# Adding extra oils to cp soap



## toyah999 (Oct 9, 2014)

Hi, I've been hearing of people who add extra oils to their cp soap not calculated for in soap calc. Is this what superfatting is? What happens to the extra oils, does it make a soap more moisturising, does it go bad quicker? Is the extra oil added at the start or at trace? I assume that the lye would probably destroy any health/skin benefits that are in the oils, is this true and is that why people add extra oils. I've started making up my micas in glycerine for my mp soap and want to use it for cp, but I'm worried I will have to add a bit and what will happen to my soap since the glycerine is unaccounted for? And is adding fresh honey to soap ok, will it make my soap go bad quickly. I'm still fairly new to soap making, hence all the stupid questions lol. Thanks for the help!


----------



## Susie (Oct 9, 2014)

You can't add "extra oils" to CP and hope that you get a good outcome.  You need to figure the superfatting in using a good lye calculator.  If you find your soap is drying, just up the superfatting %, and lower the cleansing number until you are happy with it.  You need to figure the amount of oil you add to the mica in as part of the recipe.  If it is just a gram or two, then I would not sweat it much, but better safe than sorry, especially if you are new.

You can add honey to soap.  You can either add it to the oils, or add it to the lye water, but it will increase the heat in the recipe either way, so be aware of that if you do not want gel.  I would stick to around 1 tablespoon(14 gm) PPO(per pound of oil, about 400-500 gm)

There are no stupid questions.  Especially when you probably asked what someone else needed to know, but was too shy to ask.


----------



## toyah999 (Oct 9, 2014)

Thanks Susie, that was a great help, I was very confused.


----------



## IrishLass (Oct 10, 2014)

Ditto what Susie said. You can't add "extra oils" to CP and expect them to remain un-impacted by the lye. I understand completely why your were confused about it, though, because it used to be a fairly common assumption among handmade soap-makers up until not too very long ago. It has since been proven definitely to be a false assumption, but because it's in many of the handmade soap-making books out there, the myth lives on. 

 HP may be another story, though. You may have a better chance of the superfatting oils surviving the lye monster by adding them to the cooked soap batter after there is no more zap. I say 'may' because I've run into some discussions lately that question whether or not that 'better chance' is as big as we imagine it to be. Hopefully, Dr. Dunn (or somebody else) will be able do some lab experiments with superfats in HP like he (Dr. Dunn) did with CP and give us a definitive answer on that as well.  


 IrishLass


----------



## The Efficacious Gentleman (Oct 10, 2014)

I would be interested in those discussions!


----------



## Susie (Oct 10, 2014)

I completely missed a statement you made.  You said you were adding micas to glycerin, and I read oil.  I am so sorry.  Glycerin is not an oil.  It is, for the purpose of soap, considered a water product.  So, you do not need to worry that it will change the amount of oil.


----------



## IrishLass (Oct 10, 2014)

The Efficacious Gentleman said:


> I would be interested in those discussions!



Three of the discussions I've run into are here (from a few years ago):

http://www.soapmakingforum.com/showthread.php?t=14185&highlight=static

http://www.soapmakingforum.com/showthread.php?t=10707&highlight=static

http://www.soapmakingforum.com/showthread.php?t=9228&highlight=static


and a long, much more detailed one can be found here:

http://www.thedishforum.com/forum/i...perfatting-saponification-timeline/?hl=static

and a small one here:

http://www.thedishforum.com/forum/i...ionhow-do-you-partially/?hl=swap#entry1939715


IrishLass


----------



## The Efficacious Gentleman (Oct 10, 2014)

You're a star! Some light reading for me


----------



## Seawolfe (Oct 10, 2014)

I've used glycerin and mica on and in my CP soap - it made lovely gold splashes on top, but if you use too much glycerin the color will stick but they might not absorb and it will be a bit wet on top until you turn the soap on its side and let it dribble off 

Some micas color the inside of CP soap really well, and some don't - you want to be sure you have the CP soap stable type.


----------



## The Efficacious Gentleman (Oct 10, 2014)

IrishLass said:


> Three of the discussions I've run into are here (from a few years ago):
> 
> ................
> 
> ...


