Propoxyfiend (Stranger)
02-21-03 14:12
No 410543
      Nitrotoluene Troubles(quaaludes ala cheapskate)  Bookmark   

A 1 L 2 neck flask was fitted with a glass stopper and 0-300c therm.  Then was submerged in a salt ice water bath 294 grams of sulfuric acid and 120g of Nitric Acid was added with vigours stirring.  Over approx 1 hour toluene was slowly added(5-10 ml / 100g total).  The temp never climbed above 29c(EVEN WHEN REMOVED FROM THE BATH for more than 20 min)  During the toluene addition a slight tint of yellow was noticed by the stir bar.  This yellow eventually turned 'white'.  The toluene addition has been finished for approx 1 hour.  3 hours of stirring left then time for seperation.

Swim's concerns:

According to cheapskate and others the mixture is susposed to be brown.  It's a light milky color.  Every now and then there seems to be a tad of yellow.  However, swim feels this is just what his eyes want him to see(yellow).  Swim assumes the yellow comes from the nitric acid, correct?  Their fingers are still alittle stained(after several washes).  Swim has been told even though he used less nitric acid than reccomended (120 instead of 149 - quaaludes ala cheapskate) this should not be a problem.  Other than the fact yield may suffer.  Swim's main concern is the color of this milky white liquid.  On more than one occasion cheapskate references the color. 

the acid layer will be yellow and the nitro layer will be lighter


Then after seperation he states


Stir in NaOH the water layer will turn yellow and the nitro toluene layer will be a bright yellow



Will swim's layers ever turn orange and yellow?  Or should swim just break out a flash light & dildo to do the best seperations they can and not worry about comparing colors? Or after the 1st seperation will colorchanges take effect?


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    Aurelius
(Hive Addict)
02-21-03 18:49
No 410621
      Didn't you get the hint?  Bookmark   

?
 
 
 
 
    epistemologicide
02-21-03 19:25
      you fucking manaic!! :)
(Rated as: off-topic)
 Bookmark   
 
 
 
    Propoxyfiend
(Stranger)
02-21-03 20:53
No 410648
      Nitrotoluene(Quaaludes ala Cheapskate)  Bookmark   

A 1 L 2 neck flask was fitted with a glass stopper and 0-300c therm.  Then was submerged in a salt ice water bath with 294 grams of sulfuric acid and 120g of Nitric Acid was added with vigours stirring.  Over approx 1 hour toluene was slowly added(5-10 ml / 100g total).  The temp never climbed above 29c(EVEN WHEN REMOVED FROM THE BATH for more than 20 min).  During the toluene addition a slight tint of yellow was noticed by the stir bar.  This yellow eventually turned 'white'  After 5 Hours of stirring the whole mess was placed into a sep funnel.  The nirtotoluene was seperated from the acid layer.  Just to be sure the acid layer was tossed back in the sep funnel and nothing was left(milky white color).  Water 2x the volume of the nitro was placed into a large beaker with 1 teaspoon of naoh and stirred until disolved.  The water layer looked like pineapple juice and the nitro layer was bright yellow. Approx 146.9g of a bright yellow liquid(nitrotoluene) was recovered.  Then 2x the volume of water was added  and along with 1 teaspoon of naoh and stirred.  Once again 2x the volume of water was added to the nitrotoluene and stirred.  Both layers looked similar as described before(nitro was alittle brighter).  However, swim was unable to distinguish between the 2 layers.  Alittle water was added to see which layer it went into.  The pour spout of the water broke and water flooded the mixture.  Swim is now left with approx 600-700 ml of a brightly urine colored liquid in his sep funnel.  The flashlight and dildo were used without success.  Swim is certian the nitro is in there. . . How does he get to it?  There is entirely too much water in the sep funnel and the layers are not visible.  What does swim need to do?
Swim checked the mixture again.  No layers are to be found The only other useful information swim feels may help others help him is their appears to be a layer of 'scum' floating on top, a few ml at max.

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    algebra
(Stranger)
02-21-03 20:53
No 410649
      rdx  Bookmark   

hes dreaming about mono-nitro toluene not trinitrotoluene.
 
