Shampoo Bar - Thanks Lindy!!

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Adding citric acid to HP after the cook will do the same as adding it to CP. The lye binds more strongly to citric acid, and so will UNBIND from the fatty acids in order to cozy up to the citric acid, leaving you with a higher superfat and no real change in pH. (This is one thing that LS makers have to watch out for when using citric acid to neutralize the intentionally-lye heavy base. Using more citric acid than excess lye will cause cloudiness from the oils that are un-soaped by the citric acid.)

Sure would be nice to find a way to reduce the pH in my shampoo bar. So what you are saying is that after all the lye and oils have reacted and created a soap during HP, that once you add the acid, the lye will then revert back to lye, leaving me with a puddle of oil and some compound of lye and citric acid? There, is a bad high school chemistry class gone very wrong! ;)

Edit: just read that citric acid and lye combine to make sodium citrate. So I'm guessing here that the acid pulls the lye off the oil molecules to make sodium citrate. Ok, back to trying to find a shampoo that doesn't have SLS or other detergents I'm allergic to. Argh!
 
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Using a small sliver of this as hand soap waiting for the balance to cure. The first few days it was very creamy and not much lather but today there is more lather. Nice soap and looking forward to trying on my hair. Doubt I can wait a month.
 
I made Lindy's original recipe a few months after it was posted by Genny. I made a ginormous batch and I am still using it - so I have been using this instead of commercial shampoo for over a year, with no additional styling products. I swim 4x a week so because of that I wash it often, but on my off days I feel comfortable skipping a wash/style. I have made a couple observations and was wondering if anyone else noticed the same:

1. My hair blows dries faster than with commercial shampoo - I was wondering if the oil in the shampoo bar had something to with this, like maybe it repels water
2. My hair is thick but naturally very straight, doesn't hold a curl or style well. Using a shampoo bar though gives it "tooth" - as if maybe the hair cells aren't laying down flat (although it does look shiny). I don't know why this is but it has more hold with no additional products - maybe again because of the oil.
3. I left a bar one time in a plastic bag in my gym bag, in my car on a hot day. When I came out the bar was liquid and never hardened back up at room temperature. My other bar of homemade soap (goats milk & honey) did not do that.

Any feedback is welcome - thanks everyone!
 
I am finding this conversation on citric acid interesting and informational! I recently have begun using Lindy's shampoo bar recipe (soy bean swapped for sunflower because I didn't have soy), and my hair is loving it after several washes. I haven't used citric acid in soap at all, but in doing a little more looking I found a shampoo bar post on Soap Queen that uses citric acid. Down in the comment section one of the commenters got rather nasty and belligerent about using citric acid and how the Soap Queen's post was "rubbish" (I noticed in her several comments that not once did she ever offer any credentials, scientific proof, etc, or anything that would give her point credibility :roll::roll:). Anyway, Anne Marie said that they were aware of this and, therefore, added the citric acid at trace which lowered the ph. Anyway, I wondered if anyone had seen this or had any comments on it- all in the spirit of learning :)
Cheers!
Anna Marie
 
Adding citric acid to any soap, even at trace, will give you free fats and trisodium citrate. Period. All you're doing is creating a chelator and adding more superfat. That's not to say that adding citric acid can't be beneficial--trisodium citrate will make it easier to rinse the soap out of your hair even in hard water. It's just the claim that it lowers the pH is not held up by science. (Citric acid is often used the neutralize liquid soaps, but if you add too much it gets cloudy because suddenly it's superfatted. Same deal with bar soaps, only you don't have the handy visual indicator.)
 
Adding citric acid to any soap, even at trace, will give you free fats and trisodium citrate. Period. All you're doing is creating a chelator and adding more superfat. That's not to say that adding citric acid can't be beneficial--trisodium citrate will make it easier to rinse the soap out of your hair even in hard water. It's just the claim that it lowers the pH is not held up by science. (Citric acid is often used the neutralize liquid soaps, but if you add too much it gets cloudy because suddenly it's superfatted. Same deal with bar soaps, only you don't have the handy visual indicator.)

