Natural glycerin in CP soap

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samirish

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While I know that lye and oils combine during the saponification process to produce soap and glycerin, I was wondering do certain oils result in the end product soap having more glycerin vs using other oils?

For example will a soap made with all olive oil have more glycerin in the finished soap vs a soap made with all coconut oil? Or vice versa? Or do all soaps have the same amount of glycerin regardless of which oils and fats are used?

Is so, is there a chart somewhere that shows a list of oils and the amount of glycerin they leave in the finished soap?

Thanks
 
I am sure a proper science-soaper will come along shortly, but I will also have a stab at it -

Oils that we use for soaping are triglycerides. For us, an important take-away from that is that the molecule contains glycerine. When they saponify, the molecules break down and reform with the lye to make soap. The non-glycerine parts of the oil molecule combine with the lye to make soap leaving nothing for the glycerine to combine with, which gives us soap and glycerine.

So with that in mind, I would say that the oils with the higher amounts of molecules would give the most glycerine. These would be the oils with higher SAP values - if they have higher SAP values, they need more lye molecules so should have more molecules themselves.

I think - this may be totally wrong and I await a proper answer from someone who actually knows things!
 
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I think it's simpler than that - I think that all the oils are triglycerides and no matter what the oil, they all shed the 3 triglycerides on their tail when they make soap. So the magic number is 3 per molecule of oil, no more, no less.

Of course, I am often wrong too :)
 
I think it's simpler than that - I think that all the oils are triglycerides and no matter what the oil, they all shed the 3 triglycerides on their tail when they make soap. So the magic number is 3 per molecule of oil, no more, no less.

Of course, I am often wrong too :)

Yes, but if 1kg of oil A needs 75g lye and 1kg of oil B needs 125g lye, then oil B has more molecules per 1kg batch, so more glycerine per 1kg batch.
 
I think it's simpler than that - I think that all the oils are triglycerides and no matter what the oil, they all shed the 3 triglycerides on their tail when they make soap. So the magic number is 3 per molecule of oil, no more, no less.

Of course, I am often wrong too :)


So what your saying Seawolfe is that no matter the oil or fat, it result in the same amount of glycerin in the finished soap? Correct me if im wrong..
 
Okay, I promise I didn't read that thread before answering! A chemist friend of mine visited from Chicago recently and showed me using what ever was on my dining table - forming the triglyceride with pens. He was really excited to have an avid listener.

So the way to calculate IS by the amount of lye needed, as oils with a higher SAP number have more molecules by weight and so there is more glycerin by weight.
 
If the info in the thread that Lenaree provided is not clear, please let me know. I'll take another stab at explaining things in a different way. The short answers to Sam's questions are:

Look at the saponification value for each fat. Fats with high sap values are better "glycerin makers" on a per weight basis....

0.77 grams glycerin are produced by saponification for every 1 gram of NaOH in the soap recipe. The relationship between NaOH and glycerin produced is a tidy, simple solution. It will work regardless of the amount and type of fats in the recipe. It is totally independent of the amount of superfat in the recipe as well. The only time when this relationship won't work is with a lye heavy recipe....

The fats that create a higher % of "natural" glycerin from saponification are the same fats that have a "high cleansing" number -- coconut, palm kernel, babassu, and the like.... The reason why these fats make more glycerin by weight during saponification is that they are physically smaller molecules. Each molecule of fat, regardless of size, will make just one molecule of glycerin. That fact does not change. What is different is that more molecules of coconut oil are packed into a gram than a physically larger fat like olive oil....

The weight of glycerin produced based on the fats in the recipe will vary with the saponification value of the fats, the percentages of the fats, and the actual superfat. Since there are infinite number of fat and superfat combinations, there are an infinite number of solutions to that problem. One can create a spreadsheet to calculate the answer, but it doesn't translate into a tidy table....
 
Thank you guys for explaining it so well. I am looking to make a soap that is on the high end of the glycerin range so now I know which oils to choose from.

