Sciencemadness Discussion Board - H2S on CNN: rash of suicides in Japan using OTC materials

H2S on CNN: rash of suicides in Japan using OTC materials

Sauron - 24-4-2008 at 06:38

According to major media reports, Japanese are killing themselves and sometimes endangering their neighbors by mixing laundry detergent and cleanser, or other OTC mixtures, to generate hydrogen sulfide.

The techniques are reported to be promulgated on various pro-suicide web sites.

I am wondering if anyone can shed any light on the chemistry or chemistries involved. Bath salts and liquid cleaners have also been mentioned, but the media are being vague about the brand names and compositions.

Such OTC generation of H2S might be of more than passing interest to some of us, though hopefully not for purposes of self-immolation.

Douchermann - 24-4-2008 at 07:06

Well paraffin wax and sulfur has worked for me for H2S (obviously not for suicide); paraffin wax can be bought by the pound in a grocery store, and sulfur in the garden section of super markets usually. That's quite OTC.

C25H52 + 26S ----> 26H2S + 25C

Sauron - 24-4-2008 at 07:17

The question was not how to make H2S. The question was how these Japanese are making H2S, and from what OTC materials precisely, and what is the chemistry?

I'm sure we can all come up with x-number of unrelated and irrelevant ways to make H2S.

not_important - 24-4-2008 at 07:23

http://smt.blogs.com/mari_diary/2008/04/customers-who-b.html

Sauron - 24-4-2008 at 07:36

OK, one component is called Sanpore in Japan. The rest of the links are useless to me as they are in Japanese.

I will google Sanpore and see what if anything I can find in English about its composition, I am not optimistic.

No luck in Google.

[Edited on 24-4-2008 by Sauron]

not_important - 24-4-2008 at 08:16

First I read of it said "medical products", which makes me suspect an acidic cleaner and something like http://www.drugs.com/cons/selenium-sulfide-topical.html

Sauron - 24-4-2008 at 08:42

A simple sulphide and an acid would certainly do the trick, but is boring chemically. I was hoping for something a wee bit more entertaining. Oh well.

Back in horse and buggy chemistry days this was done in a Kipp apparatus, which is a neat looking bit of glass that I have not seen sold for a long time, using iron pyrites ("fool's gold") and an acid. Usual general chemistry lecture was to demonstrate identification of metal ions by precipitation of their colored water-insoluble sulphides by bubbling H2S through. This was a routine high school level demonstration in the 60s and earlier.

Very little was made of H2S toxicity as I recall. More of a bad smell than a poison, was the attitude. Times have changed.

The Japanese are talking about banning the 1993 best selling book that teaches suicide techniques, while the Dutch are now publishing a similar volume, I am not sure if it is a translation or a fresh book. Go figure.

garage chemist - 24-4-2008 at 10:57

You try to make H2S from pyrite and acid? It doesn't work, FeS is needed for that. FeS2, remarkably, is inert against aqueous acids as far as I know.

Formatik - 24-4-2008 at 16:47

According to this: http://news.3yen.com/2008-04-17/japanese-fad-rotten-egg-suic...

They mix Sunpole® toilet cleaner (9.5% HCl) with MUTOUHAPPU (calcium sulfide) bath salts, to generate H2S.

-jeffB - 24-4-2008 at 16:54

Calcium sulfide bath salts?

Formatik - 24-4-2008 at 17:18

Yeah. That's what I thought too. Never heard of that. Here's a picture of the stuff:

A liquid solution.

not_important - 24-4-2008 at 17:22

Also known as 610 (you can see the number on the label)

http://ja.wikipedia.org/wiki/%E7%9F%B3%E7%81%B0%E7%A1%AB%E9%...

http://utumatari.blog110.fc2.com/blog-entry-197.html

Sauron - 25-4-2008 at 06:07

Japan has lots of volcanos, hence lots of volcanic hot springs rich in sulfur and people go soak in these for health. Try reading a good tourist guide to Japan.

So, I conclude that this calcium sulfide bath salts product is for people who want to simulate a mineral hot spring in their own tub.

Just a guess. Anyone have a better explanation?

not_important - 25-4-2008 at 06:30

Diluted it is used as a treatment for ringworm, but the major promoted use for products of this type is agricultural, with a minor use of staining metals. It could very well commonly be used off-label as a bath additive, the Japanese are almost as crazy as Americans when it comes to new uses.

