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Author: Subject: hemicellulose solvents, glycerine and alkali react?
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[*] posted on 21-3-2018 at 21:31


Most wood sold for lumber where I am is kiln dried. The process is faster and the shipped wood is lighter. But, for the most part ... drying kilns don't make uniform steam. The inside of the wood seldom gets above boiling from what I understand. The lumber yards want to use as little fuel as possible to get the wood dry. So, mostly the surface of the wood of regular lumber shows signs of having been steamed ... but the inner wood doesn't. Killing off micro-organisms only requires the inside of wood reach temperatures of around 130 to 170F when moisture is present. Eg: the cooking temperature of poultry is the highest needed. I expect the same is true of balsa's pests. As long as the inner wood hits 75C while still moist ... pretty much all pests are dead!

When I look closely at the balsa I have, the surface of the wood is different and darker than the fibers in the middle on some sides, but not others. I wonder if that's related to the kiln drying....

Thanks for looking. Collecting information is always good!

I think I'm beginning to understand what's going on with the Glycerol, as well. Methanol's -OH radical is more like the outer two -OH radicals on glycerol and not the center one which is less chemically active; so, when excess methanol is present ... it reduces the amount of CaOH2 reacting with the glycerol by competing chemically. When methanol is in excess of glycerol, the color changes ? Perhaps -- If I substitute another alcohol for methanol that has the same structure as glycerol, but only has one -OH on the center carbon; that will cause the yellow color to come back even when the evaporating alcohol is in excess of glycerol.

Since glycerol is a propane structure - tri-ol ... if I remember right ... then the mon-ol would be a propane structure with only one -ol on the center carbon.
Is propyl in iso-propyl stand for propane? eg: isopropyl should be a mon-ol with the -OH on the center carbon (iso=symmetric-position), correct?



[Edited on 22-3-2018 by semiconductive]
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[*] posted on 22-3-2018 at 06:33


I would keep in mind Methanol is tree alcohol, spirit from wood or whatever it was called. Sugar needs to be transported especially at spring time with sap rising.

Two things we know, water has to be involved because trees use alot of it and why would a tree have methanol if it didnt help transport stuff and stop the xylem blocking?

Pine resin dissolves in it, methanol is water soluble and sap contains sugar. Anything i have missed? I know i have simplified things but its that time of year here. Tree are waking up so samples from branches etc might give some answers, also Venice back then was fairly acidic (dont have a ref its a library book and i forgot to grab the ref), apparently VERY anaerobic to the point that the central canals gave off hydrogen sulphide.

Microbes likely to be all Archaea or methanogens, one the down sides of cleaning up the canals is the wood is now rotting.

I was told by the forestry guy that wood from that era fetches a fortune, being the mini ice age its extremely dense. he says they have a place near Mochram that has a very old forest part.

Its a kind of wildlife park now, the trees look around 70 years old but are infact a couple of hundred, they are stunted because of that time period.

He says the density while not near Lignum Vitae is not a million miles off. Hence why no one is ever going to build an instrument like that again. Not that your trying to.

Fascinating subject, now i am on the trail of quantifying the different sugars.

[Edited on 22-3-2018 by NEMO-Chemistry]
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[*] posted on 22-3-2018 at 06:54


There is a method of determining the amounts of each in wood, so to see how much you have removed use one of these before your experiment and then again after. one is called the TAPPI method (not found it yet) the other is in this paper.

At least then you have specific numbers of how much your removing and how much was there to begin with.


Attachment: DeterminationofStructuralCarbohydratesandLignininBiomass.pdf (421kB)
This file has been downloaded 241 times

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[*] posted on 22-3-2018 at 10:43


Quote: Originally posted by NEMO-Chemistry  
I would keep in mind Methanol is tree alcohol, spirit from wood or whatever it was called. Sugar needs to be transported especially at spring time with sap rising.

Two things we know, water has to be involved because trees use alot of it and why would a tree have methanol if it didnt help transport stuff and stop the xylem blocking?