 
 
 
    Propoxyfiend
(Stranger)
02-21-03 23:31
No 410685
      Clarify  Bookmark   

Is this just an ignorant question?  Is the answer in TFSE? Doea swim need to give more details or clarify? 

Edit: Someone told me salt or food coloring??  Should swim give this a try.  Edit 2:
How long will this nitro last?  It's been sitting in a 'stopped' flask for atleast 5 hours now. . .

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    hermanroempp
(Hive Bee)
02-22-03 07:51
No 410765
      Try this  Bookmark   

Acidify with conc. HCl, the water phase should change in colour (colour should become lighter), whereas the nitro phase remains mainly unaffected. The lower phase should be the nitro phase as nitrotoluene has a higher specific gravity than water. Then separate the layers as usual in a sep funnel or by using a pipet or eye dropper (tedious, but it works). Then do the base wash of your nitro again, but please, use only about 1/10 the volume of your nitro of aqueous NaOH. Do this base wash several times and then proceed as usual with the purification of your nitrotoluene - water wash etc.
Alternatively, if you really can't distinguish between layers (I know some people for some unknown reason can't do) acidify with HCl as mentioned before and add a few tiny crystals of potassium permanganate -> water layer becomes instant violet, phase separation should now be possible.

Quidquid agis, prudenter agas et respice finem!
 
 
 
 
    Propoxyfiend
(Newbee)
02-22-03 08:14
No 410771
      Thanks  Bookmark   

The first time swim added water and Sodium Hydroxide the layers were clearly visible.  When swim added water with out Sodium Hydroxide there are no layers.  Even after 5 house of sitting.   Swim is gonna go try it now!

Thanks


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    Propoxyfiend
(Newbee)
02-22-03 09:22
No 410783
      No phase seperation  Bookmark   

This is what swim did: As suggested above a few drops of HCL were added, ph tested no change.  A few more, no change.  Then a few more and wooosh the whole thing instantly turned clear.  The end of a match was used to add a few grains of potassium permanganate and the funnel was lightly rocked.  Now instead of a yellow or clear solution everything is purple.  Swim can't understand why they can't tell the layers apart.  Should they attempt to re-basify?  Throw the whole thing back into the beaker?  They know they have atleast 148 ml of nitro in there, they saw it, they smelled it.  I used to chuckle when people has issues with safrole distillation.  This seemed like such a simple task to me.  However, swim can't even tell 2 layers apart.  This is such a simple step and process, right. . .

Edit:  The whole shabang was placed into a beaker and stirred.  It was terribly acidic so a pinch of naoh was added.  This turned some of the purple liquid back the the original yellow color.  The liquid was placed back inro the sep funnel and allowed to sit.  Overtime purple gunk collected at the bottom(potass perm, swim assumes).  Now the bulk of the liquid is back to it's original color. However, it now has something suspended in it(floaties).  These are slowly falling to the bottom of the funnel and are being drained and collected.  

Swim is certian they lost quite a bit of nitrotoluene.  However, they are certian it's still in there.HELP ANYONE?

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    yellium
(I'm Yust a Typo)
02-22-03 13:05
No 410842
      If it is a milky white emulsion you might try...  Bookmark   

If it is some sort of emulsion you might try adding a shitload of salt to your solution, and see what happens then.
 
 
 
 
    Propoxyfiend
(Newbee)
02-22-03 14:05
No 410860
      Last try  Bookmark   

I think swim's days of making Quaaludes are numbered(until they get more nitric acid next week)  Here's the wrap up and final post.  It's obvious no one wants to help or can.  More than likely the situation is not being explained properly.  However, swim thanks all of you who have offered valuable input.