Mr. Wizard - 25-4-2008 at 06:31

Just as general information, the color of the stuff looks like the Calcium Polysulfide solution sold as a "Dormant Disease Control" for fruit growing. I'm not going to mention a brand name. You mix the stuff with water and spray the fruit trees before they leaf out in the spring. It has the familiar H2S smell. Mixed with water about 20:1 it will immediately blacken shiny copper. It is quite effective at removing the copper layer from US pennies (post 1982), leaving a shiny zinc core.

peach - 13-1-2011 at 04:47

Hello Sauron

I just mentioned this (the sulphide suicides) in an entirely unrelated topic then, googling around the question, found you'd mentioned it.

The bath salts they are using is Mutohappu; I suspect others will work as well.

As formatik says, it functions because the product contains sulphides, as per the iron sulphide method with the kipps generator you mentioned.

I believe the product is likely made by evaporating off mineral well water. A lot of countries have historical wells and springs that people either used to bathe in or drink from due to the high mineral content. I have had a taste from two of these. One in Ireland and another in Poland. In both examples, they are clearly rich in sulphides because I could smell the unmistakable rotting eggs as soon as I went into the buildings. It'd be a bad day the day they get some cleaners in and they dump hydrochloric in there.

With that in mind, you'd be after bath salts that say something like "Natural spring minerals for ultimate awesome healing powa!" on the front. Some of them are kind enough to list the main components on the back. It is quite likely a lot of the ones you pick up will only have small amounts of the sulphides in them. If the components aren't listed, you could have a rough guess based on where it says they've come from.

Pyrite will react with concentrated hydrochloric, this was a test used to discern fools gold from real gold.

Remember that iron sulphide and hydrochloric are usually warmed in such a generator to get it going at a decent rate. It will likely also benefit from a session with a hammer prior to combining the two. Choosing samples based on their level of crystal size may make this process easier.

I haven't tried it with a lump myself, having only seen demonstrations of it when looking around, but I do have a nugget of gold in the post* and will foolishly give it a try with warm hydrochloric.

Maybe a video is in order, depending on how things work out (I have tried rending one on manganese now probably ten times, with various codecs and it taking an hour to do per ten minutes worth, then another half hour to upload, and it keeps coming out wonky; so it's annoying me and wasting a lot of time at present).

*I actually had a nugget of it lying around the house all of the time I was growing up. I tried burying it in the garden and then pretended I'd amazingly struck gold by digging it up later in front of my brother. Now I want some to try it, the things gone missing.

ScienceSquirrel - 13-1-2011 at 05:15

Alkalis like potassium, sodium and calcium hydroxides readily react with sulphur to form a mixture of sulphides and other things.
I am half tempted to try and make some.
There is a video here;
http://www.youtube.com/watch?v=ifoj7Dcj6JQ

Add a few drops of hydrochloric acid and I would guess fanny's your hydrogen sulphide

peach - 13-1-2011 at 06:02

Looks like he's getting ready to shoot up in the bathroom

But it's a good link!

You can produce zinc sulphide by igniting a pile of fine zinc powder with sulphur present in an equal state. There will be a flash as it goes.

Dripping HCl onto that certainly produces hydrogen sulphide, I've been doing it the last few weeks to check the results of things I'm trying with it.

The reaction doesn't work if the zinc is in big lumps. It likely does work, but the rate is so slow it's basically worthless.

It does also work with aluminium. Which is now VERY easy to get big bags of in micronic form as so many people want to have a go with thermite in the garden. The aluminium is produced by blowing molten aluminium through nozzles and into a cooling chamber, where microscopic droplets of it solidify and fall out as the dust.

To produce my zinc sulphide (trying to keep the number of components other than the battery starting point as low as possible), I've been dissolving battery casings in sulphuric (which will happily nomnom through them), then heating the resulting sulphate with sulphur - because the idea was to find a method that involved people buying the fewest number of other things; and grinding the casings up will introduce contamination, as will burning it in the open air.

Unlike the liver of sulphur method, you get pretty much pure zinc sulphide out of this - you can buy a stick of sulphur from the pet store (it's put in dogs' water bowls in the summer to heat them cool off; something to do with sweat and electrolyte I suppose, and the bar means it's unlikely to be cut with some other rubbish, and it's easy to smash it up into fine dust).

I was after the purest sulphide possible using basic, under the sink, chemicals for others to try with. The combustion methods would involve contamination as far as the needs of my work, but it'd be fine for hydrogen sulphide generation I'm thinking.

I have some aluminium and powdered sulphur out in the utility room.

Considering the ease of getting those two, that it only involves mixing them together and igniting them, that seems like a nice way to get a big lump for your generator. It doesn't matter if said lump isn't ultra pure, it just has to have a lot of sulphide in it.