Trees have two vasular systems, xylem and phloem. This refers not to the material these are made of, but to the location of the vessels (like blood vessels) in the bark and cambium of the tree. One system is believed to transport inorganic salts and water from soil up to the leaves, the other is believed to transport sugars from the leaves down the tree to the root. In actuality, the relationship is a little more complicated than I've outlined; but the deviations from the simple outline aren't significant for what I'm trying to do.

Wood, proper, does not have either of these vessels. Wood itself, even in a live tree ... is already dead. Only the bark layer / cambium on the outside of the tree is alive with transport vessels and moving sugars. Inner wood is only designed to passively wick water upward, but that's all.

I don't think trees have free Methanol. Methanol is made by heating polymerized wood sugars to the point that they chemically break down. It's destructive distillation of a polymer. eg: pyrolysis.

Glycerol and perhaps mannitol are found chemically free in tree's, but I've never come across an article measuring methanol in tree sap or leaves. You might want to look for it.

Water definitely is the solvent that sugars are normally transported around in by trees. However, there is some evidence that there are carrier checmicals or proteins that the tree will generate to actively attach to sugar and aid in "pumping" it around. I don't recall the exact chemicals involved.... and it's been too long for me to be sure of my memory. It had something to do with the formation of starch, and storage of that under the bark.

What I do know is that Glycerol is very aggressive at de-polymerizing some of the structural components of wood; but Methanol is not.

As a note, Glycerol when mixed with isopropyl did produce a creamy yellow color after mixing with Ca[OH]2. So, even though I don't know exactly what kind of chemical reaction lime has with glycerol, I have a qualitative idea of what's interfering with solubility of lime in Glycerol.

When powdered Ca[OH]2 comes into contact with glycerol, the glycerol sticks to it. SInce the Ca[OH]2 particles are a solid, they tend to increase the viscosity of the glycerol. What little chemical reaction that does happen is enough to immobilize the glycerol when there is too concentrated an amount of slaked lime present. That's the main barrier to solubility of slaked lime in glycerol -- there's a physical barrier that forms around the lime particles. By mixing the lime with a less viscous alcohol, like methanol or isopropyl before mixing it with glycerol .... the particles are dispersed uniformly into the glycerol. Much more of the lime comes into contact with the Glycerol that way before becoming a solid mass.

That stuff I saw on bottom of the vial where I thought I was seeing polymerization, are likely just places where larger lime particles eventually got coated with glycerol and sank to the bottom.

I'm heating the glycerol + IPA + lime mix, now, 55C and rising slowly ... and watching for the temperature that causes the Glycerol to discolor from yellow to brown or cement-grey.


[Edited on 22-3-2018 by semiconductive]
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[*] posted on 28-3-2018 at 13:14


Quote: Originally posted by NEMO-Chemistry  
There is a method of determining the amounts of each in wood, so to see how much you have removed use one of these before your experiment and then again after. one is called the TAPPI method (not found it yet) the other is in this paper.

At least then you have specific numbers of how much your removing and how much was there to begin with.


Thanks for the link. Most of the equipment is out of my price range, but yes ... that's the general idea of what I need to do.

Liquid chromotography appears to use a mass balance accurate to 0.1mg. That's 10x more accurate than I have available for amateur use. So, there's no way I can follow that particular lab procedure. They are interested in separating all the sugar components and giving values for each kind separately. I probably don't need something that accurate. I'm really only interested in total dissolved sugars.

Digesting the wood with acids, and turning it into something that can be measured with a photometer is possible.

For future reference,
I've been looking into making a spectrometer, but in the IR wavelengths:

https://www.sciencemadness.org/whisper/viewthread.php?tid=78...

I'm not familiar with UV-Vis spectroscopy, but I assume that means visible light.
https://en.wikipedia.org/wiki/Ultraviolet%E2%80%93visible_sp...

Still, the principle is the same ... the amount of absorption of light is proportional to the concentration of a given molecule in solute. Do you have any experience with how accurate a measurement this will typically give?

