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Common Calculations

Molarity (given density and % composition) = (Density in grams per liter)(% concentration / 100) / (Molar Mass of Solute)

The Synthesis of Aqua Regia

Rxn 1. HNO3 + HCl → NOCl + 2H2
Rxn 2. 2NOCl 2NO + Cl2

Combine the acids together in the correct proportions and mix thoroughly. The acid solution will change to a golden yellow or orangish color. Once this is complete the Aqua Regia is ready for use. Aqua Regia must always be made fresh before use as it rapidly decomposes over a matter of hours.

Piranha Solutions - Acidic and Basic

Ensure that minimal residue remains on the glassware. Add the hydrogen peroxide to the sulfuric acid or concentrated ammonia (not the other way around) with good stirring to prevent temperature spikes that could cause boiling. Always prepare fresh before use. 

Chromosulfuric Acid Solution for Cleaning Glassware

Combine the chromate salt with enough distilled water to make a paste. Slowly add the sulfuric acid to the paste and stir until an homogenous paste forms. The chromic acid wash is used to decompose organic residues  as well as some mineral deposits. Use this wash until it turns green (CrVI → CrIII). Heavily soiled items may need soaking overnight to be cleaned. Use of this wash will contaminate glassware with heavy metal ions which may interfere with some experiments.  Chromic acid burns are treated with dilute aqueous solutions of sodium thiosulfate.

Synthesis of Elemental Iodine (Source: NurdRage)

2HCl + 2KI + 2H2O2 → I2(s) + 2KCl + 2H2O + Δ

  1. Add the KI to a 150 mL beaker and dissolve it into 10 mL of distilled water with gentle heating.
  2. Add the concentrated HCl to the solution in the beaker with stirring. A pale yellow suspension will form.
  3. Slowly add the hydrogen peroxide to beaker with stirring. This reaction is exothermic and care should be taken to minimize the formation of I2 vapor.
  4. The solid iodine is filtered off and washed once with ice water.
  5. The iodine is dried on top of some folded paper towels before being pressed between more folded paper towels to dry it as much as possible and squeeze the iodine into solid chunks.
  6. The iodine is then placed into a clean beaker and enough 98% sulfuric acid is added to cover the iodine.
  7. The beaker is heated until the iodine melts. The melt is allowed to sit under the hot, concentrated sulfuric acid for a short time before the heat is turned off.
  8. The sulfuric acid is decanted and as it will be full of iodine crystals is saved for iodine recycling. The chunks of iodine are dried and bottled.

Synthesis of Azeotropic Nitric Acid (Source: Nile Red)

KNO3 + H2SO4 → KHSO4 + HNO3


  1. Set up for distillation using a 300mm or longer Liebig condenser cooled with ice water. The use of a short Vigreux column is recommended to capture sulfuric acid aerosols which will contaminate the crude product. These aerosols are kicked up by stirring and boiling of the reaction mixture and thus are to some extent unavoidable.
  2. Dissolve the nitrate salt into the water in a one liter boiling flask.
  3. With strong stirring slowly and carefully add the 98% H2SO4 to the nitrate solution. Connect the boiling flask to the distillation train.
  4. Turn on slow stirring and high heat. At first dilute nitric acid comes over at a temperature near the boiling point of water. The total amount of dilute nitric acid that distills over is about 175-200 mL.
  5. Next concentrated nitric acid comes over. The temperature will rise to about 121oC and brown NO2 gas will fill the distillation apparatus. The total amount of concentrated nitric acid that distills over is 175-200 mL.
  6. Once the distillation is complete about 400 nmL of ~30% nitric acid will be in the receiver. This nitric acid will be contaminated to some degree with sulfuric acid. If desired this can be tested for by combining a few drops of the distillate with a few drops of aqueous barium nitrate. A white precipitate indicates the presence of sulfate ion.
  7. Fractionally distill the distillate using a 400 mL Vigreux column and collect that portion that comes over above 120.5 oC. This will be the azeotropic nitric acid. 

Synthesis of Fuming Nitric Acid (Source: Nile Red)

KNO3 + H2SO4 → KHSO4 + HNO3

Distill this as described in the azeotropic nitric acid synthesis above. Pure HNO3 boils at 83 oC and is degraded by heat. The yield of fuming nitric acid is approximately 25 mL to 30 mL. This can be fractionally distilled itself if sulfuric acid contamination is a problem. This can be tested for as described under the azeotropic nitric acid synthesis however in this instance the filtrate should be diluted with 5 times it's volume in water and then tested with barium nitrate solution. The reason for the dilution is that barium sulfate is soluble in concentrated strong acids so they must be diluted before testing. Red fuming nitric acid can be converted to white fuming nitric acid by removing dissolved NOx species at reduced pressure. To carry out this operation the red fuming nitric acid is subjected to a pressure of 200 mmHg (26.664 kilopascals) for 10 to 30 minutes.

Synthesis of Potassium Iodate (Source: ChemPlayer)

Net Equation: 2KClO3 + I2 → 2KIO3 + Cl2(g)


  1. Dissolve the potassium chlorate into the water. Heating will be necessary and the temperature shoud be about 80 oC by the time the potassium chlorate dissolves.
  2. Add the I2 crystals to the KClO3 solution followed by the azeotropic HNO3 catalyst. The solution should turn a browish purple color.
  3. Add a stir bar to the flask and cover the flask to prevent I2 from escaping.
  4. Stir the mixture and maintain it at temp of 88 oC. Do not allow the temp to exceed 90 oC as unwanted side products will form (i.e. ClO4 from the disproportionation reaction of ClO3-)
  5. Once all of the iodine has reacted the solution will become clear. Uncover the flask and allow the solution to boil for 5 minutes to drive out the Cl2 produced by the reaction
  6. Remove the solution from heat, cover the flask with plastic wrap, and place it in an ice bath that has been salted with NaCl.
  7. Add flakes of solid KOH bit by bit until the solution is weakly alkaline in order to neutralize the iodic acid which is the actual product of the reaction. 
    1. NaOH should not be used in place of KOH.
  8. Chill the mixture to approximately 2 oC and filter out the precipitate using vacuum filtration.
  9. Wash the precipitate sparingly with ice water and dry the product as much as possible. Save the filtrate for a second round of crystallization.

Recycling of Silver Metal 

  1. Take the raw material containing the silver to be recycled and boil it in the nitric acid until all of the silver has been converted to silver nitrate.
  2. Filter off the silver nitrate extract.
  3. Add enough of the NaCl solution to precipitate all of the silver as silver chloride.
  4. Allow the silver chloride to settle out of the liquid and decant off all but the top 2-3 cm of the clear water from above the precipitate.
  5. With stirring slowly add solid flakes of NaOH to the liquid in which the silver chloride is suspended. The end point is reached when no more black disilver monoxide is produced.
  6. Add the finely powdered sucrose to the still stirring liquid to precipitate silver metal powder.

Synthesis of Elemental Bromine  (Source: Nile Red)

TCCA + 6NaBr + 3H+  Cyanuric Acid + 3Br2 + 3Cl-+ 6Na+

  1. Combine the H2O, NaBr, and TCCA in a one liter flask. Set up for simple distillation and lute the joints of the apparatus with 98% sulfuric acid. 
  2. After thoroughly stirring the contents of the flask into a homogenous mix add the HCl to the flask. Quickly attach the boiling flask to the distillation train and add ice to the coolant reservoir if it has not already been done. 
  3. The heat is turned on high and the distillation is continued until the red color has left the boiling flask. The material in the flask should be a pale yellow when the distillation is completed. 
  4. The distillate is transferred to a separatory funnel and the bottom layer of Br2 is drained off into another separatory funnel. 
  5. Add 25 mL of 98% H2SO4 to the Br2 in the separatory funnel. Close the flask, shake gently, and vent frequently to avoid pressure building up in the flask. As the process continues less and less vapor is generated and the ventings become less energetic but do not neglect venting the flask for any reason. 
  6. Allow the contents of the funnel to settle and separate thoroughly. The dry dibromine is drained into a bottle specifically designed to hold volatile, reactive chemicals or it is partitioned into glass ampoules. 

Synthesis of Hydrobromic Acid #1 (Source: NurdRage)

NaHSO4 + NaBr  HBr(aq) + Na2SO4

  1. Combine all of the reagents into a beaker and stir until all of the granules are dissolved. If some cloudiness remains that is alright so long as the granules dissolve. Heating will facilitate dissolution.
  2. After all of the solids dissolve cover the beaker with plastic wrap and chill overnight. This will precipitate the sodium sulfate product of the reaction which has a low solubility at low temperatures. 
  3. Filter out the liquid and then distill its entire volume to remove the remaining Na2SO4 and isolate the aqueous HBr. 
  4. Fractionally distill the distillate taking care not to overheat and degrade the azeotropic HBr. 

Azeotropic HBr boils at 124.3 oC at STP and corresponds to a concentration of 47.6% HBr by weight. Its density is 1.486 grams / mL. Hydrobromic acid may be kept colorless for long periods of time by storage in a dark bottle in the refrigerator.