Quote:

Liver of Sulphur is the alchemists' name for a chemical mixture that is produced by heating potassium carbonate with sulphur and was made as long ago as 776AD by the celebrated Arab alchemist Jabir Ibn Hayyan. It is not a true compound but a metastable mixture of potassium polysulphides and potassium sulphate. (K2S, K2S2, K2S3, K2S4, K2S5, K2SO4). Since the end point of the reaction used in Liver of Sulphur production varies from batch to batch, the exact constituents of Liver of Sulphur also vary from batch to batch.

^^^ Metalclayuk

[Edited on 13-1-2011 by peach]

ScienceSquirrel - 13-1-2011 at 08:09

I would guess that the attraction of liver of sulphur to the Japanese is that it is soluble in water and has mildly fungicidal properties.
It is probable that a weak solution in hot water would do wonders in clearing up athletes foot, dandruff, nadger itch, etc.
Aluminium sulphide is supposed to hydrolyse quite readily on contact with water, much like aluminium phosphide which is used to kill moles.
I wonder how effective it would be as a home made mole killer?

peach - 13-1-2011 at 18:43

I had a quick go at making some Aluminium Sulphide last night by simply mixing the two powders, I think I used 6.9g sulphur and 3.6? of aluminium.

Tried igniting it with a blow torch, but it didn't seem to do a lot.

Being on the way to bed, I went with sticking a strip of lithium in it to help it ignite, set it out in the garden in a ceramic ramekin and pressed 'hot'. It does crackle and spit sparks as it goes, so best not done inside, or with it too close to the precious new flesh of videodrome.

Going back inside, there was some unreacted sulphur melted and cooled onto the walls of the dish, a bit of aluminium powder and a sizeable blob of something fused (fused tightly enough the ramekin fell apart long before the blob, in fact.... it's like chipping rock trying to get it back off).

I put a few drops of water on a small fragment (about the size of your small finger tip, with a thin coat of this fused blob on it), it began to effervesce. I could very easily detect the smell of rotting eggs, quickly.

I decided to leave it, not wishing to wake up dead in the utility room, and went back inside. Where in I was immediately met by someone upstairs saying they could smell "shit, eggy shit", coming under the door, which is through some double glazing, through the house and upstairs.

I ran that test at about 4pm. It's now 2.41am, and it still smells of egg in the house. The samples are outside, but I think it's getting in through a gap in the door frame.

I guess that'd be a fairly easy way to make it based on the persistence and strength of smell coming off these little lumps.

Doesn't even seem to need hydrochloric no, I didn't use any and I think the lumps are now reacting with damp in the air out there, I would expect it to have cleared the air by now if it wasn't.

[Edited on 14-1-2011 by peach]

mr.crow - 13-1-2011 at 20:29

Yikes for a minute there I thought Sauron was back

ScienceSquirrel - 14-1-2011 at 04:29

Quote: Originally posted by mr.crow

Yikes for a minute there I thought Sauron was back

Not the Dark Lord himself!

I live in Jersey most of the time but I have a lot of friends in Brittany and I visit quite a lot.
Jersey is pretty tame but Brittany is very French with a slight air of Hazzard County, a strong sense of DIY and an up yours attitude towards Paris.
In most of France if you have a wasps nest you call in the pompiers ( firemen ) and they get rid of them.
However in Brittany you pour a couple of litres of petrol, diesel, paraffin, etc down the hole. Opinions vary as to which is best and how much to add.
Home made aluminium suphide for mole slaughtering would probably get me in with the Kronenbourg drinking locals down at the cafe tabac.

peach - 14-1-2011 at 04:32

The stuff became a problem last night.

At 4am, with the cooker hood and toilet extractor having been running all night, the entire house still stank of it.

A family member went out to Tescos and heard two members of staff asking if they could smell something odd (since tesco's sells a lot of food, the smell of rotting food is something they won't want in a megastore); meaning there was enough of it on their clothes for people to smell it walking past.

Worried about what could be going on with the concentrations and exposure, I ended up having to go back outside, collect all the bits together, put them in a paper bag, then double bag that inside two plastic ones to try and get rid of the smell. I expect the neighbours can smell it, as two windows and the door to the garden are open out there.

The smell is FINALLY starting to die down a bit in the house now it's bagged and away from the damp air (it'd been raining overnight), but it's still clear when you walk back in and particularly if you go out to the utility room.

So a bit of aluminium powder and some sulphur will get you a nice supply of it for your generator.

This method has both strong positives and negatives.

Firstly, the materials are very easy to get in large amounts, it seems to be yielding a good amount of usable product, making the sulphide is super simple (the reaction runs for about five seconds) and it doesn't involve wasting acid or having glassware full of it sitting on the desk.

