ChemisTryptaMan
Rising Star
- Merits
- 42
Hello Nexians, I wanted to share some basic knowledge of chemistry that comes in handy when performing an extraction. There are several topics in chemistry that one should have a firm grasp on in order to understand exactly what is happening throughout the extraction process. These include:
1) Solubility
2) Partition Coefficients
3) Ionic Strength
4) Acid/Base Chemistry
Solubility:
Solubility is the extent to which a solute(anything being dissolved) can dissolve in a particular volume of solvent(the liquid holding the solutes). In a chemistry classroom what they will tell you is that "likes dissolve likes". This refers to the polarities of the molecules that one is attempting to dissolve. In general, non-polar molecules will dissolve in non-polar solvents(oils) and polar molecules will dissolve in polar solvents(water). This is why oil and water don't mix. The molecules of each are not soluble in each other, so they wont mix. The term miscibility is usually used for liquid-liquid situations, like ethanol being completely miscible with water means that they can be mixed in any proportion and it will form a homogeneous mixture. The truth of the matter is that oil and water do mix, just in such small amounts that we cant see it. As far as extraction goes, this means that there is some amount of naphtha in the water, and some amount of water in the naphtha. This is because at low ionic strengths(more on this later) most of the water molecules are neutral and do not repel the non-polar molecules as strongly as strongly as a fully charged ion in solution. Spice can exist in different forms that have different solubility in both water and naphtha. Solubility in both will increase at higher temperatures, as this is the case with most solutes and solvents. Higher temperatures mean higher solubility.
Partition Coefficients:
Partition Coefficients are a measure of how a solute will behave in a biphasic(2 layered) liquid system. These have values that are given in terms of the concentration in the non polar layer divided by the concentration in the aqueous layer. The standard solvent system which most literature values is given are for an octanol:water system. The goal when performing these extractions is to get the highest Partition Coefficient for the DMT so that most of it will end up in the non-polar layer(naphtha). This process of finding the optimum PC is different for every solute in every solvent system. We are mostly working with freebase DMT in a Naphtha: water system. We do this by attempting to decrease the solubility in the water layer while increasing the solubility in the naphtha layer. How can we do this? Well heating the entire solution will increase the solubility in both layers, to different extents, but the bottom line here is that you want the bottom layer to be cool when your pulling the spice from it, so if your going to use temperature your best option is to heat the naphtha before adding it to the cool(room temp) water and mixing as much as possible before the temperature equilibrate(which happens within seconds). There is another way to achieve our goal though, and that is by increasing the ionic strength of our aqueous layer in order to decrease the solubility of the spice in the aqueous layer. This also has the added benefit of decreasing the solubility of the water within the naphtha and the naphtha in the water, which is why adding salt results in less emulsions forming at higher ionic strengths, a more complete separation of the two layers is achieved.
Ionic Strength:
Ionic strength is essentially a measure of how much charge is present in a solution. It has a value that is calculated by taking the concentration of every solute in solution, raising that concentration to its charge, and then adding these all together. This means that molecules with more than one unit of charge have a much greater effect on the ionic strength. Calcium and Magnesium both have a charge of +2, While sulfate and phosphate ions have varying charges based on the pH of the solution, but at the high pH's that we run the extractions at they carry a charge of -2 and -3 respectively. pH plays an important role in ionic strength for reasons we will get into momentarily. I don't like to encourage the use of distilled water, I prefer filtered water and for this reason alone, distilled water has had its ionic strength lowered to the lowest possible level intentionally, what you are buying is de-ionized water. With filtered or spring water you have had anything that might be harmful to the process removed and are left with a plethora of ions such as sodium, potassium, chloride, magnesium, calcium, and many, many more. I understand the desire to start with distilled water but from a chemists perspective it is not really necessary and may actually decrease your yield if a high enough ionic strength has not been reached.