Synthesis of Hydrobromic Acid #2 (Source:

Rxn 1. 2S + Br2 → S2Br2
Rxn 2. S2Br2 + 5Br2 + 8H2O → 12HBr + 2H2SO4

  1. One hundred and fifty grams of bromine are weighed into a glass-stoppered bottle in the hood and 10 g of powdered sulfur are quickly introduced. The bottle is then agitated and the sulfur rapidly dissolves to yield a red oily liquid.
  2. Two hundred grams of ice are placed in a 500 ml glass-stoppered bottle and the vessel is immersed in ice. About one-third of the sulfur-bromine mixture is added; over the course of about one hour the red oil disappears. Cooling in plain water is maintained throughout the hydrolysis. 
  3. The second third of the sulfur-bromine compound is now added, followed by the last portion about 30 minutes later.When all the mate­rial has dissolved and reacted, a pale yellow liquid remains which is fractionally distilled as usual. Yield is about 300 g of HBr. 
    1. YouTube demo of the synthesis
    2. BitChute demo of the synthesis 

Synthesis of Potassium Bromate and Potassium Bromide (Source:

Rxn 1. Br2 + OH- → Br- + H2O + BrO-
Rxn 2. 3BrO- → 2Br- + BrO3-

  1. Combine the KOH and the 200 mL of water in a one liter beaker. Cool the resulting 5M KOH solution to room temperature. 
  2. Turn on stirring and begin adding the bromine in ~1 mL increments. On the first addition the solution turns yellow. Afterwards it will turn red as a portion of Br2 is added before quickly changing back to yellow. At the end of the reaction the red color will remain and this will be followed shortly by the precipitation of KBrO3.
  3. The solution is then heated to boiling to expel excess bromine. The yellow color will remain but the smell of bromine diminishes. 
  4. Once this is completed transfer the beaker to an ice bath and cool the contents to 10 oC. 
  5. Obtain the crude potassium bromate by filtration. Save the filtrate for the KBr synthesis. 
  6. Dissolve the potassium bromate in four times its mass of boiling water and then chill back to 10 oC. Filter the recrystallized KBrO3 and dry. Make sure to save this filtrate as well for the KBr synthesis.
  7. If an even higher purity is desired repeat the recrystallization steps. To test the KBrO3 for purity take a drop of an aqueous solution of the potassium bromate product and add a drop of aqueous silver bromide to it. If KBr is still present a white precipitate of AgBr will form. 
  8. Combine the filtrates from steps 5 and 6 and boil the solution down to a white, salty paste. 
  9. Mix the paste with the powdered charcoal and "heat to redness in an iron crucible for 20 minutes". This will not only destroy the KBrO3 contaminant in the filtrate paste but it will also convert it into KBr thus increasing the yield of the KBr product. The KBr/KBrO3/charcoal mix will start off black but by the end of this calcination step it will have been converted into a grayish-white solid. 
  10. Allow the solid material in the crucible to cool to room temperature and then mix it with water. This mix is boiled for ~5 minutes and then filtered to remove all particulates suspended in the solution.
  11. Boil the filtrate down to obtain crude KBr crystals. These crystals should be tested for the presence of bromate.
    1. To do this add a drop of 98% sulfuric acid to a few drops of the hot, concentrated filtrate. An orange color caused by the formation of Br2 is a positive test for bromate.
    2. Another test for bromate is to combine a few drops of a cold, concentrated solution of the KBr product with a few drops of BaCl2 solution. A white to slightly yellow precipitate confirms the presence of bromate. 
  12. The KBr crystals can be further purified if necessary by grinding the crystals up, combining them with 10 grams of charcoal, and repeating steps 9 through 11. Once the crude KBr has been established to be free of bromate it can be recrystallized from distilled water. 

Synthesis of Alkyl Nitrite Esters (A General Reaction Illustrated with n-Butyl Nitrite) (Source: DougsLab)


  1. Chill the HCl and the 70% butanol solutions down to ice cold. Transfer the cold BuOH to an ice bath equipped with magnetic stirring.
  2. Slowly add the sodium nitrite to the chilled alcohol and allow the mixture to stir. The sodium nitrite may or may not fully dissolve.
  3. Add the HCl solution to the chilled alcohol solution ~0.5 mL at a time with vigorous stirring. The addition of the HCl produces blue nitrous acid which disappears as it reacts with the alcohol to produce the nitrite ester. 
  4. Stir for 5 to 10 minutes after adding all of the HCl.
  5. Transfer as much of the oil and as little of the solid as possible to a separatory funnel containing 40 mL of distilled water. 
  6. Swirl gently and then drain the water layer and discard.
  7. Add the saturated NaCl solution to the separatory funnel and swirl gently several times in order to remove water from the alkyl nitrite. Be careful not to vaporize the product on the room temperature walls of the separatory funnel. 
  8. Drain the sodium chloride solution completely and transfer the n-butyl nitrite to an air-tight amber bottle 
    1. YouTube demo of the synthesis
    2. BitChute demo of the synthesis

Synthesis of Ammonium Metavanadate (Source: NileRed)

Rxn 1. V2O5 + Na2CO3 + Δ → NaVO3 + CO2
Rxn 2. NaVO3 + NH4Cl → NH4VO3(s) + NaCl(aq)

  1. Prepare the sodium carbonate solution and heat it to 90 oC.
  2. Add the V2O5 to the solution slowly to minimize CO2 production. 
  3. Add about 150 mL of water to the mixture. The solution should have a yellow color at this point.
  4. Filter the solution into a clean beaker.
  5. Add the ammonium chloride solution to the filtrate. 
  6. Stir thoroughly and allow the solution to cool. Cover the beaker and chill the solution to precipitate the ammonium metavanadate. This precipitation step can take several days to complete.
  7. If crystallization does not occur after a few days add about 5 grams of ammonium chloride to the solution with stirring. 
  8. Chill the filtrate on ice.
  9. Filter off the product and wash with ice water. The NH4VO3 tends not to crystallize without having to carry out step 7. It appears as a whitish crust on the beaker walls. Dry the product and store normally.

Dragendorff's Reagent

Stock Solution: Dissolve the KI into 50 mL of water to create a 50% solution. In a separate beaker dissolve the bismuth subnitrate into the 20 mL of glacial acetic acid and 80 mL of water. Combine this with the KI solution and transfer the stock solution to an amber bottle for storage. This stock will keep indefinitely if well stored.
Working Solution: Combine 10 mL of the stock solution with 20 mL of glacial acetic acid and then bring up to a total volume of 100 mL with distilled water.

Dragendorff's Reagent is potassium tetraiodobismuthate (CAS 41944-01-8). It reacts with tertiary amines to form an insoluble complex which manifests as an orange to yellow precipitate. The reagent can be tested before analytical use by reacting it with a sample of nicotine (bright orange ppt), triethylamine (bright orange ppt) and a sample of hexamine (bright yellow ppt).

Beam's CBD Reagent (Source: Wikipedia)

This reagent is made up by dissolving 5% KOH in 95% ethanol.

Solid samples should be finely divided before testing. Place the sample in a test tube and add a few milliliters of the reagent. Samples containing CBD will exhibit a purplish color after approximately 10 minutes. Temperature extremes will have an effect on the time needed for the reaction to occur. This test is specific to CBD and THC does not react.

0.01N Dimethylglyoxime and 0.5 M Dimethylglyoxime in 1 M NaOH

Dissolve 0.6 grams of dimethylglyoxime in 500 mL of 95% ethanol to produce the 0.01N solution. This reagent forms a bright red complex with nickel ions and a yellow complex with palladium ions. In acidic solutions palladium can be precipitated selectively from nickel whereas in alkaline solutions nickel will precipitate. When the goal is to precipitate palladium from other noble metals an aqueous dimethylglyoxime solution in NaOH is usually preferred. To prepare a 0.5 molar dimethylglyoxime solution in 1M NaOH start with 4g NaOH dissolved in 100 ml distilled water, then add 5.81 g dimethylglyoxime and filter when it has dissolved. To precipitate 1.00 g of palladium 2.5 grams of dimethylglyoxime is used and this corresponds to 43 ml of the above alkaline solution. When using the alkaline solution the pH value of the sample containing the dissolved palladium cations must be kept acidic to keep nickel from precipitating if it is present.

Marquis' Reagent (Source: Wikipedia and experimental data)

Dissolve 10 mL of 37% formaldehyde in 50 mL of 98% H2SO4. An alternate formulation is 5 ml of 40% formaldehyde in 95-98% H2SO4. Methanol may be added to slow down the color changing polymerization reaction. Color change table for Marquis' Reagent.

  1. The Marquis' Test results develop very quickly and due to reactions with moisture and oxygen in air. Any changes after the first 60 seconds should be discarded (note that this window may need to be adjusted if methanol was added to slow down the reaction). If the reagent is to be kept for any period of time it should be stored in a freezer in order to maximize shelf life. The reagent can be tested before analytical use by reacting it with a small sample of two or more of the following:
    1. Acetylsalicylic Acid (Aspirin) = Bright Red
    2. Ascorbic Acid (Vitamin C) = No Reaction
    3. Granulated Sugar = Brown  → Rapid Black
    4. Butylated Hydroxytoluene = Brown → Rapid Reddish-Black
    5. Disodium EDTA = No Reaction
    6. Triphenylphosphine = No Reaction
    7. Tryptophan = Brown → Rapid Black
    8. Camphor = Bubbling → Rapid Brownish-Yellow
    9. Indole-3-Acetic Acid = Yellow  → Dark Brown
    10. Hydroquinone = Brownish-Black
    11. Sodium Chloride = Bubbling 
    12. Dimethylglyoxime = Slow Orange
    13. para-Dimethylaminobenzaldehyde = Dissolves but no reaction. 
    14. Hexamine = No reaction.
    15. Phenylacetic Acid = Rapid Yellow → Orange  → Brown  → Dark Brown
    16. Nicotine = No Reaction
      1. YouTube demo of the test
      2. BitChute demo of the test

Mandelin's Reagent (Source: Wikipedia and experimental data)

Dissolve 0.5-1 grams ammonium metavanadate in 100 mL of 95-98% H2SO4. This reagent has a strong orange-yellow color before use. Color change table for Mandelin's Reagent.

  1. The reagent can be tested before analytical use by reacting it with a small sample of two or more of the following:
    1. Acetylsalicylic Acid (Aspirin) = Dark Greenish-Black
    2. Ascorbic Acid (Vitamin C) = Light Blueish Green
    3. Granulated Sugar = Brown → Black
    4. Butylated Hydroxytoluene = Brown → Dark Brown/Black → Dark Reddish Black
    5. Disodium EDTA = No Reaction
    6. Triphenylphosphine = Dark Yellow → Brown
    7. Tryptophan = Dark Orange/Black
    8. Camphor = Reacts (Bubbling)/Rapid Dirty Yellow → Brown 
    9. Indole-3-Acetic Acid = Brown → Rapid Black
    10. Hydroquinone = Rapid Brownish Black
    11. Sodium Chloride = Reacts with bubbling, foaming and evolution of heat but no color change.
    12. Dimethylglyoxime = Greenish-Brown
    13. para-Dimethylaminobenzaldehyde = Rapid Black → Very Rapid Brown → Yellowish-Brown
    14. Hexamine = Reacts with mild bubbling → Rapid Yellow Rim With a Sea-Green Center
      1. YouTube demo of the test
      2. BitChute demo of the test

Mecke's Reagent (Source: Wikipedia and experimental data)

Dissolve 1 gram of selenious acid or 1.34 grams of sodium selenite in 100 mL 95-98% Color change table for Mecke's Reagent.

