Martin Suenson. Titration of soap and soap making ingredients.

The method of titrating can be used for several purposes.

Check that a CP soap or a cream soap paste is lye-free.
Calculate the amount of neutralizer needed to neutralize a batch of liquid soap paste.
If you make your cream soap paste without superfat in the first phase, it just takes a
tiny error in weighing (or KOH a bit purer than you thought) to leave a bit of residual
lye and the paste will continue to show pink with Phenolphthalein. Rather than chuck
the batch, measure the amount of residual lye and calculate the amount of additional
stearic acid needed to make a neutral paste.
Measure the purity of NaOH or KOH. Particularly for KOH, that can be useful if you
have had KOH sitting on the shelf for some time and it has absorbed water.
Measure that SAP value of an oil exactly.
For the full range of possibilities, I refer you to the book Scientific Soapmaking by Kevin
Dunn.
Being European, I use grams. If you share the view of Sally Brown from The Peanuts on the
metric system: A centimeter? If any centimeters come crawling into this room, I'll step on
'em!, you can convert to pounds, ounces, fathoms per fortnight or whatever units you like.

Weighing

In the following, you need to distinguish between weighing analytically and weighing
synthetically.

Weighing analytically, it is not necessary to hit the target weight precisely, but you need to
know the exact weight. If you need to weigh 10 g of something analytically, 10 g + or minus
10 or 20% is fine, provided that you note the exact quantity that you actually weighed off.

Weighing synthetically you must hit the target weight within the accuracy of your scales (and
the accuracy of the scales must be sufficiently fine). A balance that is accurate to 0.01 g can
be used to weigh down to 1 g with a 1% error for example.

Weighing synthetically, I often weigh reverse: If I need to weigh 100.50 grams of say
NaOH, I charge a beaker or bowl with somewhat more than 100.50 grams, say 120 g. I
place the beaker or bowl on the balance and tare the balance. I then scoop (or pipette for
liquids) from the bowl to the final recipient until the balance reads -120.50 g. The advantage
is that if I overshoot, say I have too much NaOH on the last scoop, I can return some NaOH
back to the bowl without contaminating the NaOH. When finished, I have pure NaOH in the
bowl and can return it to my NaOH container. If you weigh directly into the final recipient that
maybe already contains other things and you overshoot, you cannot go back.

Notation and habits

I also use the notation ppt as parts per thousand and I only use concentration as weight
per weight so a 250 ppt NaOH solution has 250 g of NaOH per 1000 g of solution.

Since I use the same method for checking my solid soaps, checking cream soap pastes and
neutralizing liquid soap pastes, I consistently express excess lye as ppt NaOH equivalent.
1.4 ppt KOH residual lye is equivalent to 1 ppt NaOH. I use 1 ppt residual NaOH as the cut-
off point for my CP soaps. Above that I dont release them for consumption. To check a
cream or liquid soap on a similar basis, the residual KOH should be below 1.4 ppt, but since
I always convert to NaOH equivalent basis, the check point remains 1 ppt.

I also keep a tight, dated, journal, noting down what I have done, the weights involved etc.

Equipment and materials

You will need a good balance, accurate to 0.01 g. A balance that weighs up to 200 g is fine.
Beware of really cheap balances. They may display 0.01 g, but they are unstable and drift. A
lot!

I have been fortunate and found a gem on Ebay, a used high end Japanese balance that
weighs to 3400 g with a readability of 0.01 g so I can do most things with just one balance.
However, I have been told that the Myweigh iBalance series, say iBalance 201 is a good
compromise price/quality and it will set you back some 80-90$. It will also allow you to weigh
small quantities like essential oils precisely, so not a bad investment.

Three dropper bottles to keep the solution of 1% Phenolphthalein in ethanol, the 5 ppt citric
acid solutions and the 5 ppt KOH solution. You can also use normal bottles and use a
transfer pipette. In that case, you should use reverse weighing, taring the balance with the
solution bottle and note the weight lost after the titration.

A small bottle. I use small (200 cc) conical Pyrex bottles called Erlenmeyer flasks. The
advantage with Pyrex is that you can heat it directly and save time.


You need five ingredients.

Pure alcohol (90% or higher)
Citric acid powder
KOH
Demineralized water.
A solution of 1% Phenolphthalein in ethanol.

I use denatured alcohol. Since the alcohol will not go into a finished product, you do not
need the special grades for cosmetics and standard household cleaning alcohol is cheaper.
However, it is important that the alcohol does not contain significant amounts of acids. Some
denaturing agents are acidic. The alcohol I use is denatured with MEK, isopropanol and
butyl alcohol. It is the standard household cleaning or burning alcohol. Normally this works
fine, but I have had bottles of alcohol that were a bit acidic and I have not used them. You
will check that as part of the titration procedure.