 
Had a read through the ones on here but it seems to be more about adding things at trace, even with HP, which is different from adding things after the cook in HP.  After the cook, there is no lye left, just finished salts of fatty acids. So what is added at that point is then unable to react with lye, surely?


----------



## LBussy (Oct 10, 2014)

The Efficacious Gentleman said:


> Had a read through the ones on here but it seems to be more about adding things at trace, even with HP, which is different from adding things after the cook in HP.  After the cook, there is no lye left, just finished salts of fatty acids. So what is added at that point is then unable to react with lye, surely?


You are correct in my experience (which admittedly pales in comparison to the other experience here).  I make my HP soap, let it "cook", and mix in my superfats with the fragrance oils after the cook is done.


----------



## IrishLass (Oct 10, 2014)

The postulation that caught my attention in the links I provided is this one:



			
				carebear said:
			
		

> ]soap is not static and the fatty acids do a little dance swapping in and out of the salts *so that even if you superfat an HP soap you may not end up with that particular fat still intact.
> *


 
 Bolding mine.

 In the link I gave you to that longer, more detailed thread over on the Dish, the same point was made by a different person with a chemistry background whose source was her old chemistry manuals.

 I sure would love for Dr. Dunn to tackle this one to settle it once and for all in a more concrete, definitive manner (or to see those old chemistry manuals!). For now, I'm left wondering if our current thinking in regards to superfatting in HP after the cook will turn out to be the same kind of (wrong) assumption we all use to make in regard to superfatting at trace in CP? I feel like I'm in limbo land now. 

 Maybe DeeAnna could weigh in on this?


 IrishLass


----------



## new12soap (Oct 10, 2014)

IrishLass said:


> The postulation that caught my attention in the links I provided is this one:
> 
> 
> 
> ...



This is my understanding as well, but I may have read it in the same place.

Even if superfatting does work, let's do the math...

I am superfatting my soap after the cook at 5% and decide I want to use shea butter. Let's say my bar is 100g total weight. My total shea butter content is going to be a little less than 5g (because my SF was based on oil weight, not total batch weight, and some of the water will cure out). So we have a little less than one teaspoon of shea butter per bar of soap.

Now, let's say that my bars last me approx 30 showers. So I am getting less than 0.2g of shea butter on all of my skin, along with the soap that is also pretty much washing it back off as I go, where it remains just long enough for me to finish washing and get rinsed.

You are talking about less than 1/5 of a gram of shea butter spread so thin that it covers your entire body for probably less than 2 minutes. How much benefit can there possibly be? I personally have trouble believing that such a negligible amount will really feel or perform any differently than say, olive oil, or the combination of oils you started with.

And remember, we are also assuming that the lye was completely used up and your sap values were spot on when you started. Also pretty unlikely.

IMO the only point to superfatting after the cook is possible label appeal.


----------



## LBussy (Oct 10, 2014)

I think superfat does work (forgetting for a moment WHICH fat it is) because I work with soap having a strong coconut oil base that is on my face for an extended period.  I know without superfat that the soap dries my face out.  

I think that the hypothesis that there is some "dance" between the salts is baseless.  (see what I did there?)  In order to react, there needs to be a reactive component.  It is our goal to NOT have a reactive component left after let's say an HP cook so what exactly causes the reaction?  Salts are relatively non-reactive as are fats, so what catalyzes this "dance?"

Any reactions I was able to find which caused a salt to dis/re-associate was catalyzed by an excess of base which we don't have.  Perhaps in CP for that 24 hour period there's an opportunity for the solution/suspension/emulsion to reach it's own stasis, but I can't see it in HP.

(sits back and waits for the inevitable smart person to prove me wrong)


----------



## new12soap (Oct 10, 2014)

I completely agree that superfatting not only works, it is absolutely necessary.

All I am saying is that IMO superfatting after the cook with a particular oil isn't going to do much good or make a noticeable difference. Formulate a good soap up front and don't sweat it.

JM2C


----------



## IrishLass (Oct 10, 2014)

LBussy said:


> I think superfat does work



Yes- just to clarify, I don't doubt for a moment that adding extra fat to one's soap works. I'm just questioning whether or not we are assuming too much by hoping or believing that whatever particular fat we might choose to add after the cook will remain free/unsaponified. 