  1. The reagent can be tested before analytical use by reacting it with a small sample of two or more of the following:
    1. Acetylsalicylic Acid (Aspirin) = Dark Yellow
    2. Ascorbic Acid (Vitamin C) = Reacts to produce red selenium with generation of gas.
    3. Granulated Sugar = Greenish-Yellow → Rapid Orange → Slow Black
    4. Butylated Hydroxytoluene = Greenish-Yellow → Rapid Orange → Slow Black
    5. Disodium EDTA = No Reaction
    6. Triphenylphosphine = Slow Pale Pink
    7. Tryptophan = Black → Rapid Black Orange
    8. Camphor = Reacts with bubbling and gives Yellow
    9. Indole-3-Acetic Acid = Very Dark Yellowish-Brown
    10. Hydroquinone = Black
    11. Sodium Chloride = Reacts with bubbling but no color change
    12. Dimethylglyoxime = Very Pale Yellowish-Brown
    13. para-Dimethylaminobenzaldehyde = Brown
    14. Hexamine = No Reaction
      1. YouTube demo of the test
      2. BitChute demo of the test

Liebermann's Reagent (Source: Wikipedia)

Dissolve 1 gram sodium or potassium nitrite in 10 mL of 98% Color change table for Liebermann's Reagent.

  1. The reagent can be tested before analytical use by reacting it with a small sample of two or more of the following:
    1. Acetylsalicylic Acid (Aspirin) = Orangish-brown→ Black
    2. Ascorbic Acid (Vitamin C) = Reacts with bubbling. Pinkish-Brown → Dark Reddish Brown
    3. Granulated Sugar = Reacts with bubbling. Orange → Rapid Brown → Black
    4. Butylated Hydroxytoluene = Very Dark Red
    5. Disodium EDTA = Very Pale Yellow
    6. Triphenylphosphine = Yellow → Light Brown
    7. Tryptophan = Very Dark Orange
    8. Camphor = Reacts with bubbling. Orange 
    9. Indole-3-Acetic Acid = Very Dark Brown
    10. Hydroquinone = Black
    11. Sodium Chloride = Reacts with bubbling. Very pale off-white
    12. Dimethylglyoxime = Yellow → Yellow-Orange
    13. para-Dimethylaminobenzaldehyde = Reacts with bubbling. Light brown with flecks of blue-green (nitrous acid?) → Brown → Dark Brown → Black
    14. examine = Reacts with bubbling. Dark Brown → Rapid Brown → Dark Brown
      1. YouTube demo of the test
      2. BitChute demo of the test

Froehde's Reagent (Source: Wikipedia)

Dissolve 0.5 grams of Na2MoO4 or molybdic acid in 100 mL 95-98% H2SO4. The mixture is heated to dissolve the salt which can take 2-4 hours to dissolve in cold acid. Color change table for Froehde's Reagent.

  1. The reagent can be tested before analytical use by reacting it with a small sample of two or more of the following:
    1. Acetylsalicylic Acid (Aspirin) = Purple
    2. Ascorbic Acid (Vitamin C) = Reddish Brown → Yellow
    3. Granulated Sugar = Greenish-Yellow → Orange → Brown → Black 
    4. Butylated Hydroxytoluene = Purple → Red-Orange
    5. Disodium EDTA = No Reaction → Orange Streaks
    6. Triphenylphosphine = Very Pale Brown
    7. Tryptophan = Brownish Yellow → Mustard Yellow
    8. Camphor = Reacts with bubbling. Reddish Orange
    9. Indole-3-Acetic Acid = Light Orangish Red → Brown
    10. Hydroquinone = Very Dark Purple
    11. Sodium Chloride = Reacts with bubbling but no color change.
    12. Dimethylglyoxime = Peach Orange
    13. para-Dimethylaminobenzaldehyde = Yellow → Rapid Brown → Reddish Brown
    14. Hexamine = No Reaction
      1. YouTube demo of the test
      2. BitChute demo of the test

Ehrlich's Reagent (Source: Wikipedia and experimental data)

Dissolve 0.5-2 grams of para-dimethylaminobenzaldehyde in 50 mL 95% ethanol and 50 mL concentrated HCl. Use fresh. Color change table for Ehrlich's Reagent.

  1. The reagent can be tested before analytical use by reacting it with a small sample of two or more of the following:
    1. Acetylsalicylic Acid (Aspirin) = No Reaction
    2. Ascorbic Acid (Vitamin C) =No Reaction 
    3. Granulated Sugar =No Reaction 
    4. Butylated Hydroxytoluene =No Reaction 
    5. Disodium EDTA =No Reaction 
    6. Triphenylphosphine =No Reaction 
    7. Tryptophan = Purplish Red
    8. Camphor = Reacted with bubbling but no color change. 
    9. Indole-3-Acetic Acid = Purplish Red
    10. Hydroquinone = Slow pinkish-purple
    11. Sodium Chloride = No Reaction
    12. Dimethylglyoxime = No Reaction
    13. Melatonin = Reddish Purple
    14. Hexamine = Greenish Yellow
      1. YouTube demo of the test
      2. BitChute demo of the test

Improved Ehrlich's Reagent (Source: Wikipedia and experimental data)

Create a 1:1 solution of 5% para-dimethylaminobenzaldehyde in concentrated H3PO4 (specific gravity 1.75) to methanol. Use fresh. Note that the Improved Ehrlich's Reagent will give different color results than the normal Ehrlich's Reagent does. However, the improved reagent has a greater sensitivity. Positive tests tend to be indicated by the formation of a reddish color with purplish hues although this is a general rule of thumb and is not always true.

  1. The reagent can be tested before analytical use by reacting it with a sample of:
    1. Melatonin tablet (slow reddish-violet > violetish-red)
    2. Indole-3-acetic acid (slow orange)
    3. Hydroquinone (no reaction)
    4. Tryptophan (bright yellow > bright orangish-yellow)
    5. Hexamine (light yellow)
    6. Acetylsalicylic acid (no reaction)
    7. Granulated sucrose (no reaction)
    8. Ascorbic acid (no reaction)

Improved Preparation of Brady's Reagent

To a clean dry 125 mL Erlenmeyer flask and magnetic stir bar add 3 grams of 2,4-dinitrophenylhydrazine, 20 mL of H2O, and 70 mL of 95% ethanol. Place the flask in an ice bath. Stir and allow the mixture to cool to 10 oC. With rapid stirring begin the slow addition of 15 mL of H2SO4 trying to avoid boiling. If the temperature exceeds 20 oC halt the addition and allow the mixture to cool back to 10 oC. When the sulfuric acid has been added remove the flask from the ice bath and place it on a hotplate. Stir and warm the flask until the DNPH dissolves or the temperature reaches 60 oC, whichever comes first. Then continue to stir without heating. When the solution has cooled filter through a fritted funnel if necessary. 

A positive test is indicated by the formation of a red, orange, or yellow 2,4-dinitrophenylhydrazone precipitate. If the carbonyl compound is aromatic then the precipitate will be more red and an aliphatic carbonyl compound will tend towards the yellow. The mechanism of action can be found here

Detection of Ionic Species by the Formation of Insoluble Cesium Salts (Source: Wikipedia)
Author's Note: The following equations are non-stoichiometric and only represent the identities of the reagents involved. This is due to their intended use in analysis where the amounts of the reactants are unknown.

Synthesis of 57% Hydriodic Acid (Source: NileRed)

  1. Charge a boiling flask with the KI, the H3PO4, and a few boiling chips (stir bars can be used in lieu of boiling chips). Set up for distillation as normal and attach a hose to the vacuum outlet on the adapter connecting the receiver to the distillation train. To the other end of the hose attach a small funnel and place this funnel upside down in the 10% aqueous NaOH. Commercial phosphoric acid is contaminated with varying amounts of sulfur depending on the grade of the acid. This sulfur is converted into H2S gas during the synthesis and this foul smelling, poisonous gas is removed by reacting it with OH to form S2- and H2O. Also, add some of the NaOH solution to the receiver. A better product can be obtained if one excludes light from the distillation (particularly UV light). Wrapping the distillation apparatus in foil is a simple and effective means of accomplishing this. 
  2. Begin distillation on high heat. H2S, if it is present, will react with the NaOH in the receiver and trap to form a milky precipitate. Continue until the distillate become reddish-brown in color.
  3. When the distillate changes color swap out the receiver with the NaOH/sulfide solution and replace it with an empty, clean receiver flask. Replace the trap with one containing only distilled water. Turn the heat up on the boiling flask to maximum.
  4. Distill the mixture until no more distillate comes over. The trap will capture any HI gas that may have escaped the apparatus. 
  5. When the mixture is fully reacted and distilled combine the liquid in the receiver with the liquid from the trap.
  6. Distill the mixture into an empty receiver. Everything that comes over under 125-127 oC is dilute HI. Once the temperature reaches 125-127 oC remove the boiling flask from the heat and allow it to cool. What remains in the boiling flask is azeotropic 57% hydriodic acid. It is not necessary to distill this although one can do so if one wishes to obtain a clearer, purer product. 

This reaction is not very efficient on this small scale but according to NileRed it's efficiency increases as the batch size increases. 