Thank you :)
 
If the info in the thread that Lenaree provided is not clear, please let me know. I'll take another stab at explaining things in a different way. The short answers to Sam's questions are:

Look at the saponification value for each fat. Fats with high sap values are better "glycerin makers" on a per weight basis....

0.77 grams glycerin are produced by saponification for every 1 gram of NaOH in the soap recipe. The relationship between NaOH and glycerin produced is a tidy, simple solution. It will work regardless of the amount and type of fats in the recipe. It is totally independent of the amount of superfat in the recipe as well. The only time when this relationship won't work is with a lye heavy recipe....

The fats that create a higher % of "natural" glycerin from saponification are the same fats that have a "high cleansing" number -- coconut, palm kernel, babassu, and the like.... The reason why these fats make more glycerin by weight during saponification is that they are physically smaller molecules. Each molecule of fat, regardless of size, will make just one molecule of glycerin. That fact does not change. What is different is that more molecules of coconut oil are packed into a gram than a physically larger fat like olive oil....

The weight of glycerin produced based on the fats in the recipe will vary with the saponification value of the fats, the percentages of the fats, and the actual superfat. Since there are infinite number of fat and superfat combinations, there are an infinite number of solutions to that problem. One can create a spreadsheet to calculate the answer, but it doesn't translate into a tidy table....

DeeAnna, Very interesting. How much glycerin is produced using 1g of the 90% KOH sold by Essential Depot?
 
...and then there is the processing and knowing what level the sap value you have i based on... not a tidy table indeed...
 
If the info in the thread that Lenaree provided is not clear, please let me know. I'll take another stab at explaining things in a different way. The short answers to Sam's questions are:

Look at the saponification value for each fat. Fats with high sap values are better "glycerin makers" on a per weight basis....

0.77 grams glycerin are produced by saponification for every 1 gram of NaOH in the soap recipe. The relationship between NaOH and glycerin produced is a tidy, simple solution. It will work regardless of the amount and type of fats in the recipe. It is totally independent of the amount of superfat in the recipe as well. The only time when this relationship won't work is with a lye heavy recipe....

The fats that create a higher % of "natural" glycerin from saponification are the same fats that have a "high cleansing" number -- coconut, palm kernel, babassu, and the like.... The reason why these fats make more glycerin by weight during saponification is that they are physically smaller molecules. Each molecule of fat, regardless of size, will make just one molecule of glycerin. That fact does not change. What is different is that more molecules of coconut oil are packed into a gram than a physically larger fat like olive oil....

The weight of glycerin produced based on the fats in the recipe will vary with the saponification value of the fats, the percentages of the fats, and the actual superfat. Since there are infinite number of fat and superfat combinations, there are an infinite number of solutions to that problem. One can create a spreadsheet to calculate the answer, but it doesn't translate into a tidy table....

Is it the length of the carbon chain that also determines the cleansing factor of the soap as well? The shorter chains in mysritic and lauric acid makes more soap molecules by volume and thus more oil grabby ends? So more grabby soap by volume in a coconut bar than a olive oil bar of equal weight?? or does the oil graby end of lauric soap have a stronger grab???
If you ever make soap related chem youtube vids I will watch the crap out of them.
 
Is it the length of the carbon chain that also determines the cleansing factor of the soap as well? The shorter chains in mysritic and lauric acid makes more soap molecules by volume and thus more oil grabby ends? So more grabby soap by volume in a coconut bar than a olive oil bar of equal weight?? or does the oil graby end of lauric soap have a stronger grab???
If you ever make soap related chem youtube vids I will watch the crap out of them.
+1,000 on this.
 
Boyago and CPA -- Not ignoring you -- I'll get you answers later today. Just taking a quick lunch break and don't have time at the moment....
 
"...How much glycerin is produced using 1g of the 90% KOH sold by Essential Depot? ..."

I'm going to give you the set-up for this problem. See if you can come up with the answer, okay?

First thing to know is the chemical conversion between the two lyes:
1 g of NaOH is the equivalent of 1.4 g of KOH.
Said another way, 1 g of KOH is the equivalent of 0.7 g NaOH.