Downsides... the ones I'm experiencing. If you spill it, moisture gets in the bottles it's stored in, it will stink the place out and could potentially become dangerous - especially if you fall asleep and it gets going overnight. It makes disposal harder to deal with, as the sulphide will do the same thing in the bin. So the bin and everywhere around it will absolutely stink. Again, it could also be dangerous as it will build up in the bin to a potentially explosive / lethal concentration with the lid closed.

Zinc sulphide, however, doesn't do this. Neither does iron.

Those have a disadvantage against aluminium because finely divided zinc and iron may be harder to find. Although, iron filings aren't so bad (they won't be as fine as the aluminium, so you may not get as thorough a reaction when producing the sulphide).

It would probably benefit from a sprinkling of magnesium powder in the mixture to get it all going.

I made a short video of me doing this, now I need to get the bastard to render correctly.

[Edited on 14-1-2011 by peach]

ScienceSquirrel - 14-1-2011 at 04:44

There are a few hints here, it might have been best to Wiki it before making it!

http://en.wikipedia.org/wiki/Aluminium_sulfide

ScienceSquirrel - 14-1-2011 at 04:53

I have made iron sulphide by melting iron filings and sulphur together.
It is pretty easy and it only reacts with strongish acids so it is a lot more convenient as a source of hydrogen sulphide.
Aluminium sulphide sounds a little too excitable!

The WiZard is In - 14-1-2011 at 07:54

Quote: Originally posted by peach

The stuff became a problem last night.

At 4am, with the cooker hood and toilet extractor having been running all night, the entire house still stank of it.

A family member went out to Tescos and heard two members of staff asking if they could smell something odd (since tesco's sells a lot of food, the smell of rotting food is something they won't want in a megastore); meaning there was enough of it on their clothes for people to smell it walking past.

Worried about what could be going on with the concentrations and exposure, I ended up having to go back outside, collect all the bits together, put them in a paper bag, then double bag that inside two plastic ones to try and get rid of the smell. I expect the neighbours can smell it, as two windows and the door to the garden are open out there.

The smell is FINALLY starting to die down a bit in the house now it's bagged and away from the damp air (it'd been raining overnight), but it's still clear when you walk back in and particularly if you go out to the utility room.

So a bit of aluminium powder and some sulphur will get you a nice supply of it for your generator.

Tell the WiZ (donald j haarmann)
American Fireworks News #38
http://www.fireworksnews.com/
November, 1984.

USES FOR PYROTECHNICS YOUR MOTHER NEVER TOLD YOU ABOUT
THE PYROTECHNIC BLANKET

Because steel reinforced portland cement concrete bridge decks are susceptible
to premature and severe corrosion damage during use caused by the
absorption of water and salt solutions, Internally Sealed Concrete was
developed. Wax beads are uniformly distributed throughout. The portland
cement concrete mix at the time of mixing. After the concrete cures, the wax
beads remain as such in the concrete. To become effective the beads must be
melted so that the wax can flow into the pores, capillaries and cracks of the
concrete. And therein lies the problem; how to heat up a bridge!

Electric blankets were tried with little success. Therefore as "Pyrotechnic
materials are portable self-contained energy sources that can produce large
quantities of heat", the pyrotechnic blanket was developed.

Because of cost requirements, a maxim heat output for minim money input was
desired., therefore a hybrid system of iron and aluminium powders (fuel) and
sulphur (oxidizer) was used. Finely divided aluminium and iron powders each
react with sulphur (2 Al + 3 S = Al2S3 and Fe + S = FeS) to produce producing
1470 and 455 BTU per pound. The reaction temperature for the sulphur and
aluminium being 1200oF (650oC), the iron sulphur reaction temperature is
510oF (275oC). By controlling the mixture, temperatures between these limits
can be produced. Maximum use of aluminium was preferred due to its higher
exotherm and the resulting better thermal cost efficiency. However, iron was
desired to reduce both the maxim temperature and the burning rate of the
pyrotechnic, thereby increasing the length of time heating would take place.

The composition adopted as representing the best blend of fuels (powdered
metal), oxidizer (sulphur) and fillers was the following:

Sulphur 39.06
Medium Sand 14.85
Carbon Black 7.62
Aluminum 12.50
Iron 25.97

The ingredients were mixed and then heated until the sulphur melted, with the
resulting, mass allowed to cool in molds.

Significant savings in" material costs was obtained by using reclaimed and re-
processed aluminum scrap (cans) obtained from Alcoa. ($0.50 lb)

There is, of course, a large problem with this process; the end products of the
reaction between both aluminum and iron with sulphur are sulphides. The iron
(ferrous sulphide) is of no concern. However aluminium sulphide is another
animal, a rotten smelling one at that! For aluminium sulphide and moisture will
react to form aluminum hydroxide, and good old hydrogen sulphide! One could
foresee both esthetic and health problems, as hydrogen sulphide is more
poisonous than hydrogen cyanide gas!

