Sciencemadness Discussion Board

Making Reducing agents and oxidizing agents

symboom - 31-7-2020 at 19:54

Reasoning Doing this project help me learn there interesting reducing agents using galium and Indium along with hyponitrite and hydroxylamine. Anyone is welcome to help me improve the list before it will not let me edit.
I'm chosing one that I feel may be possible for an amature chemist to synthesize the compound.

Organized by reduction/oxidation potential
The top of the list is the most powerful reducing agent
The bottom of the list is the strongest oxidizer


Diisobutylaluminium hydride
Superhydride (Lithium Triethylborohydride)
Stryker's reagent
Aluminum Hydride
>>lithium aluminium hydride and aluminium trichloride.
Lithium Aluminum Hydride
>> Lithium hydride and aluminium chloride
Sodium aluminum hydride
> from elements under high pressures of H2 at 200 °C
Lithium borohydride
>>sodium borohydride and lithium bromide
Sodium borohydride
>>sodium hydride and trimethyl borate at 250–270 °C:
Lithium Indium Hydride
>>LiH and InCl3 "in situ" in Org. synthesis as a reducing agent
Lithium galium Hydride(Lithium tetrahydridogallate)
>>LiH and GaCl3/GaBr3 at -80 °C cool to room temperature
Lithium hydride
>>Lithium metal and hydrogen gas at 600C for high yield
Rubidium hydride
>>Rubidium and hydrogen (very powerful reducing agent)
Potassium hydride
>>Potassium and Hydrogen
Sodium hydride
>>Sodium and hydrogen
M-SG reducing agent
>>(alkali metal absorbed on activated silica)
Lithium
>>Electrolysis of LiCl (55%) and KCl (45%) melts at 430°C
+> https://m.youtube.com/watch?v=eytU_eY-dfk
Caesium
>>caesium chloride and lithium metal
Sodium
>>NaOH and Mg (menthol catalysis)/Electrolysis of **NaOH**
Rubidium
sodium and rubidium chloride.
Potassium
>>KF and CaC2 // sodium or lithium and potassium chloride
Sodium-potassium alloy NaK
>>Sodium and potassium
Diborane
>>Borohydride salt and tin (II) chloride
Borane
>>Aluminium boride reacts with acid forming borane.
Stannane
>>reaction of SnCl4 and LiAlH4.
Stibine
>>Lithium antimonide and water
Lithium antimonide
>>electrolysis to obtain lithium but with antimony cathode
Silane
>>Magnesium boride and hydrochloric acid
Cerium
>>Cerous fluoride with calcium
Lanthanum
>Lanthanum chloride and Lithium
Samarium
>>Lanthanum metal and samarium oxide
Silicon
>Mg and SiO2/sodium hexafluorosilicate and Na/Ga and SiO2
Magnesium
>>Magnesium oxide and potassium or silicon
Calcium
>>Calcium iodide with Sodium
Aluminum
>>Sodium and aluminum chloride
Aluminum amalgam
>>Mercury and aluminum
Aluminum borohydride
>> sodium borohydride with aluminium chloride
Sodium cyanoborohydride
>>sodium cyanide and borane.
Sodium triacetoxyborohydride(STAB)
>>sodium borohydride with acetic acid
samarium (II) iodide (decomp. SmI3) reduces H2O to hydrogen
>>samarium and diiodomethane
>Diiodomethane from iodoform and Phosphorus
_____________________
Galium suboxide
>>Galium and Silicon dioxide -- (decomposes at 500 °C)
Reduces Sulfuric acid to Hydrogen Sulfide
_____________________
indium(I) iodide
>>InI3 and indium metal in refluxing xylenes/ In and I2
Hydroxylamine
>> nitrous acid or potassium nitrite and bisulfite:
Hydrazine
>>Urea and Sodium hypochlorite
Diimide
>>hydrazine and H2O2/decarboxylation of azodicarboxylic acid
Hypophosphorous acid
>>Sodium hypophosphite and hydrochloric acid
Diphosphorus tetraiodide
>>Decomposition of phosphorus triiodide in dry ether
Hydrogen iodide
>>Phosphorus and iodine
Sodium hypophosphite
>>white phosphorus in a hot solution of sodium hydroxide
Copper hydride
>>Sodium hypophosphite and copper sulfate
Zinc hydride
>>Zinc bromide and lithium hydride
Sodium Hyponitrite
>>Sodium amalgam metal and sodium nitrite
Thiourea dioxide
>>thiourea and hydrogen peroxide
Titanium hydride
>>Titanium powder heated with hydrogen gas then to cool
Titanium(III) chloride
>>Titanium (IV) chloride and aluminium or hydrogen gas
Phosphorus acid
>>phosphorus trichloride and water
Chromium(II) salt
>>Chromium(III) and zinc metal
Zinc
>>Carbon and zinc oxide/magnesium and zinc chloride
Hydrogen
>>Zinc/aluminum and hydrochloric acid
Devarda's alloy
>>alloy of aluminium (45%), copper (50%) and zinc (5%)
Raney nickel
>>Activated nickel powder from nickel–aluminium alloy
Jones reductor
>>Zinc amalgam
Rongalite
>>sodium dithionite and formaldehyde:
Sodium dithionite
Zinc and sulfurous acid(0C)=> zinc dithionite + sodium acetate
Sodium bisulfite
>>Sodium hydroxide/carbonate and Sulfur dioxide
Sulfur dioxide
>> Burning sulfur in oxygen/Disulfite and HCl
Tin(II) chloride
>> Tin and HCl
Copper (I) salt
>>Sulfur dioxide and copper chloride
__________________
Other top reducing agent
>>>Sodium triethylborohydride<<<
from a hot toluene mix of sodium hydride with triethylborane.

