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Organikum
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[*] posted on 15-12-2003 at 07:31
SnCl4


I will make some SnCl4 soon and this is my idea how to do this:

Chlorine generator:
HCl dropped onto bleaching powder.

Wash and dry:
bubbling through a washbottle with H2O followed by by one with conc. sulfuric acid.

Reaction-chamber:
A vessel with a outlet at the bottom and a condensor on top. Usual plumbers tin is put in the middle of the vessel on a perforated plate - chlorine vented into the chamber and the formed SnCl4 is boiled to recondense and drop on the tin again (standard "dry" procedure to remove tin from tincans). On the bottom hopefully SnCl4 - thats a liquid - will collect and will be withdrawn after some time and immediately chilled. Aircontact will be avoided as far as any possible.

ideas?
better ways?
flames?

questions:
inhowfar will the Pd and antimone interfere?
actually I guess the Sn will react predominantly with the Cl2 - but the antimone so present?

[Edited on 15-12-2003 by Organikum]
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[*] posted on 15-12-2003 at 09:19


Quote:

questions:
inhowfar will the Pd and antimone interfere?
actually I guess the Sn will react predominantly with the Cl2 - but the antimone so present?

[Edited on 15-12-2003 by Organikum]

If you grind up the tin, you're reaction will be faster; a powder would be ideal.
Can you heat up the tin at all?
I wish I could just trot down to the chemistry library. The following URL
http://a257.g.akamaitech.net/7/257/2422/14mar20010800/edocke...
implies that the direct reaction of tin and chlorine produces stannous chloride, but it's been a long time since I had this kind of thing memorized! The internet is kind of weak when it comes to details of preperatory chemistry...
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[*] posted on 15-12-2003 at 09:55


No, reaction of Cl2 and Sn should lead directly to SnCl4. If he was using HCl, SnCl2 should be expected. I seem to recall that the reaction between Cl2 and Sn is vigorously exothermic once started.

Finely divided antimony reacts vigorously (to the point of combustion) with Cl2, but I do not know if/how the chloride formed will interfere in your final application.

According to the Journal of Applied Chemistry of the USSR, a 3:2 (weight) ratio of cobalt and iron salts is an effective catalyst to make calcium hypochlorite yield Cl2 when heated dry, or O2 when heated with water. I know cobalt is expensive but I think this is interesting in case one might need Cl2 and doesn't want to use a lot of H2SO4 drying it.
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Organikum
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[*] posted on 15-12-2003 at 10:08
thanks so far


guaguanco:
As Polverone told, the reaction of tin and and Cl2 is already very exothermic so tin in powderform might be a bad idea - I prefer a slow reaction here.

Polverone:
H2SO4 isnt the problem as it can be concentrated again with ease, also I dont expect to much water being taken up by the chlorine as I use a slow flow of the gas to control the - rather violent reaction.

The refluxing and dropping the condensed SnCl4 over the tin again seems to be the trick.




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[*] posted on 15-12-2003 at 10:16
Additional information


SnCl4 is easy to be handled so it is chilled to 0°C - it is told that no fuming occurs at this temperature.

Also it is a effective drying agent - also it was told to be somehow expensive for this kind of use.
Not if made by oneself I want to add.

(both was found at the HIVE)

In my opinion the relative stability to air so chilled and the liquid form make SnCl4 a much more usable Lewis-Acid than AlCl3 for example, easier to produce and to handle and of often better selectivity.

Question:
Does AlCl3 or FeCl3 dissolve in SnCl4?




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[*] posted on 15-12-2003 at 10:28


Quote:
Originally posted by Polverone
No, reaction of Cl2 and Sn should lead directly to SnCl4. If he was using HCl, SnCl2 should be expected. I seem to recall that the reaction between Cl2 and Sn is vigorously exothermic once started.

Finely divided antimony reacts vigorously (to the point of combustion) with Cl2, but I do not know if/how the chloride formed will interfere in your final application.

According to the Journal of Applied Chemistry of the USSR, a 3:2 (weight) ratio of cobalt and iron salts is an effective catalyst to make calcium hypochlorite yield Cl2 when heated dry, or O2 when heated with water. I know cobalt is expensive but I think this is interesting in case one might need Cl2 and doesn't want to use a lot of H2SO4 drying it.