FHWA-RD-79-144
Self Contained, Expandable Pyrotechnic Blankets for Heat-Treating internally
Sealed Concrete.
75 pages;
NTIS PB82-108820

The WiZard is In - 14-1-2011 at 08:00

Quote: Originally posted by Sauron

A simple sulphide and an acid would certainly do the trick, but is boring chemically. I was hoping for something a wee bit more entertaining. Oh well.

Aluminium phosphide (insecticide) is commonly used to end all troubles.

MMWR September 13, 1991 / 40(36);619-621,627-629
Epidemiologic Notes and Reports Chlorine Gas Toxicity from Mixture of Bleach
with Other Cleaning Products – California

From October 1987 through November 1989, five episodes of chlorine gas
exposure with toxicity to at least 14 persons occurred at two state hospitals in
California. Each hospital provides inpatient treatment to approximately 1000
forensic psychiatric patients. As part of their rehabilitation programs, selected
patients perform cleaning duties under the supervision of janitors or nursing staff.
Each incident occurred during the performance of these duties and involved the
mixture of bleach (sodium hypochlorite) and a phosphoric acid cleaner by
inpatients. This mixture produced chlorine gas and other chemical byproducts
(Figure 1a and 1b), and resulted in temporary illness in exposed persons.
Hospital A

Episode 1. On October 18, 1987, a patient poured an undetermined amount of a
4% phosphoric acid cleaner into a bucket containing diluted bleach. A chemical
reaction occurred immediately, releasing an irritating gas. The patient was
assisted from the room, and the cleaning solution was diluted with water and
poured down a drain. Windows were opened to ventilate the area, and the ward
was evacuated. The patient complained of anxiety, chest tightness, difficulty
breathing, and heartburn; physical examination revealed scattered bibasilar
pulmonary rhonchi. He was treated with supplementary oxygen, and most
symptoms subsided after 1 hour.

Episode 2. On December 19, 1987, a patient mopped a bathroom floor with a 4%
phosphoric acid solution, then rinsed the floor with water. Immediately after he
applied a bleach and water solution to the floor, a noxious gas with a strong odor
was emitted. The mixture was poured down a drain, and the floor was again
rinsed with water; however, because the room's exhaust fan was inoperative and
windows had been sealed shut, the gas dispersed throughout the ward and
caused symptoms in other patients. The ward was evacuated; patients and staff
returned after 1-1/2 hours when the odor had dissipated. Within an hour of their
return, additional patients and staff complained of symptoms including nausea,
eye irritation, tearing, sore throat, headache, cough, and chest tightness; one
patient had an acute exacerbation of asthma. The ward was reevacuated until
the following day. The local fire department assisted with ventilation.

Episode 3. On December 25, 1987, a patient mixed approximately 1/2 L of
bleach and 1 L of a 4% phosphoric acid cleaner in a bucket, creating a noxious
gas. The patient rapidly developed eye irritation followed by fatigue; four
employees developed symptoms that included a lightheaded dizziness, nausea,
eye and nose irritation, headache, and chest tightness. The ward was evacuated
until chemical residues on the bathroom floors had been rinsed and air exchange
had been completed using the existing exhaust fan system. For some persons,
symptoms persisted for several hours. More than an hour after the episode, two
employees entered an enclosed nursing office 50 feet from the gas release site;
despite the absence of a detectable chlorine odor, both promptly experienced
recurrent symptoms.

Following these three incidents, patients and employees were interviewed to
establish policies to prevent recurrences. Each incident involved the same
phosphoric acid formulation. The three patients had been supervised by different
staff; they denied mixing the chemicals intentionally to create a disturbance,
denied knowing each other, and denied knowledge of previous episodes. Each
incident occurred on a weekend or holiday, when janitors were off duty and the
patients were cleaning bathroom floors while being supervised by ward nursing
staff without constant observation.

Beginning December 29, controls were instituted on the storage and use of the
phosphoric acid cleaner at hospital A. The cleaner was dispensed by
housekeeping supervisors to janitors, who kept it locked in storage areas
accessible to employees only.

Episode 4. Despite more stringent controls over the use of cleaning products, a
fourth episode occurred. On November 3, 1989, a patient supervised by a new
employee was allowed in a locked storage area and poured an undetermined
amount of 4% phosphoric acid cleaner into a bucket containing bleach and water,
immediately producing a cloud of noxious vapor.

The employee assisted the patient from the area, then returned to the area and
poured the contents of the bucket down a sink. The employee, who was exposed
to the vapors for less than 1 minute, reported immediate throat and nasal burning
that persisted for more than 24 hours, as well as transient dizziness and nausea.
Supplemental oxygen was administered at a local acute-care hospital emergency
room for 3 hours. The employee completely recovered within 36 hours following
exposure. The patient had no symptoms.