Triethylborane
prepared from trimethyl borate with triethylaluminium

Triethylaluminium
>> generated from ethylaluminium sesquichloride which arises by treating aluminium powder with chloroethane.
>>Reduction of ethylaluminium sesquichloride with an alkali metal such as sodium gives triethylaluminium
____________________________
Oxidizing agents

Potassium ferricyanide
Ceric ammonium nitrate
Lead dioxide
Potassium nitrite
Oxygen
Nitrous acid
Iodine
Zinc peroxide
Potassium nitrate
Potassium chromate
Potassium dichromate
Potassium chlorochromate
Bromine
Dinitrogen tetroxide
Osmium tetroxide
Potassium iodate
Potassium periodate
Potassium bromate
Potassium chlorate
Potassium perchlorate
Potassium hypochlorite
Potassium Chlorite
Chlorine
Antimony pentachloride
Chromyl chloride
Potassium peroxymonosulfate
Potassium persulfate
Potassium tetraperoxochromate(V)
Sulfur trioxide (rouge rose) I'm kinda guessing on this one
Calcium peroxide
Barium peroxide
Hydrogen Peroxide
Potassium permanganate
Potassium ferrate
High-valent iron
Potassium bismuthate
Chlorine nitrate
Potassium peroxide
Nitronium perchlorate
Dichlorine heptoxide
Potassium superoxide
Ozone
Manganese hyptoxide
Periodatonickelate
Perbromic acid



[Edited on 1-8-2020 by symboom]

[Edited on 1-8-2020 by symboom]

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[Edited on 2-8-2020 by symboom]

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[Edited on 2-8-2020 by symboom]

karlos³ - 1-8-2020 at 00:49

You forgot red-al, very good stuff, used this already some times.
It belongs directly under LiAlH4.

Sigmatropic - 1-8-2020 at 01:02

Lithium Borohydride above sodium aluminum hydride? I don't think so.

njl - 1-8-2020 at 04:26

Also Samarium Iodide has very interesting reducing properties. Also, is straight silane a useful reducing agent? could it reduce carbonyls to alkanes with SiO2 as a byproduct?

unionised - 1-8-2020 at 04:28

So far, this thread has nothing to do with its title.

karlos³ - 1-8-2020 at 04:32

Quote: Originally posted by unionised  
So far, this thread has nothing to do with its title.

I miss the making part too.

Syn the Sizer - 1-8-2020 at 05:22

At the very top under the thread description but above the list there is an explanation of a couple synthesis preceded by >>.