Synthesis of Sodium Hexanitritocobaltate(III) a.k.a. Sodium Cobaltinitrite (Source: Handbook of Preparative Inorganic Chemistry, Vol. 2, pg. 154)

  1. Dissolve 150 grams of sodium nitrite in 150 mL distilled water and cool the solution to 55 oC. Some sodium nitrite will precipitate.
  2. Add the 50 grams of cobalt nitrate hexahydrate to the solution with stirring. Allow it to stir for a minute or two after the cobalt nitrate hexahydrate appears to have fully dissolved. 
  3. Add the 50 mL of 50% acetic acid in small portions (1-2 mL at a time every several seconds) with stirring.
  4. Run a hose from an air pump down into the mixture and bubble air through it for 30 minutes. This step is best done in a large Erlenmeyer flask tilted at about 45o.
  5. Allow the mixture to stand for two hours.
  6. Filter off the brown precipitate. The filtrate will be dark but must be perfectly transparent.
  7. Add 50 mL of the distilled water heated to 80 oC to the precipitate sludge and stir thoroughly. Filter this as above and combine the two filtrates. Discard the extracted solids.
  8. To the combined filtrates (volume ~300 mL) add 250 mL of 96% ethanol. 
  9. Allow the precipitate to settle for about two hours.
  10. Filter out the precipitate and dry it by vacuum suction for approximately five minutes. 
  11. While continuing suction wash the precipitate four times with 25 mL portions of 96% ethanol followed by two washes with 25 mL portions of diethyl ether. Continue suction for about 5 more minutes. 
  12. Spread out the orange solid on a clean glass plate and break it up into a powder. Allow it to air dry for at least 30 minutes although several hours is better. 
  13. If further purification is needed then dissolve the orange product in a minimal amount of hot water. Using this solution repeat steps 8-12 making reasonable modifications of the amounts as needed.

Sodium Cobaltinitrite will give a precipitate with NH4+1, K+1, Rb+1, Cs+1, and Tl+1 cations. 

Synthesis of Sodium Nitroprusside a.k.a. Sodium Nitrosyl Cyanoferrate (Adapted from Handbook of Preparative Inorganic Chemistry, Vol.2, pgs. 1768-1769)

Rxn 1. K4[Fe(CN)6] + 6HNO3 + Δ → H2[(NO)Fe(CN)5] + 4KNO3 + NH4NO3 + CO2
Rxn 2. H2[(NO)Fe(CN)5] + Na2CO3 → Na2[(NO)Fe(CN)5] + CO2 + H2O

  1. Place the powdered K4[Fe(CN)6] into a 500 mL beaker equipped with a stir bar.  
  2. With stirring slowly add the nitric acid to the beaker. Allow the mixture to stir until the evolution of gasses has ceased and the solids are dissolved. The mixture in the beaker will take on a light blue-green color at this stage. 
  3. Place the beaker in a hot water bath and heat its contents until mixture produces a dark green precipitate when a drop of it is combined with a few drops of aqueous ferrous sulfate solution instead of a dark blue precipitate of Prussian Blue. As the mixture in the beaker is heated it will change from a cyan color to a dark reddish color. However, heating should be continued past this point until the dark green precipitate is obtained from combination with ferrous sulfate. This may take an hour or more and ideally the mixture should be evaporated down to about half it's original volume once this step is completed. 
  4. Cover the beaker and allow the mixture to cool slowly overnight (one source says 1 to 2 days). A very dark liquid contained crystallized contaminated nitrates (usually as black needles or stellated masses) should be obtained.  
  5. Decant the liquid into a clean beaker and discard the nitrate crystals. With stirring neutralize the liquid using dry sodium carbonate. This will take some patience on account of the foaming of the liquid that often occurs. Take care not add an excess of sodium carbonate (a slight excess to ensure complete neutralization is ok but minimize it as much as possible). 
  6. The neutralized reddish solution is heated until it boils at which point it is filtered into a clean beaker equipped with a stir bar.
  7. Place the beaker on a hot plate and heat it with moderate stirring to concentrate the filtrate by evaporation to about half its starting volume. Remove the beaker from the hot plate and allow the liquid to cool to about room temperature. 
  8. Once cooled an equal volume of 95% ethanol is added to the beaker to precipitate most of the remaining potassium nitrate.
  9. The nitrate crystals are removed by filtration and the solution is quickly re-concentrated to remove the ethanol. 
  10. Once the ethanol has been removed the solution that remains will yield dark red crystals on standing. These crystals are suction filtered and washed with a minimal amount of ice water. 
  11. A second crop of crystals may be obtained by reducing the volume of the filtrate and allowing it to stand for a period of time. Addition of a seed crystal from the first batch of crystals may be helpful although it is not difficult to get sodium nitroprusside to crystallize. Attempts to obtain a third crop of crystals have failed due to contamination of the product with nitrates. 

Synthesis of Potassium Bismuthate (Source: Handbook of Preparative Inorganic Chemistry, Vol. 1, pgs. 628-629)

Bi2O3 + 6KOH + 2Br2 → 2KBiO3 + 4KBr + 3H2O

  1. Create a suspension of 165 grams of bismuth oxide in 1.5 liters of 50% KOH.
  2. Heat the suspension until it boils. 
  3. With vigorous stirring add a total of 500 grams of dibromine in small portions of 0.75 to 1.5 mL to the boiling suspension. Large amounts of splattering as well as bromine vapor are created by the chemical and physical reaction of the bromine hitting the boiling suspension so this reaction is best done in a large conical flask. Once all of the dibromine is added a dark violet precipitate results. 
  4. An additional 500 mL of hot 40% KOH is added and the solid material is filtered off after settling. 
  5. The filtered precipitate is washed with 40% KOH and then suspended in 3-5 liters of water and agitated for a few hours. 
  6. Allow the solids to settle and decant the liquid. 
  7. Wash the solids in cold water and filter.
  8. Dry the bright red solid material obtained in a desiccator over 98% H2SO4

Synthesis of Sodium Bismuthate (Source: Handbook of Preparative Inorganic Chemistry, Vol. 1, pgs. 627-628)

Bi2O3 + 6NaOH + 2Br2 → 2NaBiO3 + 4NaBr + 3H2O

  1. Create a suspension of 170 grams of bismuth oxide in 1.5 liters of 40% NaOH. 
  2. Heat the suspension until it boils. 
  3. With vigorous stirring add a total of 300 grams of dibromine in small portions of 0.75 to 1.5 mL to the boiling suspension. Large amounts of splattering as well as bromine vapor are created by the chemical and physical reaction of the bromine hitting the boiling suspension so this reaction is best done in a large conical flask. As soon as the dibromine has begun to be added the solids in the suspension will change from a pale yellow to a mid-toned brown. Once this color change has been fully established by the second or third addition of dibromine the solids retain this color for the rest of the dibromine addition.
  4. Filter off the brown precipitate and wash it with 40% NaOH. 
  5. Suspend the washed solids in 3 liters of water and agitate the suspension until its color changes to a more yellowish-toned color. 
  6. Allow the solids to settle and then add them to 1.5 liters of 53% NaOH. Reflux for 30 minutes with stirring.
  7. Filter off the brown solids, wash them with 50% NaOH, and then add them to 3 liters of water. Briefly agitate the solids in the water.
  8. Stop the agitation and allow the yellowish solids to settle.  
  9. Filter off the solids and wash thoroughly with water. Dry on clay.

Synthesis of Cesium Dichloroiodate(I) (Source: Handbook of Preparative Inorganic Chemistry, 2nd Ed., Vol. 1, pg. 296)

2CsCl + I2 + Cl2  → 2 CsICl2

  1. Prepare a solution of 16.8 grams of cesium chloride in 170 mL water in an Erlenmeyer flask.
  2. Add 2.7 grams of I2 to the solution and bring the solution almost to boiling. While the solution is heating set up a Cl2 gas generator using the reaction between TCCA and concentrated HCl to generate the Cl2. Run a tube from the gas generator to a glass pipette making sure the tube is long enough for the pipette to reach the reaction flask.
  3. Once the reaction mixture is almost boiling put the pipette tip into the reaction flask and bubble chlorine gas into the solution with stirring until all of the iodine dissolves. An excess of Cl2 should be avoided in order to prevent the formation of cesium tetrachloroiodate. The solution should be kept below boiling while the Cl2 is being introduced to prevent vaporization of the I2. However, the temperature must not be allowed to fall too low or the rate of reaction drops off dramatically.
  4. Once all of the I2 reacts remove the Cl2 source from the solution and allow the solution to cool to room temperature. 
  5. Seal the flask and chill it in ice water for about 15 minutes (do not allow the solution to freeze). 
  6. Remove the flask from the ice water and filter out the first crop of crystals. This first crop of crystals tends to be a mass of largely white crystals mixed with small orange to yellow-orange crystals. It is obviously two different substances that have precipitated together but the exact identity of the white component (which makes up the bulk of this first crystallization) is unknown. It can be stored normally and saved for future experimentation or it can be thermally decomposed to recycle any iodine and cesium chloride it contains.
  7. Transfer the filtrate to a clean beaker and boil it down to about 75% it's starting volume.
  8. Remove the flask from the heat and as before allow it to cool to room temperature before sealing the beaker and putting it in ice water for about an hour. Again take care not to let the solution freeze.
  9. Remove the flask from the ice water and filter out the second crop of crystals. This second crop of crystals tends to come in the form of a jumbled mass of very tiny orangish-yellow needles. All hints of the white solid from the first crystallization should be gone and this step yields the first batch of pure cesium dichloroiodate product.
  10. Transfer the filtrate to a clean beaker and boil it down to about 20-25% it's starting volume. Once complete repeat step 8. 
  11. Remove the flask from the ice water and filter out the third crop of crystals. This third crop tends to come in the form of spectacular bundles of orangish yellow needles that can be as long as the beaker is wide (see the picture below). 
  12. Filter off the crystals and combine these with the crystals obtained in step 9. If the filtrate from step 11 is of sufficient volume a fourth run of crystallization can be carried out in a manner similar to the other three. However, only a small amount of product would be obtained at best and it may be more desirable to simply combine whatever liquid remains with the solids from the first crystallization in step 6 for recycling of iodine and cesium chloride. 
  13. The combined crystals from steps 9 and 11 are generally of good purity and can normally be dried in a desiccator and used as is. However, if further purification of the CsICl2 product is deemed necessary it can be recrystallized from a small amount of hot HCl (1:1) and washing with a small amount of cold HCl. 

Orangish-yellow crystals which melt at 238 oC in a sealed tube, evolving labile halogen at 290 oC. CsICl2 is much more stable than KICl2. Cesium dichloroiodate decomposes according to the equation: CsICl2 → CsCl + ICl whereas cesium tetrachloroiodate decomposes according to the equation: CsICl2 → CsCl + ICl3. The characteristic bundles of needles obtained from the third crystallization step are pictured below. For a sense of scale these crystals were photographed in a 100 mL beaker. It has been suggested that during this run the product was over-chlorinated and these crystals are actually CsICl4. So far as I can tell that assessment is probably correct.