I use working solutions of KOH and of citric acid. For titrating soaps, I use the 5 ppt citric
acid solution. Since it is difficult to weigh 5 grams of citric acid and 999.5 grams of water with
an accuracy of say 1%, I make a working solution of 500 ppt citric acid, dilute it to make a 50
ppt citric acid solution and dilute this to make a 5 ppt citric acid solution. When my 5 ppt
solution is used up, I make more from the 50 ppt mother solution and when that is used up,
back to the 500 ppt solution.

Citric acid solutions are stable. They will not react chemically or absorb water, so once
made, they can be used for a long time. The KOH solutions will absorb water, react with
carbon dioxide from the air etc. so their real KOH concentration will change over time. That
doesnt matter since I dont use the precise KOH concentration and keeping them in will
stoppered bottles, I have kept mine for quite some time.

Note that citric acid is sold in two forms: It can exist either in an anhydrous (water-free) form
or as a monohydrate. It is important that you know which form you have. If you are in doubt, .
the monohydrate can be converted to the anhydrous form by heating above 78 C so give it
a good heating in a 90 C oven, turning in the powder from time to time.

Preparation of working solutions

Making X g of 500 ppt citric acid solution from anhydrous citric acid.

Weigh analytically X/2 grams of citric acid into the recipient bottle. Weigh synthetically X/2
grams of water into the recipient bottle.

Making X g of 500 ppt citric acid solution from monohydrate citric acid.

Weigh analytically 0.5469 * X grams of citric acid into the recipient bottle. Weigh synthetically
X*0.4143 grams of water into the recipient bottle.

Making X grams of 50 ppt citric acid solution.

Weigh analytically X/10 grams of 500 ppt citric acid into the recipient bottle. Weigh
synthetically X/90 grams of water into the recipient bottle.

Making X grams of 5 ppt citric acid solution.

Weigh analytically X/10 grams of 50 ppt citric acid into the recipient bottle. Weigh
synthetically X/90 grams of water into the recipient bottle.

Similarly, I make working solution of KOH of 500 ppt, 50 ppt and 5 ppt.

Titrating a sample of soap.

Weigh approximately 50 g of alcohol into the small bottle.

Add 3-4 drops of Phenolphthalein.

Add 5 ppt KOH solution, drop by drop, until the content is ever so slightly pink, held against a
piece of white paper. If it takes significantly more than 2-3 drops, your alcohol contains acidic
components and is not well suited for the task at hand.

Place the bottle on the scales and tare the scales.

Weigh analytically circa 1 2 g of soap or soap paste into the bottle. Note the weight of the
soap added.

Wait until the soap has dissolved completely. Here it can be helpful to heat the bottle a bit.
Avoid open flames since alcohol vapors can catch fire. Placing the bottle in a bowl of hot
water will do the trick. The alcohol may boil a bit, but it should not be violent boiling.

Replace the bottle on the scale and re-tare to compensate for any loss of alcohol.

If you have completely neutralized soap, the solution will have lost its pink tint and there is
no reason to go further, you can note nil as residual lye.
If the solution became a deeper pink after the soap was added, there is residual lye. In that
case, add drops of 5 ppt citric acid solution until the solution is just pink again or colorless.
Swirl the bottle well between each drop added to avoid overshooting.

When the solution has become very slightly pink or colorless, note the weight of the citric
acid solution added.

The calculation is simple.

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(detailed explanation below for the chemically minded)

I use this for all my finished products. I do not release a soap for consumption unless it
contains less than 1 ppt NaOH equivalent. I adapted this methodology because pH
measurements of solid soaps are impractical, for low water content soaps like cream and
liquid , pH measurements are no really reliable and some soaps, particularly cream soaps,
show high pH although they are completely neutralized. .

I also use this methodology to neutralize liquid soap pastes where I deliberately overdose
the lye and cream soap pastes where I have mis-measured ingredients.

To calculate the amount of neutralizer:

For citric acid:

( ) ( )

For stearic acid

( ) ( )

Example.

Liquid soap paste sample: 1.82 g
Grams of 5 ppt citric acid added to neutralize: 1.25 g
Residual lye: 2.14 ppt NaOH equivalent

Size of paste batch: 1500 g
Citric acid needed to neutralize batch: 5.15 g.


Calculation explanation.

X grams of 5 ppt CA solution contains X *5/1000 g of CA = X*5/(1000*192) moles of NaOH.

Since one mole of citric acid will neutralize 3 moles of lye, this is equivalent to

X*5*3/( 1000*192) moles of OH- or X*5*3*40/(1000*192) g NaOH or
1000* X*5*3*40/(1000*192) ppt NaOH = X*3.125