I personally don't add extra fat after the cook in HP myself, but when asked, I've always steered those soapers who've hoped to have that kind of control over an 'intact' superfat, in the direction of HP, and now I'm just wondering if I need to re-think that, or else add the disclaimer of "_may_ remain intact" or "may have a better chance of remaining intact" instead (until I have more concrete references). 




			
				new12soap said:
			
		

> All I am saying is that IMO superfatting after the cook with a particular oil isn't going to do much good or make a noticeable difference. Formulate a good soap up front and don't sweat it.
> 
> JM2C



That is my attitude, too.

By the way, thank you very much for doing the math and for putting things into perspective. 



			
				LBussy said:
			
		

> (sits back and waits for the inevitable smart person to prove me wrong)



LOL I'll sit with you, but I for one will be glad to just have the matter cleared up and proven definitively either way. 


IrishLass


----------



## LBussy (Oct 10, 2014)

Okay I read all those, searched, read some more.  I think it distills down to this person repeating the same thing:



carebear said:


> for CP soaping, it's been shown that it doesn't matter if you add them at the beginning (my recommendation) with all the other oils, or at trace.  The vast majority of the saponification happens in the mold.  PLUS, soap is not static - the fatty acids swap themselves in and out of the "salts" (the saponified fatty acids are then salts, go figure).



What we know is that a strong base combined with a triglyceride cleaves off a glycerine molecule, then the metal combines with the fatty acid replacing part of the hydrogen with the cation and creating a salt.  By it's very definition it is the product of a neutralization reaction of an acid and a base.  

In our soaps, especially a HP soap, the solution is supersaturated - there is not enough water to dissolve the salts so there is little opportunity for dissolution.  Therefore there is likewise little opportunity for cation migration between the salts which is a process that relies upon a solution first, then dissolution.  The fats added for superfat (at the end in HP) will not be exposed to free lye, therefore will not be converted to salts, and therefore will not be a product of any migration of cations between the salts.  All this because they cannot be solubilized to begin with.  

Now if we had salts of sodium and potassium in the same soap and let's say for the sake of argument we went to the trouble to batch the stearic acid with KOH and the CO with NaOH, both of these salts *would* be at least soluble and therefore could be subject to migration of the cations rendering that process a moot one.  

All that to say fats added to a 100% reacted soap remain those fats.  Mixed salts may not remain those that were originally intended.   At least to my Civil Engineer becomes IT mind.

I don't know who Carebear is but if there's any proof of salt cation migration I'd very much like to see it.  Otherwise it seems to be implausible.  Of course solubility equilibria and related calculations are WAY outside of my comfort zone but so far this seems like a reasonable believe absent proof of the opposite.


----------



## IrishLass (Oct 10, 2014)

I don't know if brings anything to the discussion or not, but I happened upon the following article as I was searching under chemical equilibrium as it relates to soap. Here's the link to the entire wiki article:

http://en.wikipedia.org/wiki/Chemical_equilibrium

The following quote from the article caught my attention I as I was reading it, but I don't know enough about chemistry to be able to know if the process explained in the quote can be extrapolated to the microscopic behavior that goes on inside of a bar of soap at the molecular level:



> "Although the macroscopic equilibrium concentrations are constant in time, reactions do occur at the molecular level. For example, in the case of acetic acid dissolved in water and forming acetate and hydronium ions,
> CH3CO2H + H2O ⇌ CH3CO2− + H3O+
> 
> a proton may hop from one molecule of acetic acid on to a water molecule and then on to an acetate anion to form another molecule of acetic acid and leaving the number of acetic acid molecules unchanged. This is an example of dynamic equilibrium. Equilibria, like the rest of thermodynamics, are statistical phenomena, averages of microscopic behavior.
> ...


 
 It made me curious as to what kind of microscopic changes might be happening in the soap when exposed to water when bathing, or when a previously unexposed layer of soap is exposed to air.  

 IrishLass


----------



## LBussy (Oct 10, 2014)

That's good stuff IL, thanks for posting.  

I guess that's the upshot:  "the macroscopic equilibrium concentrations are constant in time, reactions do occur at the molecular level"

Even though it can happen, it's not going to change the nature of the soap.  And since that's in a solution, it's even less likely to change the nature of what we've created with an insoluble substance like oil mixed into a previously reacted soap.  For CP, completely agree.  Mixed in at the initial mix or at trace makes no difference.