Acid/Base Chemistry:
Alright so this is where I want to begin with the two different forms of DMT. These are the Salt and the Freebase forms. The only difference between the two is that in the salt an extra hydrogen nucleus(proton) has been attached to the molecule at the amine(where the nitrogen is located). This makes this form have a charge of +1 at the Nitrogen. The charge is actually spread out over the the atoms surrounding the nitrogen, but most of the charge is located right on the added proton. The rest of the molecule is still very non-polar and hence still quite soluble in the naphtha, but the charge has a powerful effect on the solubility in water because water can easily dissolve charged molecules, even when they have a large non-polar region. Every molecule that can either receive or give up a proton will exist in the two different forms with different pH's determining what state that molecule is in. This switch from one form to another happens around a particular pH for each molecule. For DMT, this pH(known as it's pKa) is around 8.5. When a molecule is dissolved in a solution where the pH is equal to it's pKa, exactly 50% of the molecules exist in each form, so in the case of DMT a pH of 8.5 will cause the DMT molecules to be 50% freebase and 50% salt. Moving one pH unit higher will make the proportion !0:1(around 90%) freebase to salt. Two pH units above the pKa(10.5), and 99% of the molecules will be in freebase form. At !!.5, 3 pH units above, 99.9% will be in freebase form and so on. So a pH of twelve is really a desirable level for the extraction. This topic is also relevant to increasing ionic strength using the protein that is present in the plant material being used. A protein carries a charge of -1 at extraction pH levels, but when a protein is heated for several hours under heat in the presence of either acid or base as a catalyst, it will break apart into it's constituent amino acids, which will each have a charge of -1 at the high pH levels being used. This could potentially have a drastic effect on the final ionic strength of the aqueous layer but I have not yet tried it myself. The pKa where most amino acids gain a charge of -1 is around 10-12, so even higher pH's will ensure that a full charge is gained by every molecule where a charge can be gained. Some molecules with amine groups like DMT itself will actually lose a charge of +1 and become neutral, but since we are already working at high pH's this effect should be be negligible.
There are other topics that need to be covered, like crystallization, but really the most important thing here is that buy reducing the volume of your pulls you are raising the concentration of spice in the NPS used. When you put your pulls in the freezer you are decreasing the solubility of the spice in the NPS and forcing the crystals to crash out.
I hope this info comes in useful for those just learning the process and I am willing to answer any questions that any of you may have. I may make a more comprehensive guide including some chemdraw illustrations when I have some time.
With Love,
CTM
edit: I just want to say that this is a basic understanding of how cybs tek really works so well and so simply. In his tek he uses all this information to fine-tune his process. I highly suggest giving that one a shot if you are new to this process.
1) Solubility
2) Partition Coefficients
3) Ionic Strength
4) Acid/Base Chemistry
Solubility:
Solubility is the extent to which a solute(anything being dissolved) can dissolve in a particular volume of solvent(the liquid holding the solutes). In a chemistry classroom what they will tell you is that "likes dissolve likes". This refers to the polarities of the molecules that one is attempting to dissolve. In general, non-polar molecules will dissolve in non-polar solvents(oils) and polar molecules will dissolve in polar solvents(water). This is why oil and water don't mix. The molecules of each are not soluble in each other, so they wont mix. The term miscibility is usually used for liquid-liquid situations, like ethanol being completely miscible with water means that they can be mixed in any proportion and it will form a homogeneous mixture. The truth of the matter is that oil and water do mix, just in such small amounts that we cant see it. As far as extraction goes, this means that there is some amount of naphtha in the water, and some amount of water in the naphtha. This is because at low ionic strengths(more on this later) most of the water molecules are neutral and do not repel the non-polar molecules as strongly as strongly as a fully charged ion in solution. Spice can exist in different forms that have different solubility in both water and naphtha. Solubility in both will increase at higher temperatures, as this is the case with most solutes and solvents. Higher temperatures mean higher solubility.
Partition Coefficients:
Partition Coefficients are a measure of how a solute will behave in a biphasic(2 layered) liquid system. These have values that are given in terms of the concentration in the non polar layer divided by the concentration in the aqueous layer. The standard solvent system which most literature values is given are for an octanol:water system. The goal when performing these extractions is to get the highest Partition Coefficient for the DMT so that most of it will end up in the non-polar layer(naphtha). This process of finding the optimum PC is different for every solute in every solvent system. We are mostly working with freebase DMT in a Naphtha: water system. We do this by attempting to decrease the solubility in the water layer while increasing the solubility in the naphtha layer. How can we do this? Well heating the entire solution will increase the solubility in both layers, to different extents, but the bottom line here is that you want the bottom layer to be cool when your pulling the spice from it, so if your going to use temperature your best option is to heat the naphtha before adding it to the cool(room temp) water and mixing as much as possible before the temperature equilibrate(which happens within seconds). There is another way to achieve our goal though, and that is by increasing the ionic strength of our aqueous layer in order to decrease the solubility of the spice in the aqueous layer. This also has the added benefit of decreasing the solubility of the water within the naphtha and the naphtha in the water, which is why adding salt results in less emulsions forming at higher ionic strengths, a more complete separation of the two layers is achieved.