Thanks. If nothing else, this board will cudgel my brain into thinking about inorganic chemistry after many years hiatus!
SbCl5 is a good Lewis Acid, so it *probably* wouldn't interfere in Freidel-Crafts type reactions.
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[*] posted on 15-12-2003 at 11:09
more data


STANNIC CHLORIDE (ANHYDROUS)

CAS No: 7646-78-8
RTECS No: XP8750000
UN No: 1827
EC No: 050-001-00-5
Tin tetrachloride
Tin (IV) chloride
SnCl4

Molecular mass: 260.5
Not combustible.
Gives off irritating or toxic fumes (or gases) in a fire. In case of fire in the surroundings: dry sand, powder, carbon dioxide, NO hydrous agents. EXPLOSION !

And now:
how stupid can a MSDS be ?? Thats in same sheet !!!

In case of fire: cool drums, etc., by spraying with water but avoid contact of the substance with water.


Inhalation: Burning sensation. Cough. Laboured breathing. Shortness of breath. Sore throat. Wheezing. Ventilation, local exhaust, or breathing protection. Fresh air, rest. Half-upright position. Artificial respiration if indicated.
Skin: Skin Redness. Skin burns. Pain. Blisters.

- Oh my god read this! -
Rinse and then wash skin with water and soap.

Here I stop with this bullshit.

I say:
Dont inhale by any means.
Dont spill on skin.
Keep icecold and dry.
--------------------------------------------------------------------------------

Boiling point: 114C
Melting point: -33C
Relative density (water = 1): 2.26
Solubility in water: reaction
Vapour pressure, kPa at 20C: 2.4
Relative vapour density (air = 1): 9.0

Appearance
COLOURLESS OR SLIGHTLY YELLOW FUMING LIQUID, WITH PUNGENT ODOUR. The vapour is heavier than air. The substance decomposes on heating producing toxic fumes. Reacts violently with water forming corrosive hydrochloric acidand tin oxide fumes. Reacts with turpentine, alcohols and amines causing fire and explosion hazard. Attacks many metals, some forms of plastics, rubber and coatings. Reacts with moist air to form hydrochloric acid.

[Edited on 15-12-2003 by Organikum]
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[*] posted on 15-12-2003 at 15:10


Just wondering but what is the use of SnCl4, the only use i know of is for tetrameric acetone peroxide. Would it be a suspicious chemical to order?
thanks.
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[*] posted on 15-12-2003 at 15:18


It's widely used as a reducing agent and as a reagent for qualitative cation analysis.



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[*] posted on 15-12-2003 at 15:49


Oh no it's not, you have your oxidation states muddled.

BTW a useful trick for drying gases is to cool them and condense out the bulk of the water before bubbling through a drying agent.
In this case, if there is water in the chlorine, it will waste tin, but it isn't likely to stop the reaction.
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[*] posted on 15-12-2003 at 15:53
SnCl4 for tetrameric AP??


SnCl4 for tetrameric Acetone peroxide? Rogue could you elaborate??
Do make it yourself though, rather than ordering it, it's a lot more fun making it yourself! And not particularly hard!

Anyway, what are the other uses of this?




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[*] posted on 15-12-2003 at 15:56


Quote:
Originally posted by rogue chemist
Just wondering but what is the use of SnCl4, the only use i know of is for tetrameric acetone peroxide. Would it be a suspicious chemical to order?
thanks.

It's a useful Lewis acid, similar to AlCl3. It's used in a variety of synthetic preparations.
For example: Ar-H + SnCl4 + CH3-O-CHCl2 ===> Ar-CHO

[Edited on 15-12-2003 by guaguanco]
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[*] posted on 15-12-2003 at 17:48


Finally found the article i first got the idea from.

http://www.rsc.org/CFCart/displayarticlefree.cfm?article=8%2...

I personally have not made it yet (tetrameric only ;) ) but i was about to send an order soon so I would like to know if it is a suspicious chem or will get you on any "lists".
I believe thet there is a thread on it i the E&W archives but now you cannot view anything there unless you are a member .:( .
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[*] posted on 17-12-2003 at 05:15
for example


many Friedels-Craft type reactions (alkylations in special) run better with SnCl4 than with the stronger AlCl3 or FeCl3 and yield less to none polyalkylated product. Also it is a useful drying agent and asscheap so selfmade.

Chemoleo your post sounds as if you have already experience in producing SnCl4? Mind to disclose some experiences?

rougue chemist: I myself prefer to order nothing from chemhouses at all - but thats just me and I have my reasons for doing so. (I had already some problems with authorities regarding my hobby and I dont want this to happen again)

guaguanco: thanks for the antimone information - my starting material will be plumbers tin which consists from 97% tin and 3% antimone - perhaps there is some ZnCl2 mixed by, but this is a (weaker) Lewis acid by its own and shouldnt interfere in any way.