Thank you for chiming in! Is there a source that I can read about this further?
Cheers!
Anna Marie
 
They don't make a point of the trisodium citrate being a chelator, but most liquid soapmaking books will cover what happens when you add citric acid to soap in their section on neutralizing the excess lye. I have Catherine Failor's book, Making Natural Liquid Soaps. It's the same chemical reactions, just with potassium instead of sodium.
 
To increase conditioning properties in your soap you can add citric acid to your water -before adding lye. 1gr citric acid need 0.6 gr NaOH to create height conditioning citrals. It give you final soap more shiny look and soft feeling on your skin and hair.
 
I agree with StarDancer. When you add a simple acid such as citric acid to a saponifying soap batter, the lye suddenly gets a choice. It can break apart the fats and react with the fatty acids to make soap or it can react with the citric acid to make sodium citrate. Citric acid gets first dibs every time because it's a far, far easier and simpler chemical reaction. If citric acid is added to a CP soap batter without any other changes to the recipe, the soap will have a higher superfat, but the pH will be the same as if the citric acid had never been added. (I can explain the reasons why, but it's a long answer that I need to write up for another time.) A soapmaker can either deal with the consequences of adding citric acid by adding the extra lye needed for the citric acid reaction, or by adding sodium citrate not citric acid to the soap batter, or by hot processing the soap and adding citric acid after the cook.

"...Hot-process soapmakers can add fatty acids (or even acetic or citric acid) to the finished soap before pressing it into the molds. Cold-process soapmakers do not have this luxury. If you add any acid to the raw soap, it will react instantly with the caustic soda [another name for sodium hydroxide, NaOH], resulting in an expensive and wasteful version of lye discounting. There will be unsaponified oil in the finished soap, but it will be just as alkaline as if you had added no acid at all. Any soap, be it a commodity or handcrafted product, made by the cold- or hot-process method, can only be acidified after saponification is complete..." Dunn, K. Scientific Soapmaking. pg 229. Comment in brackets [ ] is mine.

Hope this helps!
 
Thank you DeeAnna and StarDancer! It is good to get a clearer picture of what's going on backed up with scientific data and credentials. There is so much inaccurate info put on the internet that you really have to filter everything! I appreciate the time both of you gave to answering my query :)
Cheers!
Anna Marie
 
DeeAnna, thanks for that explanation. I have asked earlier if I could add the citric acid after the cook in hot process, however I was told that even then, it would cause the lye to "unsaponify"; leaving me with an oily mess. Based on your comment, would you agree with this statement, or could one add the citric acid after the cook to help with lowering pH?
I am only asking because I would very much like to find a shampoo bar that works for me, but as of yet, all the recipes have fallen short. Hair is either oily, straw-like or frizzy; even with an acid rinse. I'm about to give up for a sulfate-free shampoo, that hopefully won't make my hair fall out.
Thanks!
 
Shampoo soap will react with your hair better, but it was not happened right away. Everybody different. No universal shampoo formulation. One of my friends ending to make 35 recipes of shampoo soaps before she found her perfect one. For some people the best high cleaning shampoo, for other like this 0 cleaning the best. Some one love broccoli and mustard oils in them shampoos, some one lanolin, some one silk, clay, Shea butter, bees wax. It's not only about PH. Did you try simple castile on your hair? For my best shampoo bar difference ending to be in Lactic and Citric acid aded to water and Silk amino acid at the end. Don't give up
 
DeeAnna-why would it make a difference adding the citric acid to hp after the cook? For liquid soaps we know that the lye will break from the salt with the fatty acids to react with citric acid even though it's being added after the soap is cooked through saponification.
 
This discussion is so interesting. My mom would also buy Ivory because one of us had sensitive skin (it might have been my dad?). I hated the smell, but for some reason I thought this is what unscented soap smelled like. Even as a child I figured it should be unscented for sensitive skins, right?

I was so pleasantly surprised the first time I made unscented soap, that it did not smell like Ivory! I am laughing at my naivety now.