All of the Pot Perm was vac filtered(buchnered) out of the solution.  The filter was changed 2x.  Each time it was stained with a dark brown substance. Approx 30 ml of dark brown liquid was removed from the solution.  This liquid still has lots of 'gak' in it.  Swim assumes this is gak potassium permanganate.  This leaves approx 450 ml of 'clear' yellowish liquid.  Similar to the color of sprite yet cloudy.  Very little if any turbidity is noted in the liquid.  The color of the larger mass of liquid(450ml) certinaly is not the color the nitrotoluene orignally was(MUCH LIGHTER).  Most likely this solution contains: Dh20, Nitrotoluene(140ml or less now), Pot Perm(it's not visible if it's still there), HCL & Sodium Hydroxide.  Swim is attempting to seperate the nitro from the water and other stuff.  There are no visible layers.  Swim is currently adding salt to see what happens.  After this unless someone has other advice swim will purchase 500ml of nitric so they can fuck up a few runs.  However, if this batch can be saved please inform smile

Lord said to his children, "Let there be ludes".  Swim will do it.
 
 
 
 
    yellium
(I'm Yust a Typo)
02-22-03 14:12
No 410861
      I've never liked doing reactions with KMnO4.  Bookmark   

I've never liked doing reactions with KMnO4. Way to messy.
 
 
 
 
    Chromic
(Synaptic Self-Mutilator)
02-22-03 15:41
No 410886
      Purchase O-toludine  Bookmark   

Purchase some O-toluidine, it isn't that watch yet--is it??

The KMnO4 oxidation is still a bitch though.
 
 
 
 
    Rhodium
(Chief Bee)
02-22-03 16:19
No 410893
      It is watched, but I have never heard about...  Bookmark   

It is watched, but I have never heard about anyone having problems ordering it though.
 
 
 
 
    yellium
(I'm Yust a Typo)
02-23-03 07:11
No 411089
      You do work with 96% sulfuric acid/70% HNO3,...  Bookmark   

You do work with 96% sulfuric acid/70% HNO3, do you?
 
 
 
 
    hermanroempp
(Hive Bee)
02-23-03 07:37
No 411092
      Nitrotoluenes
(Rated as: excellent)
 Bookmark   

Preparation of o- and p-nitrotoluene:

In a 250ml three-necked flask, equipped with overhead stirrer, dropping funnel and thermometer 0.1 mol of toluene are cooled to 10C. Then from the dropping funnel a pre-cooled (10C) mixture of 10ml 68% nitric acid (d. 1.42) and of concentrated (98%) sulfuric acid (d. 1.84) is slowly added drop by drop while the batch is vigorously stirred. The temperature of the batch is held between 5C and 10C by cooling in an ice-bath. After the addition of acids is finished, the mixture is then stirred for 3 hours longer at room temperature (20-22C). Then the batch is dumped into 300ml of icewater (ice:water 1/1 by volume) and is vigorously stirred, the whole mix is then transferred into a sep funnel. The nitrotoluene (lower orange layer) is drained and the aqueous phase (upper layer) is extracted twice with 25ml of dichloromethane. The extracts + nitrotoluene are pooled, washed once with 50ml water, then in sucessive 50 ml portions with 5% sodium hydrogencarbonate solution until fizzing stops and the nitrotoluene gives a neutral to slightly alkaline reaction to pH paper. Then the mix is given a last wash with 50ml water. The nitrotoluene, which is always the lower phase in the washes, is then dried over 15g anhydrous sodium sulfate for 12 hours with occasional shaking.
The dichloromethane is distilled off, last traces of dichloromethane are removed by heating in a water bath at 50C when a weak vaccum is employed (about 100 Torr is sufficient). The now yellow coloured mixture of nitrotoluenes is immersed in a salted ice bath, where the white needles of the p-isomer precipitate out (the mixture itself should not be cooled below -9C!). The precipitate is filtered off quickly on a pre-cooled Bchner filter (freezer), the needles of p-isomer are then given a wash with 2 x 6ml of ice-cold petrol ether.
The filtrate, which consists largely of o-nitrotoluene, is subjected to fractional distillation over a well insulated 30cm Vigreux column in vacuum. o-nitrotoluene distills over at 95C (10 Torr), under normal pressure o-nitrotoluene distills at 222C. Only the constant boiling point fraction from 94-96C is taken. The residue in the distilling flask is again subjected to freezing as already described, to get the rest of the p-isomer. The filtrate from the freezing step is discarded, it consists of mainly of m-isomer, o-isomer and a very small amount of p-isomer...workup of this mixture again would be too difficult, so simply forget about it.
Yield is about 40% of o-nitrotoluene and 20% of p-nitrotoluene.