Following this incident, acidic cleaning products at hospital A were locked in the
offices of housekeeping supervisors; access was available only to janitors and
was denied to both nursing staff and patients. In addition, the hospital has
prohibited the mixing of cleaning products. No further incidents have occurred.
Hospital B

On December 7, 1988, a patient assisting in janitorial duties mixed bleach with
phosphoric acid cleaner. Immediately a noxious gas with a strong odor was
detected and prompted the evacuation of two wards for 1-1/2 hours. Fire
department personnel using self-contained breathing equipment disposed of the
chemicals and ventilated the area.

The patient experienced vomiting, cough, and inspiratory discomfort; elevated
blood pressure and fever were noted when the patient was treated in the
emergency room. Five employees who helped evacuate the ward complained of
symptoms including eye irritation and shortness of breath. Employees and
patients returned approximately 1-1/2 hours after the area was ventilated. After
this incident, hospital B instituted warning labels on all chemical cleaning
products and posted precautionary (i.e., "do not mix") signs on janitorial closets.
Bleach and acidic cleaning products were restricted to use by staff. No further
incidents involving phosphoric acid products have occurred at this hospital.
Product Label Investigation and Modifications

The label of the phosphoric acid cleaner involved in all five incidents did not list
the active ingredient nor warn of the potential for toxic reactions when phosphoric
acid was mixed with other chemicals. The material safety data sheet (MSDS) did
not describe potentially toxic chemical reactions or incompatibilities. The labels
and MSDSs of two other products containing phosphoric acid in use at hospital
A, including one with a 30% acid concentration, also lacked information on
reactions and incompatibilities with hypochlorite.

After notification by hospital A in December 1987 about episodes 1-3, a new
label was supplied by the chemical manufacturer in early 1988 for use by
institutional customers wishing to transfer the product into smaller storage
containers. The new label included the statement: "Do not mix with other
chemicals (such as bleach or ammonia)." In 1989, the product's label was
revised to add a similar statement. The MSDS was revised in May 1991; it now
mentions incompatibility with ammonia or bleach but still does not state what will
result from those mixtures.

The product is marketed directly by the manufacturer to institutions in Arizona,
California, Montana, Oregon, and Washington. It is not sold in stores to the
general public and therefore is not considered a consumer product by the U.S.
Consumer Product Safety Commission (CPSC) and is exempt from labeling
requirements of the federal Hazardous Substances Act. However, according to
the California Department of Industrial Relations, Division of Occupational Safety
and Health (Cal-OSHA), as a California workplace product it is subject to the
state's hazard communication standards, which require the label to list the
phosphoric acid and appropriate hazard warnings and the MSDS to include
reactivity and incompatibilities; the wording to describe the chemical interactions
is not specified by law (R.E. Erickson, Cal-OSHA, personal communication,
1991). Reported by: RP Hattis, MD, California Dept of Mental Health; JR Greer,
MD, S Dietrich, DO, S Olafsson, MD, Dept of Preventive Medicine, Loma Linda
Univ, Loma Linda; KR McAndrew, Long Beach Memorial Hospital, California.
Health Studies Br, Div of Environmental Hazards and Health Effects, National
Center for Environmental Health and Injury Control, CDC.
Editorial Note

Editorial Note: The chemicals involved in the first three incidents were a standard
household bleach (5.25% sodium hypochlorite solution [NaOCl]) and a 4%
phosphoric acid (H3PO4) cleaning agent. When sodium hypochlorite and an acid
are mixed, chlorine gas and water are released (Figure 1a). Chlorine gas reacts
with the water to form hydrochloric and hypochlorous acids (Figure 1b). Chlorine
gas may cause a variety of symptoms as a function of the severity of exposure
(1-3). Hydrochloric acid also causes inflammation that may, along with nascent
oxygen release, be one of the mechanisms of tissue damage by chlorine (4).

Mild mucous membrane irritation may occur in some persons after several hours
at levels as low as the threshold limit value (TLV) of 1 ppm (1,3); this TLV may
warrant reassessment (1). A level of at least 3 ppm may cause extreme irritation
of the eyes and respiratory tract, but a detectable odor is usually not present
below 3.5 ppm (2). Symptoms following exposure to chlorine have included
irritation of the eyes, nose, and throat; dizziness; cough; and chest pain or
constriction. Severe exposure may cause pulmonary edema, bronchiolar and
alveolar damage, and pneumomediastinum (1,2,4-6).