Going back to the shampoo bars, am I glad these work for me so well! I am not even using ACV rinse. I do not use commercial conditioner either. I have been working on a pre-shampoo hair conditioning oil. It looks like between these two things (shampoo bars and pre-shampoo conditioning oil) I will never need commercial hair products again. I do not want to bash commercial products (I think Dr Bronners is real soap and pretty good) but this gives me a sense of pride and autonomy. And, my hair is looking and feeling better, is that great or what?

I think I am allergic to something in Dr. Bronner's. Every time I have tried to use it I start breaking out.
 
"...why would it make a difference adding the citric acid to hp after the cook?..."

I should have qualified this; I was tired after a long day and didn't think things through as carefully as I usually do when I write about stuff like this. My apologies.

There are covalent molecules and ionic molecules. A fat molecule is pretty much covalent, meaning it would prefer to remain stable and intact for the most part without a lot of coaxing. A sodium hydroxide molecule is strongly ionic, meaning it will split apart into Na+ (sodium ion) and OH- (hydroxide ion) given only the tiniest bit of encouragement. A potassium hydroxide molecule is likewise strongly ionic. Soap is somewhere in between -- it has some ionic and some covalent characteristics from both of its parents.

The sodium (or potassium) end of a soap molecule is the ionic part. Given the right conditions, this ion will unhitch itself from the fatty acid part of a soap molecule fairly easily. The old soap makers knew this -- they would make a harder soap out of a soft KOH soap by adding lots of salt (NaCl, table salt) to a simmering water-and-soap solution and let it cook for awhile. Some of the Na+ from the salt would replace the K+ to make a harder sodium soap. The point to keep in mind is that this replacement reaction is not complete -- only some of the finished soap ends up being sodium soap. If the soapmaker wanted a 100% sodium soap, then they had to start with a sodium lye, not potassium lye.

(edit) Adding an acid to a finished soap is somewhat different than adding the same acid to a saponifying soap batter. The soap has to break apart first before the errant sodium ion can react with the acid, and that takes a bit more encouragement due to the more covalent nature of soap. (end edit) Adding acid to a finished soap can cause the soap to un-saponify to some degree given the right conditions. The rate of this un-saponification reaction depends on the strength of the acid, the amount added, as well as other variables such as time, water content, temperature, pressure, etc. Pure fatty acids are produced in industry and the lab by making a soap and then unsaponifying it with a strong acid such as nitric, hydrochloric, or sulfuric. When the resulting salt is washed out of the mixture -- voila -- you end up with just the fatty acids.

The success of adding an acid to an HP soap without altering the soap ~too much~ will depend on the type of acid (a weak acid is better), the amount added (less is better), the water content (lower is better), and the temperature (cooler is better). The reason why a soapmaker could have reasonable success with adding some citric acid to a solid soap but have a failure adding it to a liquid soap is likely the different water content of the two.

Okay, that said, would I personally add an acid to a shampoo soap? Nope.

Even though I think adding a ~small~ amount of citric acid to a finished solid soap might work okay in the short term, I would be concerned about gradual degradation over time. If one wants to use a shampoo bar made with lye soap, then one needs to quit expecting one product to do everything -- clean, lower the pH, and condition -- and instead look at using an acidic rinse with or without a separate conditioner.

After I shampoo with a 'poo bar, I squeeze out a dab of homemade conditioner, mix a small pinch of citric acid into the conditioner, work the mixture into my hair, leave on for 15-30 seconds, and rinse. A citric or vinegar rinse with just water didn't work well for my fine, wavy hair, but this mixture does. If a low pH in shampoo is an absolute requirement, then use surfactants with a lower intrinsic pH. They will be more chemically stable and reliable.

So now I've turned what most people want to be a black-and-white issue into a big blob of varying shades of gray. Chemistry is that way ... a lot.
 
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Its surprising how much little variation can affect the outcome. My first shampoo bars are made exactly to the recipe except for the addition of egg yolk, my second batch I had to replace part of the avocado oil with sunflower oil and I can tell a difference. It doesn't lather as good and the bars seem softer.
I'll not deviate from the original recipe again but I do recommend adding egg yolk, it makes a really nice thick lather.

At what point do you add the egg yoke?
 

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