One for sodium aluminum hydride, one for lithium indium hydride and one for lithium gallium hydride.

I am wondering if it is intended to spark conversation about the synthesis of these reagents.

karlos³ - 1-8-2020 at 06:10

Ah yes that is new.

@symboom, please add Red-Al.
Proper IUPAC is sodium bis(2-methoxyethoxy)aluminium hydride.

Syn the Sizer - 1-8-2020 at 06:58

Yes, I actually see even more added since my last post.

RogueRose - 1-8-2020 at 10:09

SO where would SO3 fit in on this scale

SO3
chlorates and perchlorates (Na, K, CU, Ba, NH4, etc)
Hypochlorites
NO2
Barium nitrate (and many others - Cu, Nickel, etc)

symboom - 1-8-2020 at 10:40

I only added potassium salts for oxidizers because it gets redundant and the list would become very long unless there is a specific reasoning that for example two chlorates magnesium and sodium but they are too simular to each other
I have a representive of chlorate as potassium Chlorite, nitrate etc...

RogueRose - 1-8-2020 at 17:17

Quote: Originally posted by symboom  
I only added potassium salts for oxidizers because it gets redundant and the list would become very long unless there is a specific reasoning that for example two chlorates magnesium and sodium but they are too simular to each other
I have a representive of chlorate as potassium Chlorite, nitrate etc...


Ok, got it. Thanks!

So would you include SO3 in the oxidizer at soe point, or does it fall under the same premise as the others? Would it be close to ozone in how strong it is? I'm guessing hey both give up a single oxygen molecule, which then drops them back to their dioxides where you have them listed already.



I was starting a spread sheet of all different salts and what their decomposition products are (when heated or acted upon by a catalyst). I think that would be interesting to look through and have it be searchable. I think something like that could be useful, what do you think? I found it a little more difficult than I thought it would be though, b/c many times they don't list the temps or conditions needed for decamp let alone what they break down into.

[Edited on 8-2-2020 by RogueRose]

symboom - 1-8-2020 at 18:43

So close have to retype about the oxidizers good thing I kept saving while working on it so I got one half

What salts were you referring to in particular
Nitrate, chlorate, iodide, I think it's a great idea some salts are unstable to heating it's nice to have everything summerized in one place
Reducing agents and oxidation agents are a must for organic chemistry without them one could not explore compounds.

[Edited on 2-8-2020 by symboom]

RogueRose - 2-8-2020 at 03:05

Quote: Originally posted by symboom  
So close have to retype about the oxidizers good thing I kept saving while working on it so I got one half

What salts were you referring to in particular
Nitrate, chlorate, iodide, I think it's a great idea some salts are unstable to heating it's nice to have everything summerized in one place
Reducing agents and oxidation agents are a must for organic chemistry without them one could not explore compounds.

[Edited on 2-8-2020 by symboom]



I've started on this project like 4-5 times and I keep realizing I'm over my head (chem is my hobby, probably 3-5th in line of my hobbies) and I've learned everything from this forum, many now defunct forums, research papers and skimming some text books. Well, I did have Chem 1 in HS and beginner/practical biochem in college - so that is why I often ask questions many people may think are obvious but to me, I had no order in which I learned things, so I try to piece things together.

The point of me saying this is I've found many discrepancies between Wiki, Scimadwiki, chemspider and many others on so many properties of various compounds and so many of the Wiki entries do not list the decomp product, and maybe I'm missing something obvious, but I actually had a hard rime even setting up the spread sheet and that is b/c so many of the compounds have many hydrates and they can either just give off water or "melt" the compound when a little H2O is released.

What got me thinking of this was I was researching magnesium acetate. I just finished an experiment where I took some anhydrous lead acetate and placed some pieces of Mg into it and I got some very interesting results (more on that later). I was planning on separating out the magnesium acetate but I couldn't find out what it would decompose into, I suspected MgO or posibly the hydroxide, thought I figured not, but what was the side product of the acetate breaking down, can I just distill out Acetic Acid? Is there any possibility to get acetic anhydride, maybe with some additions of some kind?