When bleach is mixed with ammonia-containing compounds, monochloramine
(NH2Cl) (Figure 1c) and dichloramine (NHCl2) (Figure 1d) are formed, which
may produce tearing, respiratory tract irritation, and nausea. These compounds
decompose in water to hypochlorous acid and free ammonia gas (6-8); the
former combines with moisture forming hydrochloric acid and toxic nascent
oxygen (8); the latter is a respiratory and mucous membrane irritant and can
cause pulmonary edema and pneumonia (6,7).

Only four case reports have been published of chlorine toxicity from mixing
bleach with acid cleaning agents, including one describing near-fatal pulmonary
edema, two of pneumomediastinum, and one of mild illness in which other family
members also became symptomatic. None of these reports involved phosphoric
acid; in three, inadequate ventilation probably contributed to the toxic effects (4-
6). However, the American Association of Poison Control Centers data collection
system listed 409 cases of chlorine exposure in 1990 from acid mixtures with
hypochlorite that were reported from 72 participating centers serving 77% of the
U.S. population. Of these cases, 395 (97%) were unintentional exposures and
356 (87%) occurred among persons aged >17 years; 128 required treatment in
health-care facilities. Of 340 exposures for which outcome was known, 292 were
considered to have caused minor and 30 moderate illness (9). Cases recorded
by poison-control centers probably underrepresent substantially the episodes
actually occurring; for example, no poison-control center was consulted about the
five incidents in this report.

A directive for CPSC compliance staff for monitoring the chemical product
industry requires labels on consumer products containing 5% or more
hypochlorite to include warnings against mixing with acids and other household
chemicals and for labels of products containing 3% or more ammonia to warn
against mixing with chlorine-type bleaches or other household chemicals (10).
There is no required warning for phosphoric acid, nor does the CPSC routinely
inspect any chemical consumer products. Products sold only for institutional or
other workplace use are not monitored by CPSC, and the responsible
occupational health and safety agencies (the federal Occupational Safety and
Health Administration or a state agency) rely on manufacturers/importers and
employers to be informed of potential health hazards of workplace chemicals and
to inform customers and employees by MSDSs (11,12). Agencies monitor
workplace chemical labeling and MSDSs by periodic inspections, with feedback
to companies with deficiencies (13). The probability that any given chemical
product will be reviewed by this process is low. No complete compilation has
been made of the millions of consumer and industrial chemical product
formulations, labels, and MSDSs in the United States. There is no federal
requirement that wording on labels and MSDSs be cleared by a regulatory
agency as a precondition for sale or distribution of chemical products.

Three approaches can be implemented to prevent potential toxic exposures in
institutional and other industrial settings from mixtures of bleach with other
cleaning agents:

1. Housekeeping policies should be established in institutions to educate new or
untrained employees and patients or inmates who assist in cleaning about the
potential danger of chemical mixtures and to provide constant supervision for
persons whose judgement may be impaired. When this is not possible, use of
such chemicals should be restricted to fully trained and experienced employees.

2. When chlorine gas is unintentionally released, areas in which the gas could
circulate should be evacuated until sufficient air exchanges have occurred to
ensure that the gas has been eliminated. The absence of odor is not a reliable
indicator of safety. Pending the complete evacuation of gas, employees involved
in cleanup or onsite investigation of such incidents should wear protective
respiratory equipment, and none should enter without a companion (14).

3. OSHA and state agencies designated by federally approved state occupational
safety and health plans should contact all known manufacturers and importers of
cleaning products that contain hypochlorite, acids, or ammonia and are used in
institutions and other workplaces to clarify and reinforce proper labeling and
MSDS requirements and to encourage education of their customers about
nonmixing.