I have already said that 1 g of NaOH will produce 0.77 g of glycerin, so there's another piece of the puzzle.

First, figure the "ideal" amount of glycerin produced by 100% pure KOH.

Next, figure the glycerin for impure KOH. For a 90% purity KOH, the glycerin it can make is 90/100 of the ideal.

***

"...Is it the length of the carbon chain that also determines the cleansing factor of the soap as well?..."

Um, yes and no. Sorry to be vague, but there is no short-n-sweet answer to this question. There are two issues at work here -- solubility in water and "fat dissolving" abililty.

Let's start simple by talking only about soap made from a single pure saturated fatty acid. In this case, your idea is definitely correct. Shorter chain fatty acids create soap that is more soluble in water and is a stronger cleanser than soap made with longer chain fatty acids. The more soap that can dissolve quickly into water, the more likely the soap will be a strong cleaner. The shorter the carbon chain also means the soap will be a stronger cleanser from a fat-dissolving point of view.

The solubility of soap made from saturated fatty acids, from high solubility to low: Sodium laurate (12 carbon atoms) > sodium myristate (14 carbon atoms) > sodium palmitate (16 carbon atoms) > sodium stearate (18 carbon atoms).

But there are UNsaturated fatty acids that are the same length as saturated fatty acids. Once you start comparing soap made from pure UNsaturated fatty acids and pure saturated fatty acids, then your idea breaks down a little bit when we look at solubility. For example, stearic, oleic, linoleic, and ricinoleic acids all have 18 carbons, but stearic is saturated and the others are unsaturated.

Let's stick the pure sodium oleate soap into the solubility list, since I have solubility data for that soap. The relative solubilities of all of these pure soaps would be this: Sodium oleate (18 carbon atoms, UNsat) > Sodium laurate (12 carbon atoms, sat) > sodium myristate (14 carbon atoms, sat) > sodium palmitate (16 carbon atoms, sat) > sodium stearate (18 carbon atoms, sat).

Looking at "fat dissolving" power, however, sodium oleate with its UNsaturated nature is not going to be as effective at cleaning as the shorter chain saturated soaps (laurate and myristate).

Some of this seems to run counter to "common sense", but that's chemistry for you!

Everything I've said so far relates to a PURE soap made from a single fatty acid. When you mix the fatty acids together and make soap, as is normally the case in a real-life bar of soap, the solubility and fat-dissolving power of the soap-as-a-whole will be entirely different than the properties of the individual pure soaps that make up the bar.

In general, a real-life soap will tend to be somewhere between the extremes, but the solubility and cleansing ability will often be higher than one might guess. The reason why this is true is because bar soap is a type of crystalline material. In a crystal, molecules are packed together in a more or less regular structure. Molecules that are similar in size and shape pack nicely and make tidy, dense soap crystals that are not as soluble in water. Molecules that are lumpy bumpy (UNsaturated fatty acids) or molecules in a variety of sizes can't pack together as nicely, so they make untidy, irregular soap crystals that are more soluble.

This is a complicated topic that I really don't know well. Even so, I probably know more than most and I hope I've given y'all a little bit of insight.
 
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Nice post deanna. and that boys and girls, is why castile is so wonderful.
 
Thanks for the whole post, DeeAnna! :thumbup:

Let's stick the pure sodium oleate soap into the solubility list. The relative solubilities of all of these pure soaps would be this: Sodium oleate (18 carbon atoms, UNsat) > Sodium laurate (12 carbon atoms, sat) > sodium myristate (14 carbon atoms, sat) > sodium palmitate (16 carbon atoms, sat) > sodium stearate (18 carbon atoms, sat).

Here is a graph showing the solubility of the sodium soaps depending on the temperature.
source:
The solubility of sodium and potassium soaps and the phase diagrams of aqueous potassium soaps, by James W. McBain, William C. Sierichs
Journal of the American Oil Chemists Society

solubilityoffattyacids1.jpg
 

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