That's what I think anyway ... worth what ya paid for it.


----------



## DeeAnna (Oct 10, 2014)

"...In our soaps, especially a HP soap, the solution is supersaturated - there is not enough water to dissolve the salts so there is little opportunity for dissolution...."

I have to say that bar soap is an unusual and intriguing type of solid material. It is not a liquid, supersaturated or otherwise, regardless of whether it's made using a CP or HP method.

To trot out some $5 words, bar soap is a lamellar crystalline solid. The word lamellar refers to sheets (or lamelae) of pure soap separated by thin sheets of water-based liquid. The liquid within this structure is not supersaturated. The soap molecules in these lamelae are organized in tidy geometric formations, which is where the word crystalline comes in. The whole mess is kind of like a wedding cake with layers of frosting, cake, frosting, cake, etc. I'm simplifying a lot here, because other structures are also found in bar soap, but this is the gist.

***

Soap is a salt, which is a type of ionic molecule. Ionic molecules tend to split apart easily when the circumstances are right. Some ionic molecules require very little coaxing to split apart -- examples being NaOH, KOH, and table salt (NaCl). Other ionic molecules require a wee bit more coaxing -- soap being a good example. A soap molecule can split apart into a cation (say cat-ion) which is the sodium or potassium or whatever and a fatty acid, given enough incentive.

Another type of molecule is a covalent molecule. These molecules take a lot of coaxing to split apart. Once split apart, they do not easily reform back into their original form. A triglyceride (fat) is an example of a covalent molecule. One of the reasons why we use a strong alkali (NaOH or KOH) to make soap is that it takes a lot of work to split a covalent fat molecule apart. Once the fat is split apart into fatty acids and glycerin, the actual formation of the ionic soap molecule from a cation (Na or K) and a fatty acid is pretty easy. 

***

Carebear: "...soap isn't really a static thing and I've read that soap molecules swap out so what you think is sodium palmate + cocoa butter can become sodium cocoa butterate plus palm oil on and off...."

I doubt that fatty acids and glycerin in soap can actually reform back into fats except under highly unusual circumstances. The concept of "dynamic equilibrium" in chemistry is all about energy requirements and statistical probabilities. For example, it is easy to sled down a hill, but it takes a lot of energy to walk up the hill. The statistical probability is high that a sledder will go down the hill and stay there. An input of outside energy is required to overcome this probability -- in other words, the sledder has to do the work of walking back up to the top of the hill.

To explain a bit further, a chemist can write the chemical reaction to make soap in two ways -- a "forward" reaction to soap and a "reverse" reaction back to fat:

Forward reaction: Triglyceride + Alkali => Soap + Glycerin
Reverse reaction: Soap + Glycerin => Tryglyceride + Alkali

There are statistical probabilities for each version based on energy requirements. The probability of the forward reaction (to make soap) is pretty high. Give the fat and alkali a nudge and a good stir and *voila* you get soap. Reforming three fatty acids and one glycerin back into a fat molecule is not nearly as easy and spontaneous, so the chances of the reverse reaction happening are much smaller -- not impossible, but improbable.

What Carebear may have been thinking about is the fact that ionic compounds are rather promiscuous. In the case of soap, the cations on the soap molecules are quite happy to drift around. 

For example, one can partially make a sodium (Na) soap from a pure potassium (K) soap simply by adding table salt (sodium chloride, another ionic compound) to the potassium soap. The Na ions will bump the K ions off some of the fatty acids and the result is a mixed cation soap. 

Another example is soap scum. This is formed when calcium (Ca) or magnesium (Mg) ions in "hard" water replace the regular cations in your soap. The result is sticky, insoluble magnesium or calcium soaps that make a gray deposit in your shower or tub and leave a sticky residue on your skin. This chemical reaction happens right while you lather up and rinse off -- pretty fast!

It's been a long difficult day and I'm pretty tired, so I hope this makes a bit of sense.