Another example was CuSO4 that was heated to just about boiling and I added a little ascorbic acid which turns the solution a nice green color (but IDK how much I really needed to add - and it was from 1g Vit C tablets - filtered 3x). Upon boiling I got some very fine copper particles floating on the surface but it looked like it was progressing extremely slowly, even at a nice boil (with stirring as well, won't do that next time I think). After boiling down to a point where there was no more steam coming out, the vapors started to get a bit acrid and made me cough once. I couldn't get the temp but I'm assuming that whatever was remaining from the ascorbic acid and sulfate might have made H2SO4, or maybe something else? the liquid was a brown with a green tint and there may have been VERY slight amounts of CuSO4 left, but there's no was it was hot enough to decompose the remaining CuSO4, unless whatever left was maybe giving off some SO2 or maybe SO3 vapors?

So those were my most recent reasons for wanting to be able to look at some tables or a chart and figure out what things decompose into. It's also extremely beneficial when you are looking to make something, let's say SO3, so you could sort your list for the decomp products (and the thing is, some have multiple decomp products in reactions, so I was naming them the primary, secondary, tertiary, etc products - Ex MgCO3 decomposes into the primary of MgO and the secondary of CO2). So if you wanted to see all the reactions that produced SO3, you would have to sort all the colums and look for it in each decomp product column. Then I thought about the compounds like CuSO4 that produce SO2 and SO3 (or more accurately 2CuSO4 -> 2CuO + 2SO2 + O) - much like MgSO4 IIRC. But Wiki states that both of these produce CuO + SO3 and yet others say that the SO2 can be generated with both if some carbon is added, so you would end up with any of the following depending on the source of the literature:
MO + SO2 + CO2
MO + SO2 + 2CO
MO + SO3 + CO
2MO + 2SO2 + CO2

So, my little question on what would happen if I decomposed the Mag Acetate led me down this multi hour ordeal where I was trying to figure out a way to arrainge a spread sheet that would make sense, and every time I thought I was getting close, I found another example like the ones above (funnily enough, I found ZERO info on Mag acetate decomposition other than it loosing it's water from the trihydrate. I also looked into various aluminum acetate b/c I was going to try to use aluminum in place of the Mg in the lead acetate displacement (didn't work, the only thing that happened is the solution turned from clear to milky and a slight bit of lead (probably .01g) plated on a .25g of Al even though it was boiling and being stirred. Now the magnesium, all that needed was a little heat and the lead precipitated out VERY fast until the Mg was coated and then it really slowed down.


The really odd think is that I thought I would be able to use this lead metal by melting it, like normal lead - does that make sense? it's VERY light and fluffy, less dense than Mg at the moment and it made itself into spheres b/c of the stir bar. Well I took a blow torch to it (used the bottom of a Al can as a little crucible for about .2-.25g lead ball and heated from the bottom). well even after getting hot enough to start to melt the Al, the lead never changed a bit, except it became a brittle sphere that I could crumble between fingers with 2-3lbs of force. I then appied to torch to it directly and it just would never melt.

Now this is the same thing that happened EVERY time I tried to heat the lead plates from lead acid batteries - even with an oxy acetylene and getting the lead to a bright orange glowing liquid, it wouldn't turn into metal ( I tried indirect heat, and about 10 other methods to melt the lead acid battery led and it never worked except for the grid/lattice that holds al the "lead sponge" in place. But I figures dissolving in acid and then reducing it would remedy this leaving me with pure, workable lead, not back to where I started. F'ing terrible if I do say so.

I have some pics coming, they are pretty interesting, there are some TINY lead crystals growing on one lead ball (out of 40-55+ balls - should have been about 30-31grams when finished). I think I'm going to have to try electrolytic refining as it seems the only way to do this and get quality lead.

SO if you have any idea on how to arrange some kind of table like this, I'm all ears. I'd really like to make a website where peolpe can see what the products they use break down into, like when I heard a newscaster state that ammonium nitrate was a poison, meaning just being around it, eating food that was grown with it, or breathing the air from the plants or the ground on which it was spread. Seems pretty odd considering the only elements are are nitrogen, oxygen and hydrogen, but he (or I think it was actually a she) acted like it was 100x than eating lead or methyl mercury.