Simon's Reagent (Source: Wikipedia)

Simon's Reagent is an analytical reagent used to detect secondary amines. The reagent is made up as two solutions, A and B, each of which is added to the sample being tested. Solution A: Dissolve 1 g of sodium nitroprusside in 50 mL of distilled water and add 2 mL of acetaldehyde to the solution with thorough mixing. Solution B: 2% Na2CO3 in distilled water. Procedure: Add 1 volume of solution A to the sample followed by 2 volumes of solution B. 

The amine and acetaldehyde produce the enamine, which subsequently reacts with sodium nitroprusside to the imine. Finally, the iminium salt is hydrolysed to the bright blue Simon-Awe complex. 

Robadope Reagent  (Source: Wikipedia)

The formulation of Simon's Reagent can be altered such that it gives a positive test with primary amines instead of secondary amines. The reagent is made up as two solutions, A and B, each of which is added to the sample being tested. Solution A: Dissolve 1 g of sodium nitroprusside in 50 mL of distilled H2O and add 2 mL of acetone to the solution. Solution B: 2% Na2CO3 in distilled water. Procedure: Add 1 volume of solution A to the sample followed by 2 volumes of solution B. 

The amine and acetaldehyde produce the enamine, which subsequently reacts with sodium nitroprusside to the imine. Finally, the iminium salt is hydrolysed to the bright blue Simon-Awe complex. 

Zwikker's Reagent  (Source: Wikipedia)

The Zwikker Reagent is used as a simple spot test to presumptively identify barbiturates. It is composed of a mixture of two solutions. Part A is 0.5 g of CuSO4 in 100 ml of distilled water. Part B consists of 5% pyridine (v/v) in chloroform. One drop of each is added to the substance to be tested and any change in colour is observed.

The test's lacks specificity and has a tendency to produce false positives. However, it is still of use as a TLC stain. The test turns phenobarbital, pentobarbital, and secobarbital light purple while tea and tobacco turn yellow-green. 

Dille–Koppanyi Reagent (Source: Wikipedia)

The Dille–Koppanyi Reagent is used as a simple spot-test to presumptively identify barbiturates. It is composed of a mixture of two solutions. Part A is 0.1 g of Co(CH3COO)2•2H2O dissolved in 100 ml of methanol mixed with 0.2 ml of glacial acetic acid. Part B made up of is 5% isopropylamine (v/v) in methanol. Two drops of A are dropped onto the substance followed by one drop of B and any change in colour is observed.

The test turns phenobarbital, pentobarbital, amobarbital and secobarbital light purple by complexation of cobalt with the barbiturate nitrogens.

Synthesis of Potassium Metaperiodate (Source: Rhodanide)

Rxn 1. 2KIO3 + 2K2S2O8 + 6KOH → K4I2O9 + 4K2SO4 + 3H2O
Rxn 2. K4I2O9 + 2HNO3 → 2KIO4 + 2KNO3 + H2O

  1. Add 50 mL of distilled water to a 500 mL beaker followed by a stir bar and the potassium iodate (the KIO3 will likely not dissolve which is alright) 
  2. With stirring add 15 grams of KOH to the beaker and then heat the mixture until boiling.
  3. Add 23 grams of potassium persulfate to the mixture in small portions. A color change to yellow or tan may occur which is normal. 
  4. Next add 15 grams of KOH to the mixture slowly and in small portions. 
  5. Heat the mixture for another  (30 minutes to ensure the reaction is complete. While this is happening heat 150 mL distilled water to boiling. 
  6. Add the boiling water to the mixture to dissolve the potassium sulfate produced by the reaction. 
  7. Next cool the solution in a room temperature water bath. If it is too cold potassium sulfate will crystallize. 
  8. Acidify the solution by addition of small portions 40% nitric acid with stirring. It should still be in the water bath while this is carried out. This step will convert the paraperiodate present into metaperiodate. 
  9. When the pH of the mixture becomes acidic the color will change from a yellowish tan color to white. However, this color change cannot be solely relied on and the pH of the solution should be independently confirmed before proceeding. A few extra milliliters of 40% nitric acid are added to ensure full conversion of paraperiodate.
  10. Add ice to the water bath and cool the mixture to ensure full precipitation of potassium metaperiodate.
  11. Vacuum filter off the solids. Wash the solid cake with a small amount of cold water and then vacuum filter off this as well.
  12. Remove the potassium metaperiodate and spread it out to dry. KIO4 can be recrystallized from boiling water. 

Synthesis of Anthranilic Acid Using Hypochlorite (Source:, ChemPlayer)

  1. 40 grams of sodium hydroxide is dissolved into 140 mL of distilled water and the solution is chilled on ice to 10 oC. While this is happening 200 grams of 5% sodium hypochlorite is chilled on ice to between 5 and 10 oC. 
  2. 20 grams of phthalimide is added to the chilled sodium hydroxide solution with vigorous stirring. The phthalimide will take several minutes to dissolve even with vigorous stirring and the temperature will increase as it does so by about 10-15 oC.  A small amount of water (up to about 100 mL) can be added if necessary to create a clear solution though it should be kept to a minimum.
  3. Once the phthalimide is dissolved the solution is chilled back to 10 oC.
  4. The chilled 200 grams of 5% sodium hypochlorite solution are added to the phthalimide solution with stirring and the resulting solution is allowed to stir for 15 minutes. 
  5. The solution is then heated to 80 oC after which it is removed from the heat, allowed to cool, and then chilled back down to ~10 oC. 
  6. The solution is then neutralized exactly with concentrated hydrochloric acid or sulfuric acid. The solution will go from being very slightly yellow tinted before the neutralization to a somewhat darker brown color after the neutralization. Since the neutralization must be exact it may be helpful to set aside a small amount of the alkaline solution (perhaps 20 to 40 mL) before the neutralization to use if exactly neutral is missed and the final solution is slightly acidic. This can be neutralized on its own (recommended) or added to the main solution to be neutralized there. 
  7. Once the solution is neutralized ~50-60 mL of glacial acetic acid is added with stirring to precipitate the anthranilic acid. This precipitation can take a few minutes before it begins and then will continue for several minutes. Bubbling will occur and a moderate amount of foam will be produced. Do not discard the foam as a large amount of the very light anthranilic acid product will be trapped within it. 
  8. The anthranilic acid is vacuum filtered from the solution. It is washed with ~100 mL of ice water. The crude product has the appearance of a light, granulated brown sugar although it is much lighter in weight. This crude anthranilic acid is set aside for further purification. 
  9. The filtrate is combined with 100 mL of a saturated solution of copper sulfate to precipitate remaining anthranilic acid as cupric anthranilate which is a heavy emerald green solid. This is filtered out and the dark green filtrate is discarded.
  10. The cupric anthranilate is suspended is water with stirring and hydrogen sulfide gas is bubbled through the suspension. This will displace the anthranilic acid from the copper(II) ions forming copper sulfide which precipitates as a heavy black solid.  
  11. The copper sulfide is filtered off and discarded. The filtrate is evaporated down on a hot water bath in order to retrieve the remaining crude anthranilic acid.
  12. The crude anthranilic acid from steps 8 and 11 are combined and recrystallized from a minimal amount of boiling water. The final product is an off white to light brown color and the melting point of anthranilic acid is 146-148 oC.

Bisulfite Reagent for the Precipitation of Aldehydes

"This reagent is prepared by treating a saturated aqueous solution of sodium bisulphite with 70% of its volume of rectified (or methylated) spirit, and then adding just sufficient water to produce a clear solution. The bisulphite solution obtained by passing sulfur dioxide into sodium carbonate solution is not recommended since the resulting yellow solution contains free sulphurous acid which dissolves some bisulphite compounds." A Text-Book of Practical Organic Chemistry Including Qualitative Organic Analysis, 3rd Edition, by Arthur I. Vogel. Longman Group Limited, London, 1974, page 332. (ISBN: 0582442451)

Preparation of Copper Chromite Catalyst (Source: Doug's Lab)

Rxn 1. (NH4)2Cr2O7 + 2NH4OH → 2(NH4)2CrO4 + H2O
Rxn 2. 2(NH4)2CrO4 + CuSO4 → Cu(NH4)2(CrO4)2 + 
Rxn 3. Cu(NH4)2(CrO4)2 → D → CrCuO3 + Cr2Cu2O5 + Cr2CuO4•CuO

  1. In separate beakers dissolve the ammonium dichromate in 33 mL of distilled water and the copper(II) sulfate pentahydrate in 60 mL of hot water. 
  2. Slowly add the 10% aqueous ammonia to the beaker containing the ammonium dichromate solution with stirring in order to convert it into an ammonium chromate solution. 
  3. Slowly add the solution of of ammonium chromate to the copper(II) sulfate solution with rapid stirring. The brick red copper ammonium chromate will precipitate in an exothermic reaction. Allow the mixture to stir for about 5 minutes to ensure that the reaction is complete. 
  4. Filter out the precipitate using vacuum filtration. This filtration can be difficult and it is not necessary to filter to complete dryness.
  5. Transfer the copper ammonium chromate paste to an evaporating dish and mostly dry it out over a boiling water bath. 
  6. Crush the mostly dry copper ammonium chromate to a fine powder. Return to the evaporating dish to complete the drying process.
  7. Transfer the dry copper ammonium chromate into a crucible and heat the powder over an open flame. Heat gently for about 10 minutes thereafter increasing in intensity until the temperature is approximately 400 oC. Maintain this temperature for about 10 minutes after which the powder should have turned completely black. 
  8. Once the catalyst is cooled add it to a beaker containing 130 mLs of 10% acetic acid solution with stirring. Allow to stir for about 10 minutes. 
  9. Decant the supernatant and then wash with another 130 mLs of 10% acetic acid for about 10 minutes. 
  10. Allow the solid to settle for about 10 minutes. 
  11. Separate the copper chromite catalyst from the liquid by vacuum filtration rinsing all the solid from the beaker with distilled water. 
  12. Dry the powder in an evaporating dish to obtain the dry catalyst. Copper chromite is stable with regards to moisture and air. 

