 rubber stopper with ½” dia hole
2 quart plastic funnel
plastic plate to cover mouth of funnel
magnetic stirrer/hotplate
3” magnetic stir bar
15cm Buchner funnel with filter paper
fridge for cooling to at least 8ºC (46ºF)
freezer
thermometer
small watch glass for the 1-liter E. flask
small watch glass for P-E dropping funnel fill port
bowl for use as a cooling pan for the 1-liter E. flask
ceramic dinner plate
ringstand with clamp for P-E dropping funnel
25mL beaker
250mL beaker
stirring rod
125mL Erlenmeyer flask w/stopper
250mL Erlenmeyer flask w/stopper
C. Cautions
1. Hydrazine is highly toxic.
2. Hydrazine is an environmental hazard.
3. Hydrazine is flammable.
4. Hydrazine is destroyed by air.
D. Procedure
a. Prepare the Cold NaOCl/NaOH Solution
1. Place 355mL of 10% NaOCl solution in a 1-quart jar with screw cap and cool to at least 8°C (46°F) in a fridge (or freezer).
2. Using a magnetic stirrer mix in NaOH to the cooled NaOCl solution in two 23.9g portions, cooling in between to 8°C. Try not to let the temperature rise above 20°C. Then chill in the fridge to 5-8°C.
b. Prepare the Urea/Gelatine Solution
1. Place 3mL of water in a 25mL beaker. Sprinkle in the 0.47g of gelatine, breaking it up and dispersing it with a stirring rod. Add 15mL of boiling water and stir the gelatine until dissolved.
2. Add 20mL of hot water to a 250mL beaker. Then add 34.1g of urea and stir until dissolved.
3. Pour the gelatine solution into the urea solution and stir until mixed.
c. Form the Hydrazine Solution
This is to be done in the hood as hydrazine is toxic.
(H2N)2C=O + NaOCl + 2 NaOH → N2H4 + H2O + NaCl + Na2CO3
(Hofmann degradation)
Note: A viscous, voluminous foam will be quickly formed in the following reaction. Vigorous action by the large magnetic stir bar will help keep it beaten down.
1. Place the 3” stir bar in the 1-liter E. flask and place on the magnetic stirrer/hotplate.
Insert the plastic funnel in the one-hole stopper.
Note: The following reaction should be allowed to take place for a few minutes before supplemental heating is applied. As the foam begins to dissipate heat is to be applied to steadily drive the reaction to completion at boiling.
2. Retrieve the hypochlorite solution from the freezer.
3. When the hypochlorite solution has warmed to 5-8°C, set the stir bar at speed 3 and pour the hypochlorite solution into the E. flask. Install the plastic funnel w/stopper in the E. flask. Then quickly pour in the urea/gelatine solution through the funnel into the vortex. Immediately raise the stir bar speed as required.
4. Cover the funnel with a plastic plate. The reaction initiates immediately and a snow white foam will rise to fill the flask to about the 900mL level, but possibly may even overflow into the funnel. After a few minutes the foam will begin to subside and the solution will turn translucent orange, and heat up. Turn down the stir rate to prevent foam generation. Apply heat steadily to drive the solution to boiling. The color will fade to a pale yellow then to almost clear. The clear color indicates the endpoint of the reaction. At this point heating is stopped.
5. Remove the overflow funnel and place a small watch glass over the mouth of the flask to exclude air. The watch glass will allow any CO2 to escape and also prevent a vacuum from forming. Cool the flask well in an ice bath. This is in preparation for the neutralization, during which an exotherm will be generated.
d. Neutralization with HCl
This should be done in the hood as considerable CO2 is released.
2HCl + Na2CO3 --> 2NaCl + CO2 + H2O + heat
1. While the reaction mixture is cooling measure out 122 mL of 31% HCl into a 250 mL E. flask, stopper, and place in the freezer to cool.
2. Prepare a diluted sulfuric acid solution of 38mLs of conc sulfuric acid diluted with 33 mLs of water in a 125mL E. flask. Stopper and place in the freezer to prepare for the formation of the hydrazine sulfate.
3. Attach a 24/40 to 19/22 adaptor to a 250 mL pressure-equalizing dropping funnel using a Keck clamp. Insert the outlet of the adaptor into the #9 one-holed stopper. Support the addition funnel with a ringstand and clamp and insert the stopper in the 1-liter E. flask. Add the cooled HCl from the freezer to the P-E dropping funnel (valve closed!). Place a small watch glass over the fill port of the P-E dropping funnel. This excludes air, which destroys hydrazine, yet allows the CO2 to escape as the HCl is being added. Add the HCl at 1 drop/sec to the hydrazine solution stirred on the stirrer/hotplate. The mixture will warm up.
e. Formation of Hydrazine Sulfate
NH2-NH2 + H2SO4 --> [N2H5]HSO4
1. Close the valve on the P-E dropping funnel and add the cooled/diluted sulfuric acid.
2. To the rapidly stirring mixture add the dilute sulfuric acid at 2 drops/sec. Reduce the drip rate to control foaming if necessary.
3. Continue stirring and slow the drip rate to about 1 drop/sec as crystals of hydrazine sulfate begin to appear. Stir for one hour past the addition point.
4. Place a small watch glass on the mouth of the E. flask and set aside in a cool place overnight. CO2 may continue to vent.
5. Just prior to filtering the crystals cool the flask in an ice bath for at least an hour.
f. Filtering the Crystals
1. Set up the 15cm Buchner funnel with filter paper for vacuum filtration.
2. Stir the E. flask to loosen any CO2 bubbles and clumps of crystals.
3. Remove the stir bar from the flask.
4. Decant the supernate and save it for washing crystals out of the flask.
5. Pour the crystal slurry onto the Buchner funnel and suck the supernate from the crystals.
6. Flood the wet but drained crystals with 30 mL of 70% isopropyl alcohol, stirring with a stirring rod.
7. Use a final rinse of 15 mL of anhydrous isopropyl alcohol
8. Remove the filter paper with crystals and wick away any excess liquid on a blotter paper or paper towels.
9. Air dry the crystals on a dinner plate.
E. Expected Yield
The expected yield for Mr. A’s full scale batch is about 60% based on the amount of hypochlorite used. For this reduced scale that would be 41 to 44g (0.33 mole). MP of hydrazine sulfate is 254 °C per the Baker MSDS.
F. References
1. Improved procedure of Mr. Anonymous, posted on SM 6/7/2003.
2. SM post of garage chemist on 5/19/07 providing an improvement and a reduced scale.
3. Merck patent GB392845, upon which Mr. A’s procedure is based.
4. Wikipedia entries for “hydrazine” and “Hofmann degradation.”
http://www.sciencemadness.org/talk/viewthread.php?tid=15091
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