I just hink it would be helpful if someone was like "I need to make XXX and they can look up that compound/element and see what compounds they already have, or have access to and find the most viable method of making that compound themselves. I also think it would be interesting running it all in the opposite direction, starting with basic building blocks and working up to more complex compounds.

[Edited on 8-2-2020 by RogueRose]

symboom - 2-8-2020 at 03:47

On projects try to start with a small goal so it's not overwhelming working on this the was times I wanted to put more information that I though was interesting but then it would be really long and take a while and I could not finish it in a day. It takes time to understand I feel the same way about organic chemistry but It has just been practice for example I would look up a chemical and try to figure out how I would build that organic chemical.

There is either information missing or behind paywalls that is annoying and makes learning and finding information more difficult.i feel like for sciencemadness makes chemical information more accessable and easier to read and understand. Especially the sciencemadness wiki a great site started

As for a table I'd try different layouts to see what looks best but start with a small amount of chemicals for the goal.



[Edited on 2-8-2020 by symboom]

Draeger - 2-8-2020 at 14:45

Are silanes/stibine (especially that)/stannane/boranes really feasible to make in an amateur lab? Especially stibine seems really dangerous to make.

symboom - 2-8-2020 at 15:20

In one way I'd disagree some have made phosphorus and been exposed to working with phosphine some have made borane and silane. Some have even worked with cyanide azide and hydrazine to name a few toxic chemicals. But stibine I'd have to agree with you I did not realize it was as toxic as arsine I thought it had simular reactions as Tellurium, germanium or bismith but it is below arsinic so I see why.

Eddie Current - 2-8-2020 at 16:12

I commend you on your efforts symboom.

It would be great to see the applicabilities and limitations correlated with each reagent.

JJay - 2-8-2020 at 16:54

Pyrophoric nickel (from pyrolysis of nickel oxylate): https://www.youtube.com/watch?v=4gO92eqQcB4
Ammonium formate: https://www.youtube.com/watch?v=CuiLFCaYseo
Aluminum isopropoxide: https://www.youtube.com/watch?v=SuoWnueBJaY
Platinum oxide: http://www.orgsyn.org/demo.aspx?prep=CV1P0463
Palladium on carbon
Palladium on barium sulfate

symboom - 2-8-2020 at 17:57

@Eddie Current thanks it took a bit of time and effort but I think I will pay off to have references here instead of looking everywhere a big task but as a community im sure it's possible

If any one wants to add to this list or add a short summary of applicabilities and limitations correlated with each reagent.
By all means jump into the search and add on to the post.

Jjay thanks for the add of platnium\palladium i forgot about it
Also never heard of Palladium on barium sulfate definitely going to read about it.



[Edited on 3-8-2020 by symboom]

symboom - 2-8-2020 at 18:07

I summerized the information to what its reacts with and what it forms a drawn out sentence is not needed. Yep me what you all think about this lay out hope it is strait to the point.

Many other hydride reagents are more strongly reducing than sodium borohydride These usually involve replacing hydride with alkyl groups, such as lithium triethylborohydride and L-selectride (lithium tri-sec-butylborohydride), or replacing B with Al. Variations in the counterion also affect the reactivity of the borohydride.


Diisobutylaluminium hydride,(DIBAL)
carboxylic acids, their derivatives, and nitriles to aldehydes.
α-β unsaturated esters to corresponding allylic alcohol.

LiBHEt3 is a stronger reducing agent than lithium borohydride
and lithium aluminium hydride.
Alkyl halides to alkanes
pyridine and isoquinolines to piperidines
aromatic esters to alcohols
Disulfides to thiols
lactones to diols

AlH3
aldehydes, ketones, carboxylic acids, anhydrides, esters
acid chlorides, and lactones to alcohols.
Amides, nitriles, oximes to amines.