UNODC Modified Ehrlich's Reagent (Source: UNODC Bulletin: Analytical Separations of Mixtures of Hallucinogenic Drugs)

Create a solution of 125 mg p-dimethylaminobenzaldehyde in 100 mL 1:1 H2SO4 to which 2 drops of 10% ferric chloride have been added. 

UNODC Potassium Iodoplatinate Reagent (Source: UNODC Bulletin: Analytical Separations of Mixtures of Hallucinogenic Drugs)

Create a solution of 3 mL of 10% platinum chloride solution mixed with 97 mL of water to which is added 100 mL of 6% aqueous potassium iodide solution

Synthesis of Antimony(III) Iodide (Source: Handbook of Preparative Inorganic Chemistry, 2nd Ed., Vol. 1, pg. 614, Personal Experimentation)

  1. A solution of 14 grams of iodine in 300 mL of toluene is refluxed with 7 grams of antimony until the iodine color disappears. This generally takes 3 to 4 hours. The use of rapid stirring that keeps the particles of antimony moving helps the reaction proceed more quickly.
    1. Note that antimony is present in excess so some will be left over when the reaction is complete. 
  2. The solution is filtered from the unconverted antimony and allowed to crystallize in a sealed flask immersed in a cold water bath. Do not allow the antimony(III) iodide to come into contact with water or excessive amounts of water vapor or it will react to form antimony oxyiodide. 
  3. The crystals are scraped from the sides and bottom of the flask and then recovered by filtration.
  4. The crystals can be dried in a vacuum desiccator at 40 oC or alternatively they can be rinsed 3-4 times with small portions of chloroform (cannot substitute dichloromethane since SbI3 is much more soluble in DCM than CHCl3 or CCl4) or ether and then quickly dried under a stream of hot air while being stirred. 
  5. Store the antimony(III) iodide in an airtight bottle that will protect it from moisture and humidity. 

Synthesis of Arsenic(III) Iodide

  1. As above for antimony(III) iodide. 

Synthesis of Rubidium or Cesium Dichromate from Rubidium or Cesium Chloride (Source: Handbook of Preparative Inorganic Chemistry, 2nd Ed. Vol. 1 pg. 1388)

Rxn 1. (NH4)2Cr2O7 + 2RbCl → Rb2Cr2O7 + 2NH4Cl 

  1. In separate beakers dissolve the rubidium/cesium chloride and the ammonium dichromate in a minimal amount of hot water. 
  2. Combine the solutions with stirring. Crystals of rubidium or cesium dichromate precipitate out almost immediately.
  3. Allow the solution to cool to precipitate out as much of the dichromate as possible. 
  4. Filter out the crystals of the dichromate and rinse with a minimal amount of ice cold water. 
  5. The filtrate can be concentrated to obtain another crop of crystals.

Synthesis of Potassium Hexathiocyanatochromate(III) (Source: Inorganic Laboratory Preparations, page 90)

Rxn 1. Cr(NO3)3 +  6KSCN → K3[Cr(SCN)6] + 3KNO3 

  1. The potassium thiocyanate is gently heated in an evaporating dish until the salt just begins to melt at about 170 oC. 
  2. Gentle heating is continued while the chromium(III) nitrate nonahydrate is added in 1 gram portions with stirring. The evolution of steam is allowed to subside before the next portion of the nitrate is added. 
  3. The reaction mixture, which is almost solid by the end of the additions, is allowed to cool in a desiccator to avoid deliquescence. 
  4. The cooled solid is then ground up with 25 mL portions of ethyl acetate using a mortar and pestle until no more of the material dissolves. A small green residue along with the potassium nitrate, sulfate, or chloride remains behind. 
  5. The violet colored extracts are combined and then filtered. 
  6. The ethyl acetate is evaporated off on the steam bath (or distilled off using a boiling water bath as the heat source). This is continued almost to dryness. 
  7. Drying is completed under vacuum. 
    1. Theoretical yield based on chromium(III) nitrate nonahydrate starting material is 26 grams (in practice expect an yield of about 84%). 
    2. Lustrous crystals, dark red-violet in reflected light and garnet red in transmitted light The salt remains unchanged in air or over H2SO4; it loses its water of crystallization only when heated to 110 °C.
    3. One part dissolves in 0.72 parts water and 0.94 parts alcohol.
    4. Density = 1.711 grams per cm3
  1. An alternative preparation has the chemist simply combine a "moderately concentrated" solution of potassium thiocyanate and KCr(SO4)2. However, given that neither potassium sulfate, chloride, or nitrate are soluble in ethyl acetate any of these should work as well. The mixed solutions are heated for 2 hours on the steam bath before being allowed to cool in the desiccator to a solid mass of crystals. The preparation then proceeds as above.
    1. (Source: Handbook of Preparative Inorganic Chemistry, 2nd Ed. Vol. 1 pg. 1374)

Synthesis of Potassium Tetracyanonickelate(II) (Source: Inorganic Laboratory Preparations, page 95)

Rxn 1. Ni2+ + 2CN- → Ni(CN)2
Rxn 2. Ni(CN)2 + 2KCN → K2[Ni(CN)4]

  1. The nickel salt is dissolved in 100 mL of boiling water.
  2. 7 grams of potassium cyanide dissolved in 100 mL room temperature water is slowly added to the nickel salt solution with stirring.
  3. Filter off the nickel(II) cyanide and wash with three 20 mL portions of hot water. Press down the filter cake well to dry it to a damp solid.
    1. The nickel(II) cyanide forms a very fine precipitate that is extremely difficult to filter. It may be better to centrifuge down the solution, wash the nickel(II) cyanide obtained in this way with three small portions of hot water, and then transfer the solid as a slurry to a clean beaker for the next step.
  4. Transfer the filter cake to a clean beaker and create a slurry of the nickel(II) cyanide using about 10 mL of room temperature water.
  5. 7 grams of potassium cyanide dissolved in about 15 mL of room temperature water is added to the beaker with the filter cake. Stir until all of the nickel(II) cyanide dissolves.
  6. Filter the solution and transfer the yellow filtrate to an evaporating dish.
  7. Evaporate down the solution to obtain the solid potassium tetracyanonickelate(II). 
    1. The water of hydration is removed completely if heated to 100 oC. Very soluble even in cold water. Decomposed to Ni(CN)2 by mineral acids and to higher nickel hydroxides by hypobromite and hypochlorite.

Synthesis of Mercury(II) Cyanide #1 (Source: Inorganic Laboratory Preparations, page 47)

Rxn 1. HgO + 2 KCN + H2O → Hg(CN)2 + 2KOH
Rxn 2. 2KOH + H2SO4 K2SO4 + 2H2O

  1. The potassium cyanide is dissolved in 100 mL of water.
  2. The mercuric oxide is added in small portions with good stirring. 
  3. When all but a small amount of the oxide remains undissolved the solution is filtered.
  4. The clear filtrate is transferred to a flask with a stir bar. Add two drops of phenolphthalein to the filtrate. Place the flask on the stir plate in an ice bath.
  5. With good stirring slowly add the sulfuric acid to the solution dropwise. Take great care as a small amount of HCN gas may be generated. 
  6. The mixture is evaporated to dryness of the water bath in the hood.
  7. The residue of product and potassium sulfate is treated with hot absolute methanol in 3 portions of 50 mL, 30 mL, and 30 mL, respectively. 
  8. The filtered methanolic extracts are combined and evaporated down to dryness on the steam bath.
    1. Decomposes into Hg and (CN)2 at 320 °C. 
    2. Solubility in water (per 100 mL) = 8 grams at 0 °C and 53.9 grams at 100 °C
    3. Solubility in ethanol (per 100 grams) = 10.1 grams at 19.5 °C
    4. Solubility in methanol (per 100 grams) = 44.1 grams at 19.5 °C
    5. Density = 3.966 grams per cm3 

Synthesis of Mercury(II) Cyanide #2 (Source: Handbook of Preparative Inorganic Chemistry, 2nd Ed. Vol. 1 pg. 1121)

Rxn 1. 9HgO + Fe4[Fe(CN)6]3 + 9H2O → 9Hg(CN)2 + 4Fe(OH)3 + 3Fe(OH)2

  1. The mercuric oxide is digested with the Prussian Blue in the water for a few hours. Replace water that evaporates.
  2. Once the reaction is complete filter off the ferric hydroxide and ferrous hydroxide precipitates. 
  3. Evaporate down the filtrate on the boiling water bath to obtain the mercuric cyanide.

Synthesis of Potassium Tetrathiocyanatomercurate(II) and Cobalt(II) Tetrathiocyanatomercurate(II) (Source: Handbook of Preparative Inorganic Chemistry, 2nd Ed. Vol. 1 pg. 1123-1124)

Rxn 1. Hg(NO3)2 + 2KSCN → Hg(SCN)2 + 2KNO3
Rxn 2. Hg(SCN)2 + 2KSCN → K2[Hg(SCN)4]

  1. An aqueous solution of mercuric nitrate to which has been added a few drops of nitric acid is added a stoichiometric amount of potassium thiocyanate with stirring.
  2. The precipitate is filtered off and washed with room temperature water. 
    1. If desired the mercury(II) thiocyanate may be recrystallized from from hot water or alcohol but it is not necessary for this preparation.
  3. A stoichiometric amount of potassium thiocyanate is prepared in ~100 mL of boiling water.
  4. To this is added the mercuric thiocyanate previously prepared. Stir thoroughly.
  5. Filter off the HgS precipitate.
  6. Evaporate down the filtrate on the boiling water bath until crystals begin to form.
  7. Remove from the heat and allow the solution to cool. The white, fibrous mass of crystals is filtered off and dried over P2O5
    1. Solubility of mercury(II) thiocyanate in water (per 100 mL): 0.069 grams at 25 °C. The solubility is higher in alcohol, boiling water, and potassium thiocyanate solution and less in ether. Decomposes with swelling at 165 °C.
    2. Potassium tetrathiocyanatomercurate(II) crystals are readily soluble in cold water, soluble in alcohol, and insoluble in ether. 
  8. The strikingly blue Cobalt(II) tetrathiocyanatomercurate(II) can be synthesized by the addition of an aqueous solution of excess cobalt(II) chloride to the solution of potassium tetrathiocyanatomercurate(II) with stirring. The blue compound will quickly precipitate out of solution.
    1. The synthesis can also be reversed with the synthesis of alkali tetrathiocyanatocobaltate(II) being carried out first. To a solution of this complex add an aqueous solution of excess HgCl2 and as before the blue product will quickly precipitate.