----------



## sassanellat (Oct 11, 2014)

The Efficacious Gentleman said:


> Had a read through the ones on here but it seems to be more about adding things at trace, even with HP, which is different from adding things after the cook in HP.  After the cook, there is no lye left, just finished salts of fatty acids. So what is added at that point is then unable to react with lye, surely?



There are some videos out there (ones associated with Essential Depot) where the lady there does HP all the time, adding glycerine, EOs or FOs, specialty oils, etc. after the lye reaction is complete. Theoretically, they should survive perfectly. But there is the heat to consider, because everything is added hot and heated well to allow everything to combine. I haven't tried HP yet, but doing exactly what you mentioned is at the top of my list to try. I'd love to be able to make a small batch soap with superfatted borage oil for psoriasis.


----------



## The Efficacious Gentleman (Oct 11, 2014)

This has been simply wonderful! A great thread indeed. Thank you to all.


----------



## LBussy (Oct 11, 2014)

> What Carebear may have been thinking about is the fact that ionic compounds are rather promiscuous. In the case of soap, the cations on the soap molecules are quite happy to drift around.
> 
> For example, one can partially make a sodium (Na) soap from a pure potassium (K) soap simply by adding table salt (sodium chloride, another ionic compound) to the potassium soap. The Na ions will bump the K ions off some of the fatty acids and the result is a mixed cation soap.


So trying to digest that - the "promiscuous cation dance" to which you refer is the potential of a cation to swap with another cation (either free or currently bonded to a fatty acid).  In other words if we have Sodium Cocoate and Potassium Stearate that we worked very hard to keep separate, we will likely end up with at least some Potassium Cocoate and Sodium Stearate.  

Before that you (paraphrased greatly) said the chance to turn back into "fat" is statistically improbable, so adding for example shea butter after the lye is completely reacted with the stearic acid is unlikely to result in saponified shea and unreacted stearic acid.

If I am correct in interpreting this so far:


"Special" superfats added at trace are unlikely to persist as "special" superfats, unless they have some property that makes them a less likely target for saponification.
Superfat added after a complete reaction (HP or CP rebatch) is likely to retain the character of the superfat.
A mixed cation salt will likely perform the "promiscuous cation dance"
Free cations will also result in some swapping of metals in the soap (soap scum)



> It's been a long difficult day and I'm pretty tired, so I hope this makes a bit of sense.



You should try reading it before coffee!  

Well if my bullets captured what you said then it made sense.  If not then .. well, I'll make some coffee and try again.

Oh wait, there was also some mention of cake.  Yes cake.  Love cake!


----------



## LBussy (Oct 11, 2014)

sassanellat said:


> I'd love to be able to make a small batch soap with superfatted borage oil for psoriasis.


The small HP batch is exactly how I did my shaving soap formulation testing.  I did 100g batches in small plastic screw-top disposable food containers and "simmered" those in a pan of water as a pseudo bain marie.







I did not get the "boil" that I get in a crock pot, nor any evaporation, but as a means to explore the recipe's characteristics compared across several samples it was very effective in terms of time and resources.

I just looked up Borage Oil.  Doesn't look like something I'd put in a shaving soap:  



> Bleeding disorders: There is some concern that borage seed oil might prolong bleeding time and increase the risk of bruising and bleeding. If you have a bleeding disorder, use borage with caution.


Ref: http://www.webmd.com/vitamins-suppl...eingredientid=596&activeingredientname=borage

The rest of the descriptions make it sound quite nice though.  Looks like the active ingredient may be gamma-linolenic acid which would probably be why adding it in a manner where it will not react is desirable?  Also seems evening primrose is high in this acid.

Good read on it here:

http://umm.edu/health/medical/altmed/supplement/gammalinolenic-acid


----------



## DeeAnna (Oct 11, 2014)

_...if we have Sodium Cocoate and Potassium Stearate that we worked very hard to keep separate, we will likely end up with at least some Potassium Cocoate and Sodium Stearate._

Yep -- spot on. This would be especially true when the soap is diluted in water, but it is likely to happen even in a solid bar soap to some degree. 

_...so adding for example shea butter after the lye is completely reacted with the stearic acid is unlikely to result in saponified shea and unreacted stearic acid._

Again, yes, that is what I suspect is correct.