My question on solubility of AlCl3 and FeCl3 in SnCl4 is still unanswered - I thought it might be a favorable idea to mix some of these (already during the SnCl4 production) into the liquid tin(IV)chloride for to "kickstart" the reaction (Friedels-Craft). This might allow lower temperatures and minimize byproduct without leading to excessive polyalkylated byproducts.

Yes, thats true chemistry from the 19th century - I love it! - thanks to the 19th century digital boy who brought me on this trail!

[Edited on 17-12-2003 by Organikum]
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thumbup.gif posted on 5-1-2004 at 20:13


I WANTED to post the idea of electrolysis of molten SnCl<sub>2</sub> on <i>Chloride</i> thread but I ended up with a lamp gleaming above my head!:D
look @ this diagram:
<img src="http://www.angelfire.lycos.com/rnb/pjff/SnCl4-PJFF.gif">
stannous chloride melts @ 246.8°C (which isn't that much of heat). you can recycle the tin by adding HCl to the cell boiling it away and heat till the SnCl<sub>2</sub>.H<sub>2</sub>O losses its water




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[*] posted on 30-1-2004 at 06:30
modifications


- Chlorine generator:
dil. H2SO4 dripped onto bleaching powder
- No washing, no drying.

- the Cl2 is bubbled through molten tin.
- hydrated SnCl4 should precipitate as crystals and can be filtered out,
- alternativly the SnCl4 is distilled with conc. H2SO4 to yield anhydrous SnCl4.

btw. anhydrous FeCl3 can be made from hydrated FeCl3 by heating this to dryness whereby Fe2O3 and FeCl3 are formed. HCl and water are evolved.
The FeCl3 should be extractable by any suitable organic solvent - the rust shouldnt dissolve.

Thanks to a_bab for the MOA rips.




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[*] posted on 30-3-2004 at 20:38
metal chlorides


I made some SnCl4 and FeCl3 - AlCl3 sooon to come and some pictures on the setup.

The main problem is to keep the reaction slow as once started it gets quickly VERY exothermic.

The temperatures needed to start the reaction are not very high:
Ullmann states for iron 160°C and tin reacts already at roomtemperature so finely divided - I used bigger chunks so some heating was applied.
:o




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[*] posted on 31-3-2004 at 01:53


I thought SnCl4 is unstable as it hydrolyses quickly in air to form HCl jus like SiCl4



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[*] posted on 31-3-2004 at 02:12


Huh?
Yes, of course all those metallic chlorides decompose in contact with moist air. Thats why bottles should be labeled: "Keep dry and well stoppered"

But SnCl4 isnt soooo reactive - if cooled to about zero one can handle it quite well without quick decomposition.




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[*] posted on 25-8-2004 at 13:31
FYI


http://www.tinchemical.com/products.html

There is some information on sensibilizing PLASTICS with stannic chloride for galvanisation too.....
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[*] posted on 25-8-2004 at 23:36


Because SnCl4 hydrolyses on contact with moist air to form the opaque white dioxide, SnO2, and HCl, it could be used, as a dispersed vapor or aerosol, to make smokescreens for military purposes, to cover the advance of infantry soldiers over open ground and make it impossible for the enemy to accurately fire on them. However, because of its greater molecular weight, which means it does not stay suspended in air for as long, and is heavier to transport, it is not as good for smokescreens as TiCl4, which is the militarily preferred chemical. TiO2 also is more opaque than SnO2.

An even lighter alternative than either of these for the purpose of smokescreens would be SiCl4, which would be made by firstly reducing SiO2 to the element, then reacting it with Cl2. However, reducing SiO2 to the element, for chlorination, requires much more energy than SnO2 and probably TiO2 as well, which could upset the relative economics of using SiCl4.

John W.
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[*] posted on 26-8-2004 at 07:17


Quote:
Originally posted by JohnWW
SnCl4 hydrolyses on contact with moist air to form the opaque white dioxide, SnO2, and HCl, it could be used, as a dispersed vapor or aerosol, to make smokescreens for military purposes, john W.


uh....isn't there one other wrinkle?

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[*] posted on 7-10-2004 at 05:16


The reaction of SnCl4 with the moisture of the air is truely impressing breathtaking - cough, cough.... ;)

Cooling the SnCl4 before use in the freezer helps. Mixing the SnCl4 with an inert solvent like benzeneand cooling in the fridge is better.

Best is to produce the SnCl4 in a setup which allows direct shortway distillation of the formed SnCl4 without having to open the apparatus. This avoids most problems from start and is preferable.
Forget anything like usual filtration or such where the SnCl4 is in contact with air for more than a second or more. It will not make you happy.




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