-------------------

The main issue with mass loss is to be able to determine how much of either glycerine, DMSO, etc. that are still in the wood at the end of the experiment. Everything else I need to know can be found out from weighing the dried wood.

There is another idea that I have, since sugars in alkaline solution are ionized and DMSO/GLycerine are polar; they can be attracted by electrical potentials. So, they should be able to move under electric field influence -- just like DNA can be separated by electrophoresis. If I used long teflon tubes and sensed when the potential changed on the graphite electrode, I might be able to build a liquid based mass spectrometer (amateur grade) that determined diffusion rates and percentages of various charged chemicals diffusing through the tube. If I can isolate either glycerine or DMSO percentages, that would give me the information I need.






[Edited on 28-3-2018 by semiconductive]
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[*] posted on 2-4-2018 at 12:00


I got another reply from Balsa exporters, they use alot of steam and alot of fuming chemicals, again they wouldnt say what chemicals and i suspect in most other countries its stuff like DTT, thats banned.

The reason they steam so much and take no chances is cost, shipping is the main cost to them. Every load is tested at the border in most countries for evidence of live insects. If any insects or eggs get into customs and are found, the entire load is seized and dealt with.

So because its alot cheaper for them to chop down and tree and use steam, they do that rather than risk not killing everything in the wood. Also 3 strikes so to speak and the shipping company gets a 6 months import ban.

These people also mentioned the high risk of insect population with Balsa, apparently the stuff is crawling with insects at 8-10 years of age for the tree, which is the best size to cut.

I might be able to mess with some pine and fir tree wood, but import duty makes Balsa in the UK 4X more expensive than the states.
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[*] posted on 5-4-2018 at 14:57


Thanks nemo-chem. But, even with the extra info you're getting, I don't think were learning much that's new ... The wood exporters aren't giving you gallons of water per volume of kiln and volume of wood, nor soak times nor temperatures. So, what you're really hearing is that they are saying "we are very responsible" which is what they have to say no matter what. There is also a possibility they are exaggerating a little to prevent others from "getting in" on a business. In reality, someone is using a pencil and subtracting costs off profits and deciding exactly how much fuel and water they can afford. They just know what works to kill bugs by experience and is safe.

Also, if you look back at the steam decomposition articles you sent me; they are talking about super-pressurized steam in the mega-pascal range. So even though straight steam can decompose wood ... the conditions of the article are no where near a drying kiln. The articles require a special pressurized vessel to work.

As an aside:

Neither pine nor fir would be a good substitute for a balsa wood test; Both pine and fir are gymnosperms (naked seed sowers, like pine-cones where the seed is exposed.) So those are both soft woods, unlike balsa which is a hard wood (angiosperm). They are fine if you want to do a soft wood chemical test.

The xylinase enzyme came yesterday to my house. It's in liquid form, so I put it in the refrigerator for now so that it keeps longer. I also have CaCl2 to experiment with.

Oddly enough, CaOH glycerine with Isopropyl alcohol stubbornly refuses to darken like CaOH glycerine did with methanol. In fact, glycerine forms a cream colored and waxy feeling substance when mixed with CaOH in IPA at around 100C. I'm not really sure what's going on, chemically, that's different when methanol is present ... except that maybe the CaOH is bonding glycerol to methanol and that's a darker color ?

The -OH in methanol should be more reactive than the one in isopropyl. eg: Isopropyl should be a less aggressive solvent and chemical reactant.

Here's a picture of Glycerol/Isopropyl cooking to make a buttery paste. At first there's coloidal suspension, that drops to the bottom as it warms up ... and as it cooks, the color changes very slightly milk/butter yellow (hard to see in the photo). It was most visible at 100C, but unfortunately the lid leaked before I could get a picture; so I only have it to 90C.