References
1. Arena JM. Poisoning--toxicology, symptoms, treatment. 5th ed. Springfield,
Illinois: Charles C. Thomas, 1986:298-300,316- 8,692.
2. Sax NI, Lewis RJ. Dangerous properties of industrial materials. 7th ed. Vol 2.
New York: Van Nostrand Reinhold, 1989:768.
3. Ellenhorn MJ, Barceloux DG. Medical toxicology: diagnosis and treatment of
human poisonings. New York: Elseviere, 1988:878,891,903.
4. Jones FL. Chlorine poisoning from mixing household cleaners [Letter]. JAMA
1972;222:1312.
5. Gapany-Gapanavicius M, Yellin A, Almog S, Tirosh M. Pneumomediastinum--
a complication of chlorine exposure from mixing household cleaning agents.
JAMA 1982;248:349-50.
6. Faigel HC. Hazards to health: mixtures of household cleaning agents. N Engl J
Med 1964;271:618.
7. Gosselin RE. Clinical toxicology of commercial products. 5th ed. Baltimore:
Williams and Wilkins, 1984:111-204.
8. Gapany-Gapanavicius M, Molho M, Tirosh M. Chloramine-induced
pneumonitis from mixing household cleaning agents. Br Med J 1982;285:1086.
9. Litovitz TL, Bailey KM, Mitz BF, et al. 1990 Annual report of the American
Association of Poison Control Centers national data collection system. Am J
Emerg Med 1991;9:461-509.
10. Office of the Federal Register. Code of federal regulations: hazardous
substances labeling guide. Washington, DC: Office of the Federal Register,
National Archives and Records Administration, 1984. (16 CFR 1500.121).
11. Occupational Safety and Health Administration. Preamble to final rule on
hazard communication. Federal Register 1983:48:53337.
12. Occupational Safety and Health Administration. Hazard communication.
Federal Register 1987;52:31852-86.
13. Occupational Safety and Health Administration, Office of Health Compliance
Assistance. Inspection procedures for the hazard communication standard.
Washington, DC: Occupational Safety and Health Administration, 1990.
[Instruction CPL 2- 2.38C].
NIOSH. Occupational exposure to chlorine: criteria for a recommended standard.
Cincinnati, Ohio: US Department of Health, Education, and Welfare, Public
Health Service, 1976.

blogfast25 - 14-1-2011 at 09:30

Al2S3 is my favourite source of H2S. Easy to make and requires only water to get the flow going. But you need to use it responsibly. After synth., store it in a dry and HERMETIC jar. To use: only use what little you need.

To kill it: dowse in thin commercial bleach, lots of it and dispose of the mess in an empty pop bottle, capped, when most of the smell has subsided. Bleach oxidises H2S to elemental sulphur (but you need enough of it – easily calculated).

As regards Japs taking baths with CaS in them, ‘nought queerer than folk’ as they say here. CaS hydrolyses straight to H2S but it’s little slower than Al2S3. Small amounts of CaS can be made by reacting CaSO4 with Al, thermite style. You end up with a mix of Al2O3 and CaS, less reactive than CaS or Al2S3.

peach - 14-1-2011 at 11:38

@the squiggel

Consider this did he..... but realise not how strongly the force flows with it, to bring darkness when damp is the air.

Humidity on endor at present is around 30-40% - not a lot.

Added a note on hydrolysis in the atmosphere he has to the wiki.

@Wizard

I saw those monster posts and thought... there's no way I'm reading that.

But read I did, and found them entertaining.

@Blogfast

Nice to hear you're also on the smelly quest with this.

I have read about scrubbing the gas and yes, bleach is used.

I believe the more thorough scrubbers used for larger scale problems use NaOH in a first stage, to precipitate the gas out as the sulphides, then bleach to render them inactive - so they don't start re-emitting if they get mixed with something in the waste systems.

How do you make yours blogster? Are you using a metal thimble or container of some kind, and do you bother mixing anything with it to get the whole pile going? Most of mine went, but I gave it a kick start with a strip of lithium (ala, putting a bit of mag. ribbon in thermite). There were just a few traces of unreacted aluminium powder, some signs of burning sulphur for about 20s and some yellow marks from condensation.

I used a ceramic ramekin, which split and fell apart. But I also noticed it was next to impossible to get it back off even with the ceramic in bits. I'm guessing it may be easier with a metal tin that can be bent - tuna can?

[Edited on 14-1-2011 by peach]

blogfast25 - 14-1-2011 at 14:19

Quote: Originally posted by peach

@How do you make yours blogster? Are you using a metal thimble or container of some kind, and do you bother mixing anything with it to get the whole pile going? Most of mine went, but I gave it a kick start with a strip of lithium (ala, putting a bit of mag. ribbon in thermite). There were just a few traces of unreacted aluminium powder, some signs of burning sulphur for about 20s and some yellow marks from condensation.

I used a ceramic ramekin, which split and fell apart. But I also noticed it was next to impossible to get it back off even with the ceramic in bits. I'm guessing it may be easier with a metal tin that can be bent - tuna can?

[Edited on 14-1-2011 by peach]

Aha! My Kickstart of Everything is a stoichiom. mix of KClO3+Al powder, sometimes with just a small pinch of S added. Light that ignition mix with a propane pen, sparkler or such like and it burns to > 2,500 C (you don't need much!) Once lit, the Al+S mix burns very hot. Remember it's used as a heat booster in SiO2 thermites for old fashioned 'technical silicon'... Done that, been there.

As a crucible usually an egg cup embedded in dry sand. Doesn't melt, cracks but doesn't fall apart. Ideal for my purposes. I've made niobium in one of these, T approx. 3,000C, no probs

[Edited on 14-1-2011 by blogfast25]