Ionic Strength:
Ionic strength is essentially a measure of how much charge is present in a solution. It has a value that is calculated by taking the concentration of every solute in solution, raising that concentration to its charge, and then adding these all together. This means that molecules with more than one unit of charge have a much greater effect on the ionic strength. Calcium and Magnesium both have a charge of +2, While sulfate and phosphate ions have varying charges based on the pH of the solution, but at the high pH's that we run the extractions at they carry a charge of -2 and -3 respectively. pH plays an important role in ionic strength for reasons we will get into momentarily. I don't like to encourage the use of distilled water, I prefer filtered water and for this reason alone, distilled water has had its ionic strength lowered to the lowest possible level intentionally, what you are buying is de-ionized water. With filtered or spring water you have had anything that might be harmful to the process removed and are left with a plethora of ions such as sodium, potassium, chloride, magnesium, calcium, and many, many more. I understand the desire to start with distilled water but from a chemists perspective it is not really necessary and may actually decrease your yield if a high enough ionic strength has not been reached.
Acid/Base Chemistry:
Alright so this is where I want to begin with the two different forms of DMT. These are the Salt and the Freebase forms. The only difference between the two is that in the salt an extra hydrogen nucleus(proton) has been attached to the molecule at the amine(where the nitrogen is located). This makes this form have a charge of +1 at the Nitrogen. The charge is actually spread out over the the atoms surrounding the nitrogen, but most of the charge is located right on the added proton. The rest of the molecule is still very non-polar and hence still quite soluble in the naphtha, but the charge has a powerful effect on the solubility in water because water can easily dissolve charged molecules, even when they have a large non-polar region. Every molecule that can either receive or give up a proton will exist in the two different forms with different pH's determining what state that molecule is in. This switch from one form to another happens around a particular pH for each molecule. For DMT, this pH(known as it's pKa) is around 8.5. When a molecule is dissolved in a solution where the pH is equal to it's pKa, exactly 50% of the molecules exist in each form, so in the case of DMT a pH of 8.5 will cause the DMT molecules to be 50% freebase and 50% salt. Moving one pH unit higher will make the proportion !0:1(around 90%) freebase to salt. Two pH units above the pKa(10.5), and 99% of the molecules will be in freebase form. At !!.5, 3 pH units above, 99.9% will be in freebase form and so on. So a pH of twelve is really a desirable level for the extraction. This topic is also relevant to increasing ionic strength using the protein that is present in the plant material being used. A protein carries a charge of -1 at extraction pH levels, but when a protein is heated for several hours under heat in the presence of either acid or base as a catalyst, it will break apart into it's constituent amino acids, which will each have a charge of -1 at the high pH levels being used. This could potentially have a drastic effect on the final ionic strength of the aqueous layer but I have not yet tried it myself. The pKa where most amino acids gain a charge of -1 is around 10-12, so even higher pH's will ensure that a full charge is gained by every molecule where a charge can be gained. Some molecules with amine groups like DMT itself will actually lose a charge of +1 and become neutral, but since we are already working at high pH's this effect should be be negligible.
There are other topics that need to be covered, like crystallization, but really the most important thing here is that buy reducing the volume of your pulls you are raising the concentration of spice in the NPS used. When you put your pulls in the freezer you are decreasing the solubility of the spice in the NPS and forcing the crystals to crash out.
I hope this info comes in useful for those just learning the process and I am willing to answer any questions that any of you may have. I may make a more comprehensive guide including some chemdraw illustrations when I have some time.
With Love,
CTM
edit: I just want to say that this is a basic understanding of how cybs tek really works so well and so simply. In his tek he uses all this information to fine-tune his process. I highly suggest giving that one a shot if you are new to this process.
. Might try out cybs tek on it anyway just to see what happens..