I'm entangled in other projects momentarily, so I probably won't post here for a couple of weeks. Unfortunately scimadness doesn't send me an email when someone replies, so I may be slow in responding. It won't mean I've forgotten. :)


IsoGlyCaOH2.png - 623kB


[Edited on 6-4-2018 by semiconductive]
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[*] posted on 14-4-2018 at 17:29


Data on Dry-Z-Air: I did a solutbility and drying test to get an idea if it was pure CaCl2 or not for experiments ... and the answer is definitely not. Dryzair is easy to re-crystallize from alcohol, though. CaCl2 is soluble in alcohol/methanol but monovalent alkali salt impurities are not. So, After dissolving 4g of dry-z-air in 12g of methanol; I let it sit overnight. The colloidal suspension mostly settled to the bottom at 40C heat in a sealed flask. I then transferred the liquid to a second Erlenmeyer flask (with some impurities), and dried it at 80C (to prevent spattering) with air blowing on it from a fish-air pump to accelerate evaporation. Afterward, I raised the dried salt to around 125 to 150C to attempt to dehydrate it. The partially dehydrated salt was very uniform in color/texture with a thin whiter crust on top. ( Will redissolve, decant, and crystalize again later. )

The results are that around >= 300mg/4g are non-soluble impurities meaning Dry-Z-air is approximately <= 92.5% CaCl2 of unknown hydration.
(7.5% impurities by weight)
The (partially?) dehydrated CaCl2 weighed in at 2.888g ; So I estimate the water of hydration is around 1.75 moles of water per mole of CaCl2 in fresh, store-bought-dry-z-air. It might be higher.

Edit: Second recrystalization puts a lower bound; not more than 100mg was wasted -- dehydrated at closer to 150C+ this time. Perfectly uniform crystals, no sign of color differences. I assume it's pure, weighing in at 2.65g. So, that puts the hydrated CaCl2 somewhere between 90 and 92.5% in dri-z-air by weight. The water of crystalization is therfore between 1.75 - 2.33 molecules H2O per molecule of CaCl2 EndEdit:

CaCl2 is already a base, pH measures about 8, so your friend was right in that it's probably a good thing to try to dissolve hemi-cellulose.

Since stronger bases are reported to dissolve the hemi-cellulose better than neutral, I can also add slaked lime to the recrystallized dry-z-air, to make CaOHCl ; I'll find out how soluble that is in methanol and methanol Glycerol mixes, as I don't see any data online. I ought to be able to control the pH vs. solubility by the amount of slaked lime that is added.

Edit:
To make CaOHCl, I need to add:
2.65g CaCl2 * 74.092 g/mol CaOH2 / 110.98 g/mol CaCl2 = 1.769g of CaOH2
I tried it ... and the result in 12 to 20g methanol is a colloidal suspension. Either it doesn't react quickly, or the basic chloride CaOHCl is much less soluble (like 1/4 the solubility) of CaCl2 in methanol. With time the colloidal particle size seems to be decreasing ... so it does appear to be dissolving slowly in alcohol. I tried adding 5ml of water to the alcohol, and don't see much difference in the splashes leaving powder on the glass. So, it's still colloidal. The color of the methanol is greyish white -- and /very slightly yellow. So, some minor amount of reaction appears to have happened.

Edit: dried the solution and added water to 50ml... with time the basic calcium chloride increasingly sinks to the bottom of the flask and separates from the water; so I think basic calcium chloride has low solubility in water. I think it had smaller particles in the alcohol -- so it *seems* more soluble in alcohol ... but perhaps there was no reaction...?

Some literature claims basic calcium chloride is "insoluble" in pure water but the literature is very old. Other literature claims that basic calcium chloride decomposes into CaOH2 and CaCl2 in large amounts of water. I'm not sure what to believe.

[Edited on 15-4-2018 by semiconductive]

Post note: I drove the water solution to dryness,again, and am attempting to re-dissolve the material in methanol. Adding methanol caused an immediate exothermic reaction, which is the same as when anhydrous CaCl2 dissolves. Large amounts of crystal are not re-dissolving. Exposure to air, and perhaps CO2, may have had an effect.



[Edited on 15-4-2018 by semiconductive]
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