Synthesis of Cadmium(II) Iodide

Rxn 1. Cd2+ + Mg(metal) → Mg2+ + Cd(metal)
Rxn 2. Cd + I2 → CdI2

  1. The cadmium sulfate is dissolved in a quantity of distilled water.
  2. The magnesium or zinc rod is inserted into the cadmium sulfate solution and the rod is used to stir the mixture occasionally. The cadmium is scraped off the rod occasionally to continue the reaction.
  3. Once the reaction is complete the water is decanted and the cadmium sponge is washed with clean water. This too is decanted.
  4. The cadmium sponge is transferred to a round bottom flask and then refluxed with 50 mL of water and the iodine until all of the metal has dissolved.
    1. The reflux takes about 2 hours to complete.
  5. The solution is then filtered before being evaporated down in an evaporating dish over a steam bath. The compound is finally dried in a vacuum desiccator. 
    1.  Almost colorless, lustrous plates. CdI2 is soluble in alcohol, ether, and acetone as well as water.

Synthesis of Dinitrotetramminenickel(II)  (Source: Inorganic Laboratory Preparations, pages 192-193)

Rxn 1. Ni2+ + CO32+ → NiCO3
Rxn 2. NiCO3 + CH3COOH → Ni(CH3COO)2 + CO2 + H2O
Rxn 3. Ni(CH3COO)2 + 4NH3 + 2NaNO2 → [Ni(NH3)4(NO2)2] + 2CH3COONa

  1. Dissolve the sodium carbonate into 150 mLs of boiling water. Dissolve the nickel(II) chloride hexahydrate into 100 mLs of hot water. 
  2. The solution of nickel(II) chloride is slowly poured into the solution of sodium carbonate with good stirring. The mixture is held at boiling and stirring is continued until the precipitate of nickel(II) carbonate begins to settle out well.
  3. Filter out the solid nickel(II) carbonate and wash it with 50 mL of boiling water.
  4. The moist carbonate is dissolved on the steam bath in 10 mL of water and 6 mL of glacial acetic acid. 
  5. On cooling some nickel(II) acetate crystallizes out. Add about 5 more drops of glacial acetic acid to prevent possible hydrolysis of the product.
  6. Cool the mixture and add 30 mLs of concentrated ammonia. Continue cooling and stir the violet mixture until everything goes into solution.
  7. The ammonium acetate and sodium nitrite are added to 50 mLs of water. The stirred mixture is carefully heated to 25-30 oC.
  8. When the ammonium acetate and sodium nitrite is fully dissolved the viscous mixture is added to the ammoniacal nickel solution and allowed to stand at room temperature.
  9. Precipitation of the red complex, which soon begins, is complete after one hour.
  10. When the preparation has stood overnight the the faintly colored viscous mother liquor is carefully decanted and the salt brought onto the filter with 95% ethanol. The solid is then washed with 50 mLs of ethanol (both sodium nitrite and ammonium acetate are soluble) and the product dried in air.
    1. The compound begins to lose ammonia over 100 oC.
    2. The compound is converted to the violet hexammine on exposure to ammonia gas at low temperatures. 

Synthesis of Barium Chlorate (Handbook of Preparative Inorganic Chemistry pages 314-315)

Rxn 1. 2KC1O3 + (NH4)2SO4 → 2NH4C1O3 + K2SO4
Rxn 2. 2NH4C1O3 + Ba(OH)2•8H2O → Ba(ClO3)2•H2O + 2NH3 + 9H2O

  1. A mixture of 122.6 g. of potassium chlorate, 70g. of ammonium sulfate and 350 ml. of hot water is evaporated in a porcelain dish with constant stirring until a thin slurry forms.
  2. After cooling, a fourfold quantity of 80% ethyl alcohol is added, resulting in the separation of insoluble potassium sulfate from the ammonium chlorate.
  3. The potassium sulfate residue is filtered and washed several times with alcohol.
  4. The filtrate is freed of alcohol by distillation.
  5. The ammonium chlorate residue (Caution: ammonium chlorate has a tendency to explode!) is reacted in a porcelain dish on a steam bath with a sufficient quantity of hot concentrated barium hydroxide octahydrate solution (at least 160 g. of barium hydroxide octahydrate dissolved in about 160 ml. of hot water) so that the ammonia odor disappears completely and the solution finally gives a definite alkaline reaction.
  6. It is then evaporated to dryness.
  7. The residue is dissolved in a fivefold quantity of water, and carbon dioxide is bubbled through the solution until the precipitation of barium carbonate is completed.
  8. The barium carbonate is filtered off and the solution evaporated to crystallization.
    1. Colorless, columnar prisims
    2. M.P. (anhydrous salt) = 414°C
    3. Density = 3.18 grams/cm3
    4. Solubility 
      1. 0°C = 27.4 grams per 100 grams H2O
      2. 100°C = 111.2 grams per 100 grams H2O

Synthesis of Uranium(IV) Oxalate (Handbook of Preparative Inorganic Chemistry pages 1449-1450)

Rxn 1. UO2(CH3COO)2 + 4HCl + Na2S2O4 → UCl4 + 2NaHSO3 + 2CH3COOH
Rxn 2. UCl4 + 2H2C2O4 + 6H2O → U(C2O4)2•6H2O + 4HCl

  1. Five grams of uranyl acetate dihydrate is dissolved in 100 mL of 1:10 HCl that has been preheated to 80oC.
  2. While stirring five grams of sodium dithionite dihydrate powder is added in small portions.
    1. The initial precipitate is brown but changes to whitish green.
  3. Then five mL of concentrated HCl is added and the mixture is heated for about 10 minutes on the water bath until solution is complete.
    1. The dark green solution of U(IV) salt is usually somewhat cloudy because of a haze of fine sulfur.
  4. It is filtered in the absence of air and treated while still warm at ~ 60 oC with a saturated oxalic acid solution. This is added slowly with good stirring.
  5. A heavy, dark gray precipitate forms at once. It settles in a few minutes and after about half an hour exhibits the dark green color of uranium(IV) oxalate.
  6. The compound is washed 5 times with 100 mL portions of water to remove all traces of sulfate and excess oxalate.
  7. The final product is stable in air and thus may be air-dried.
    1. The yield is almost quantitative ~5.7 grams.  

Synthesis of Ammonium Uranyl Carbonate (Handbook of Preparative Inorganic Chemistry pages 1449)

Rxn 1. 2UO2(NO3)2 + 6NH3 + 3H2O → (NH4)2U2O7 + 4NH4NO3
Rxn 2. (NH4)2U2O7 + 6(NH4)2CO3 → 2(NH4)[UO2(CO3)2] + 6NH3 + 3H2O 

  1. The ammonium diuranate is prepared by adding concentrated ammonia to an aqueous solution of uranyl nitrate hexahydrate. 
  2. The fine yellow powder is filtered off and washed with water.
  3. The ammonium diuranate is stirred with an excess of concentrated ammonium carbonate solution in a 70oC water bath for 10 minutes.
  4. The clear supernatant is decanted and allowed to sit overnight. The ammonium uranyl carbonate will crystallize out of solution.
    1. Bright yellow crystals precipitate. These are filtered and dried in air.
  5. If there is residual unreacted ammonium diuranate then it is treated with the mother liquor at 70oC as described above until crystals no longer form on cooling.

Ammonia Generator Reaction (NurdRage, Video Time Stamp = 7:36)

Rxn 1. NH2CONH2 + NaOH → NH2COOH + Na+(aq) + NH3(g)
Rxn 2. NH2COOH + NaOH → CO32- + Na+(aq) + NH3(g)

  1. Combine the water, urea, and sodium hydroxide in a flask. This flask is connected to a reflux condenser to condense water vapor. A hose runs from the top of the condenser to carry the ammonia gas to wherever it is to be used. If used to produce aqueous ammonia then the hose should run into a cooled receiver equipped with stirring.
  2. The urea-water-sodium hydroxide mixture is then heated with stirring. The solution will not generate ammonia until it is heated.
  3. Allow the generator to run for a few hours until no more ammonia gas is being generated.
    1. Theoretical yield is `~51 grams of ammonia

Synthesis of Barium Nitrite Monohydrate (Inorganic Laboratory Preparations pages 34-35)

Rxn 1. Pb(CH3COO)2 + Mg → Pb sponge + Mg(CH3COO)2 
Rxn 2. Ba(NO3)2 + 2Pb → 2PbO + Ba(NO2)2

  1. The lead acetate is dissolved in 200 mL of hot water and 5 mL of glacial acetic acid.
  2. The solution is cooled down to 40-50 °C.
  3. The magnesium ribbon is added in coils that are held beneath the solution by resting a glass rod on the metal. 
  4. The temperature range is maintained until no more gas is evolved from the reaction (about half an hour). To avoid compacting the lead sponge stirring should be avoided.
  5. Decant the supernatant liquid and gently wash the lead sponge several times with portions of hot water. Decant the wash water between washings.
  6. A solution of 10 grams of barium nitrate in 100 mLs of warm water is poured over the lead sponge.
  7. The mixture is gently boiled for 1.5 to 2 hours in a beaker covered with a watch glass to maintain a constant volume in the boiling solution. 
  8. The lead(II) oxide is filtered off.
  9. Carbon dioxide is passed through the reheated filtrate to precipitate out small amounts of lead carbonate and barium carbonate.
  10. The solution is cooled and filtered again.
  11. The filtrate is evaporated down over heat until it gets down to about 40 mLs in volume.
  12. Once the solution has a volume of about 40 mLs it is transferred to an evaporating dish placed over a boiling water bath.
  13. A pale yellow syrup that solidifies almost completely on cooling is obtained. 
  14. The residue is ground up with ~25 mL of acetone and then suction filtered.
  15. The solid residue is then digested for half an hour under reflux with a solution of 120 mL of 95% ethanol and 30 mLs of water.
  16. The solution is filtered and then evaporated down to obtain the final product.
    1. Two crops of crystals are obtained. Wash them with acetone and dry over CaCl2 or 3Å molecular sieves in a desiccator.
    2. If 32 grams of lead powder are used instead of freshly generated lead sponge the yield is cut from 6-7 grams to 1 gram even if the nitrate and lead powder are boiled together for 24 hours. 