Procedure taken from "Organikum", VEB Deutscher Verlag der Wissenschaften, 15th ed., 1981, p. 381
Modified by old Herman to suit his needs..smile

Edit: You will have to use a pressure-equalized dropping funnel!!

Quidquid agis, prudenter agas et respice finem!
 
 
 
 
    Cheapskate
(Downer Dude)
02-28-03 17:11
No 412669
      And the problem is:  Bookmark   

I wish hermanroempp had been around when I was experimenting with this way back when.  That description above would have helped a lot.

The problem here is the nitric acid.  It isn't strong enough.  I suspect that you're using 49% or so.  This is the kind of thing that happens with too little concentration of the nitric.  I've seen this too many times to admit to.  It's the major reason I finally gave up and started making the nitric myself.  I gave that up eventually and went to ordering the o-toluidine because the iron reduction is a horrible smelly mess.

You can distill the nitric to get it stronger, buy the 79% stuff or just follow chromic's advice and order the o-toluidine.  If the toluene doesn't turn brown when dripped into the acid mix, the nitric isn't strong enough or you don't have toluene.

Sorry for the late response, I don't get the chance to check in often enough anymore.

CS
 
 
 
 
    Antoncho
(Official Hive Translator)
03-01-03 06:58
No 412780
      Question?  Bookmark   

Uhhh... Guys... Have noone tried making HNO3 in situ by adding 70% H2SO4 to NaNO3?

I mean, it seems like a logical possibility of an improvement - and i really can't think of anything that would make it unfeasible!


Antoncho
 
 
 
 
    Polverone
(Hive Bee)
03-01-03 15:17
No 412880
      sure  Bookmark   

H2SO4/nitrate salt is a common nitrating agent among a different flavor of home chemist. In most cases one wouldn't deliberately dilute the H2SO4 to 70% first. 70% HNO3 is usually used because it is cheaper, not because it is better than 98%. Acid/nitrate may not be quite as clean or efficient as pure mixed acids, but it works well enough and it's a nice shortcut for those who don't want to distill HNO3.

19th century digital boy
 
 
 
 
    hCiLdOdUeDn
(Hive Addict)
03-01-03 17:02
No 412905
      Nitric acid  Bookmark   

You heat the sulfuric acid and sodium nitrate until all of the nitrate dissolves and it boils. Set this up in a distillation apparatus and the distillate will be nitric acid. . .

Chemistry is hard to learn, but its worth it.
 
 
 
 
    Megatherium
(Hive Bee)
04-05-03 08:54
No 424094
      How much H2SO4?  Bookmark   

Then from the dropping funnel a pre-cooled (10C) mixture of 10ml 68% nitric acid (d. 1.42) and ... of concentrated (98%) sulfuric acid (d. 1.84) is slowly added drop by drop while the batch is vigorously stirred.

How many ml H2SO4 is added?
 
 
 
 
    Vitus_Verdegast
(Hive Bee)
04-05-03 21:20
No 424245
      2H2SO4 + HNO3 -> NO2+ + H3O+ + 2HSO4-.  Bookmark   

Use 2 mol equivalents sulfuric acid to 1 mol eq HNO3.

so:  10 ml HNO3 d 1.42 at 16.14 mol/l makes 0.1614 mol ; 0.1614 * 2 = 0.3228 mol H2SO4 needed, this corresponds to 32.306 gram 98%

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    hermanroempp
(Hive Bee)
04-06-03 09:11
No 424318
      Amendment to Post No. 411092  Bookmark   

"Nitrotoluene" :
Shame on me, I forgot to mention how many milliliters of sulfuric acid have to be used in the preparation of the mixed acid!
Well, so...12ml were used.
Thanks to Megatherium for the reminder..wink

Quidquid agis, prudenter agas et respice finem!