LiAlH4
esters and acyl chlorides to primary alcohols,
nitriles to primary animes

NaAlH4
more powerful reducing agent than sodium borohydride
esters to alcohols

LiBH4
stronger reducing agent than sodium borohydride
esters to alcohols
primary amides to amines
will reduce esters, nitriles, lactones, primary amides, and epoxides while sparing nitro groups, carbamic acids, alkyl halides, and secondary/tertiary amides

NaBH4
ketones and aldehydes to alcohols.

LiGaH4
Ethereal solutions of LiGaH4 are strongly reductant but less than LiBH4 and LiAlH4.
acetamide and acetonitrile to ethylamine.
Aliphatic acids, aldehydes and ketones to alcohols.
NOT Aromatic nitriles, aldehydes, ketones and esters

LiInH4 ??

sodium cyanoborohydride ??

Sodium triacetoxyborohydride ??
milder reducing agent than sodium borohydride or even sodium cyanoborohydride.

Ionic hydrides
Seem to just be used as drying agents or synthesis of stronger reducing agents

Potassium hydride a super base
carbonyl to enolates.
amines to amides

NaH is a base of wide scope and utility in organic chemistry.[10] As a superbase, it is capable of deprotonating a range of even weak Brønsted acids to give the corresponding sodium derivatives. Typical "easy" substrates contain O-H, N-H, S-H bonds, including alcohols, phenols, pyrazoles, and thiols.

NaH notably deprotonates carbon acids (i.e., C-H bonds) such as 1,3-dicarbonyls such as malonic esters. The resulting sodium derivatives can be alkylated. NaH is widely used to promote condensation reactions of carbonyl compounds via the Dieckmann condensation, Stobbe condensation, Darzens condensation, and Claisen condensation. Other carbon acids susceptible to deprotonation by NaH include sulfonium salts and DMSO. NaH is used to make sulfur ylides, which in turn are used to convert ketones into epoxides, as in the Johnson–Corey–Chaykovsky reaction.

series of reduction reactions, including the hydrodecyanation of tertiary nitriles, reduction of imines to amines, and amides to aldehydes, can be effected by a composite reagent composed of sodium hydride and an alkali metal iodide (NaH:MI, M = Li, Na)

To do summerize down to just reactions
____________________
Also for those interested in lithium hydride I found this
Metallic lithium can be quantitatively hydrogenated to lithium hydride at 25–50°C under atmospheric pressure within 2–5 h

Sounds like just putting a strip of lithium in a Coke bottle with a balloon of hydrogen gas covering the top.
Reference https://onlinelibrary.wiley.com/doi/abs/10.1002/cjoc.1985003...





[Edited on 3-8-2020 by symboom]

[Edited on 3-8-2020 by symboom]

[Edited on 3-8-2020 by symboom]

Syn the Sizer - 2-8-2020 at 19:53

I think having a reference like this is a great idea. Posts with good content and information are what make the forum an asset.

mackolol - 3-8-2020 at 13:14

Those periodatonickelates seem interesting.

Wikipedia states that: "The salts were made by oxidising nickel sulfate mixed with potassium periodate (or sodium periodate) with the alkali persulfate salt in boiling water"

If only one could make periodate easily.

I wonder what periodatonickelates are especially useful for.

clearly_not_atara - 3-8-2020 at 13:54

Remember that the "reduction potential" does not by itself imply any reducing activity. KH is a stronger reductant than LiAlH4 electronically, but the latter is a much more effective reagent for reducing organic compounds.

DiBAL in particular is a highly selective reagent that happens to react with Lewis bases rather than electrophiles like other reducing agents. So esters are reduced faster than aldehydes by DiBAL, which is opposite of BH4- and AlH4- reagents.

So reducing agents cannot necessarily be strictly ordered by "power", and a similar consideration occurs for oxidizers (though in this case, some very strong oxidizers really will oxidize almost anything).

symboom - 3-8-2020 at 14:40

KH is a stronger reductant than LiAlH4
I did not know that it's more of general organization
When comparing what they can reduce or oxidize

DiBAL I when by it having more than just hydrogen so I assumed it was more powerful as it could reduce something that many other chemicals can not.

I still have lots to learn for organic chemistry.

[Edited on 3-8-2020 by symboom]