_ "Special" superfats added at trace are unlikely to persist as "special" superfats, unless they have some property that makes them a less likely target for saponification._

Yes. Kevin Dunn did a few experiments that support this hypothesis that adding fat at trace does not "protect" that fat from being saponified. In his experiments, the unsaponified fat remaining in the soap was a blend of ALL fats added to the soap pot, whether they were added at the beginning or at trace. 

What he found in some of his experiments is that saturated fatty acids (lauric, myristic) were a little more likely to be saponified than the unsaturated fatty acids (oleic, linoleic). In another experiment, the ricinoleic acid in castor oil was more likely to be saponified than the saturated fats in palm. I want to stress that he only did a few experiments on carefully selected combinations of fats, so use his results as a rough guide, not gospel truth.

_Superfat added after a complete reaction (HP or CP rebatch) is likely to retain the character of the superfat.
A mixed cation salt will likely perform the "promiscuous cation dance"
Free cations will also result in some swapping of metals in the soap (soap scum)_

Yes to all three in regards to soap.


----------



## LBussy (Oct 11, 2014)

Excellent!  The day is now free to discuss soap labels!


----------



## sassanellat (Oct 11, 2014)

LBussy said:


> The small HP batch is exactly how I did my shaving soap formulation testing.  I did 100g batches in small plastic screw-top disposable food containers and "simmered" those in a pan of water as a pseudo bain marie. {...}
> 
> I did not get the "boil" that I get in a crock pot, nor any evaporation, but as a means to explore the recipe's characteristics compared across several samples it was very effective in terms of time and resources.
> 
> ...



The plastic contains are quite clever, Lee. Boiling won't complete the reaction as fast, but it still gets you there, no fuss, no muss. 

I'm also not sure I'd go with borage oil for shaving if the anticoagulant factor is significant due to the possibility of nicking the skin (though the GLA is slick and seals the skin, in general, which would be nice for shaving soap). It does seem to work quite well for eczema and psoriasis (unlike nearly all the rest of the homespun claims) in actual scientific testing, and it's used in many commercial products for the same reason (and the GLA, which tends to help seal the skin, thus helping eliminate the immune reactions that undelie both conditions). And yes, evening primrose oil is also nearly as high in GLA, though I'm told from people that use those commercial products that EPO works better for eczema, and BO works best for psoriasis in lotions and salves. The citations are on swiftmonkey's site if you are interested.


----------



## Susie (Oct 11, 2014)

sassanellat said:


> There are some videos out there (ones associated with Essential Depot) where the lady there does HP all the time, adding glycerine, EOs or FOs, specialty oils, etc. after the lye reaction is complete. Theoretically, they should survive perfectly. But there is the heat to consider, because everything is added hot and heated well to allow everything to combine. I haven't tried HP yet, but doing exactly what you mentioned is at the top of my list to try. I'd love to be able to make a small batch soap with superfatted borage oil for psoriasis.



Be warned that you can't trust what you hear on every YouTube video, whether or not they are associated with a purveyor of soapmaking materials.  If that is who I think it is(and I am 99% sure that it is), she also says that HP soap is "cured" and ready to sell the next day.  That is not true.  I have also found some other glaring un-truths and half-truths, but none quite so egregious as that one.


----------



## sassanellat (Oct 11, 2014)

Susie said:


> Be warned that you can't trust what you hear on every YouTube video, whether or not they are associated with a purveyor of soapmaking materials.  If that is who I think it is(and I am 99% sure that it is), she also says that HP soap is "cured" and ready to sell the next day.  That is not true.  I have also found some other glaring un-truths and half-truths, but none quite so egregious as that one.



*nods* I noticed that there were some problems with some of the things she said. She's also fairly inconsistent, has terrible safety technique, and later she implies that she cuts corners because she "can't be patient to wait for more than 2 weeks" for a cure. It's why in my first post, I wanted to try some HP out, adding additional superfat at the end, and see how it went, rather than just believing (especially with a delicate oil). It does make perfect sense that if you complete the reaction, you should be able to add additional oils and inclusions at the end if it will survive the final heating to get everything evenly distributed.


----------



## The Efficacious Gentleman (Oct 12, 2014)

You don't need to heat again - add it in while it is cooler but still fluid (sodium lactate will help here) and it will stir in no worries


----------