Gunpowders (Wikipedia)

  1. Standard Formulation
    1. 75% potassium nitrate, 15% softwood charcoal, and 10% sulfur by weight. The components should be reduced to fine powders separately and then combined using a method that does not create static electricity or sparks (for example thorough rolling on sheets of paper or milling with wooden balls). Never make up large batches at any one time and store the finished product in a place that is safe from humidity, sparks, flames, static, etc. Once the black powder is created the particles can be rolled with fine graphite dust for several hours which coats the black powder particles and helps to prevent absorption of moisture from the air. 
      1. Charcoal powder is not pure carbon. Instead, it is partially pyrolyzed wood cellulose/lignin. Pure carbon has a much higher ignition temperature than charcoal so using pure carbon in a gunpowder formulation will give a burn more akin to a matchhead at best according to the literature.
      2. As illustrated in the formulae below increasing the proportion of sulfur gives a powder than burns faster making it more suitable for blasting while increasing the proportion of charcoal gives greater stability and increased shelf life but produces a slower burning powder more suitable for cannons and rockets. 
  2. French War Powder
    1. 75% potassium nitrate, 12.5% charcoal, and 12.5% sulfur. English War Powder was identical to the Standard Formulation given above.
  3. Blasting Powder
    1. 70% potassium nitrate, 14% charcoal, 16% sulfur (using sodium nitrate the amount of nitrate can be as low as 40% nitrate, 30% charcoal, and 30% sulfur).
    British Congreve Rocket Powder
    1. 62.4% potassium nitrate, 23.2% charcoal, and 14.4% sulfur. 

Synthesis of Barium Ruthenate and Barium Tetraacetyldioxoruthenate(VI) Trihydrate (Source: Handbook of Preparative Inorganic Chemistry pages 1595 and 1600, Oxidation of Alkanes by Barium Ruthenate in Acetic Acid: Catalysis by Lewis Acids see next entry)

  1. Barium ruthenate can be prepared by dissolving ruthenium metal (the powdered metal is best) into a fused mixture of KOH and KNO3 to produce a melt of potassium ruthenate. The proper ratio of reactants is Ru Powder:KOH:KNO3 is: 3:25:3 by weight. Another method is to combine the Ru powder and KOH in a crucible, heat until the KOH is molten, and then add in either KNO3 or KClO3 in small amounts with stirring until all of the ruthenium has reacted. The previously mentioned ratio of reactants presumably still applies here.
  2. Once the Ru powder has reacted to form potassium ruthenate allow the melt to cool and then dissolve the dark green melt into water to obtain an orange solution of aqueous potassium ruthenate.
  3. Combine with a mild excess of an aqueous solution of barium acetate (or another barium salt that will not produce a poorly soluble potassium salt in the metathesis reaction).
  4. Allow the barium ruthenate to precipitate out, filter it, rinse with water, and dry the product overnight in the desiccator.
    1. The filtrate can be evaporate down to obtain more potassium ruthenate but be extremely careful about allowing it to come into contact with powerful oxidizers. These can oxidize ruthenate to ruthenium tetroxide which is a very volatile and dangerous compound with properties similar to osmium tetroxide.
  1. The barium ruthenate, glacial acetic acid, and DCM are combined together at room temperature and stirred until the dark red suspension of barium ruthenate turns dark green.
  2. Stirring is continued until all of the barium ruthenate has reacted and no more red solids remains.
  3. The solution is then evaporated under vacuum to obtain the Ba[Ru(O)2(CH3COO)4].
  4. The compound can be stored in the normal way in an amber bottle. The solution can be reconstituted simply by dissolving the compound back into a mixture of dichloromethane and glacial acetic acid. This reconstituted solution is suitable for use in barium ruthenate oxidations of alkanes.

Oxidation of Alkanes by Barium Ruthenate in Acetic Acid: Catalysis by Lewis Acids (J. Chem. Soc., Chem. Commun., 1983)

Selective Reduction of Carboxylic Acids into Alcohols using NaBH4 and I2 in THF (J. Org. Chem. 1991, 56, 5964-5965)

Preparation of Sodium Thioantimonate (Schlippe's Salt) With Antimony Trisulfide, Sodium Sulfide Nonahydrate and Sodium Thioarsenate (Inorganic Laboratory Preparations pages 68-69)

Rxn 1. Sb2S3 + 3Na2S + 2S → 2Na3SbS4

  1. The sodium sulfide nonahydrate is dissolved in 100 mL of water.
  2. The sodium trisulfide is dissolved in the sodium sulfide solution with stirring.
  3. The sulfur powder is added to the solution and it is heated gently with stirring until the sulfur powder is fully dissolved (takes about 15-30 minutes).
  4. The solution is filtered and then evaporated down over boiling water until a skin of crystals forms on the solution.
  5. The solution is allowed to sit overnight (takes several hours to crystallize fully).
  6. The solid is filtered off and pressed dry.
  7. The damp filter cake is dissolved in an equal mass of water in which 0.5 grams of sodium hydroxide is dissolved.
  8. The solution is filtered and then evaporated down to 50-75 mL over boiling water.
  9. The solution is taken off the heat (no visible crystal crust will be present or it will be very slight) and left to sit overnight.
  10. The crystals of sodium thioantimonate are filtered off, pressed dry, and bottled. The final product is dried under vacuum. Theoretical yield is about 90 grams.
    1. The antimony trisulfide needed for the reaction can be easily produced by dissolving 29 grams of antimony trioxide in 2M HCl and bubbling hydrogen sulfide through the solution. The moist product may be used directly.
    2. The sodium sulfide nonahydrate can be produced by bubbling hydrogen sulfide through a solution of 24 grams of sodium hydroxide in aqueous solution. The resulting solution is evaporated down to 100 mL at which point it is ready for use. If the sodium sulfide nonahydrate crystallizes out simply heat the solution with stirring to render it soluble again.
    3. Sodium thioarsenate octahydrate may be prepared by the same procedure described above except that either 24.5 grams of arsenic trisulfide or 20 grams of arsenic trioxide are used. The solution is evaporated down as before but not to dryness nor is the product subjected to recrystallization because of accompanying decomposition. The yield, that depends on the extent of evaporation, is about 60 grams. 

Ammonium Tetrakis(thiocyanato)diammine Chromate(III) (Reinecke's Salt) And The Guanidinium Salt (Morland's Salt) (Inorganic Laboratory Preparations pages 262-264)

  1. The ammonium thiocyanate is placed in a suitably sized evaporating dish and the solid is gently heated at 140-150oC until the solid fully melts.
  2. The melt is gently stirred with a thermometer and the ammonium dichomate is sifted onto the melt in small portions. Each portion should be thoroughly stirred into the melt and allowed to fully react before the next portion is added. The temperature should be kept at about 160oC throughout the addition; too much lower or higher will effect the outcome of the reaction.
  3.  Once all of the ammonium dichromate has been added take the purple liquid melt and place it in a desiccator as soon as possible in order to prevent deliquescence. 
  4. Once solid the melt is quickly broken up with a spatula and transferred to a beaker containing 125 grams of ice. 
  5. Stir the chunks of the solidified melt with the ice until only a small piece of ice remains. Due to the presence of excess ammonium thiocyanate the temperature may drop below 0oC for a time before rising normally. 
  6. When the solution has warmed spontaneously to the point where only a small piece of ice remains the red solid is filtered off with suction and drained well without washing. 
  7. The crude solid is added to 500 mL of water at 70oC and is stirred continuously as the temperature is allowed to climb back to 60-65oC. 
  8. The purple-red solution is then immediately filtered by suction into an ice-cooled flask and rapidly cooled to 5oC. 
    1. The solid filtered off in this step is guanidinium tetrakis(thiocyanato)diammine chromate(III) a.k.a. Morland's Salt HNC(NH2)2•H[Cr(NH3)2(SCN)4]. The guanidinium forms from the thermal decomposition of ammonium thiocyanate.
  9. The complex salt crystallizes out of solution. It is filtered off, drained well, and allowed to air-dry. 

Antimony(V) Sulfide (Chemify)

The "slightly wet salt" referred to in the protocol is freshly made sodium thioantimonate. It does not need to be freshly made but if it is then it may be used directly in this synthesis.  

Mercurous Nitrate (Synthetic Inorganic Chemistry by A. Blanchard page 232)

  1. 25 grams of mercury are treated with 20 ml of 6N (25%) nitric acid by warming gently until no further action takes place.
  2. The solution of mercury(I) nitrate is cooled, separated by pouring from any remaining globule of mercury into a small dish, and left to crystallize until the next day.
  3. The next day obtained crystals are spread out on a filter, covered with a paper towel and left to dry completely at room temperature.
    1. Mercury(I) nitrate is kept in a stoppered bottle as soon as it is dry.
    2. Mercury(I) nitrate obtained by described method contains one molecule of water; mercury(I) nitrate monohydrate.

Dibismuth Tetroxide a.k.a. Bismuth Tetroxide (Handbook of Preparative Inorganic Chemistry page 629 and Atomistry)

Rxn 1. 2KBiO3 + HClO4 → Bi2O4 + 2KClO4 + O2

  1. The potassium bismuthate is boiled for approximately 10 hours with the perchloric acid until only 1 to 2 grams of a reddish-orange residue are left. 
  2. The precipitate is filtered off, washed and dried. This is the hydrate of dibismuth tetroxide. 
    1. If the potassium bismuthate is reacted with azeotropic acid the reactions seems to happen more quickly than 10 hours. Nevertheless the bismuthate salt should be digested for several hours over heat and then allowed to sit for some time (preferably overnight). The precipitate can then be filtered off, washed, and dried the next day to obtain the hydrated dibismuth pentoxide.
    2. If sodium bismuthate is used the color of the final product will be different even though it is supposed to be the exact same compound.

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