Scientific Soapmaking

Kevin M. Dunn

Summer 2008

$Revision: 1.1 $

1
Acknowledgements
Copyright © 2008 Kevin M. Dunn

Acknowledgements

• Mike Lawson/Columbus Foods

2
Why Teach Soapmaking?

Why Teach Soapmaking?

• Thriving cottage industry

Why Teach Soapmaking?

Why Teach Soapmaking?

• Thriving cottage industry

• Soapmakers generally come from a cooking/craft background
Why Teach Soapmaking?

Why Teach Soapmaking?

• Thriving cottage industry

• Soapmakers generally come from a cooking/craft background
• Soapmakers are interested in the chemistry of their craft
Why Teach Soapmaking?

Why Teach Soapmaking?

• Thriving cottage industry

• Soapmakers generally come from a cooking/craft background
• Soapmakers are interested in the chemistry of their craft
• If gen-ed students can imagine themselves as soapmakers, they
will become interested in the chemistry
Why Teach Soapmaking?

Why Teach Soapmaking?

• Thriving cottage industry

• Soapmakers generally come from a cooking/craft background
• Soapmakers are interested in the chemistry of their craft
• If gen-ed students can imagine themselves as soapmakers, they
will become interested in the chemistry
• Experiments are designed to solve real-world problems
Let’s Make Soap

Let’s Make Soap

• 100.00 g Delight (an oil blend)

• 28.80 g Lye (500 ppt NaOH)
Let’s Make Soap

Let’s Make Soap

• 100.00 g Delight (an oil blend)

• 28.80 g Lye (500 ppt NaOH)
• But how are we to weigh?
Weighing Synthetically

Weighing Synthetically

• Place cup of water on balance

• Press tare button
• Use pipet to transfer water to second cup
• What if we overshoot?
• What about the water in the pipet?
Let’s Make Soap

Let’s Make Soap

• 100.00 g Delight (already weighed)

• 28.80 g Lye (weigh synthetically into oil)
Let’s Make Soap

Let’s Make Soap

• 100.00 g Delight (already weighed)

• 28.80 g Lye (weigh synthetically into oil)
• Shake vigorously for 60 seconds
• Pour into styrofoam cup
• Measure temperature
Oil and Water

Oil and Water

Glyceryl Trilaurate

Glyceryl Trilaurate

O O

O O
Saponification

Saponification
Saponification

Saponification
NaOH O

O O

O O

NaOH NaOH

↓
O

Na
O

OH

OH OH

O
Na

O
O
Na

O
Saponification

Saponification

• Oil + 3 NaOH = Glycerol + 3 Soap

• Each molecule of oil requires 3 molecules of NaOH
Saponification

Saponification

• Oil + 3 NaOH = Glycerol + 3 Soap

• Each molecule of oil requires 3 molecules of NaOH
• What happens if you provide only 2 molecules of NaOH?
Saponification

Saponification

• Oil + 3 NaOH = Glycerol + 3 Soap

• Each molecule of oil requires 3 molecules of NaOH
• What happens if you provide only 2 molecules of NaOH?
• What happens if you provide 4 molecules of NaOH?
Saponification

Saponification

• Oil + 3 NaOH = Glycerol + 3 Soap

• Each molecule of oil requires 3 molecules of NaOH
• What happens if you provide only 2 molecules of NaOH?
• What happens if you provide 4 molecules of NaOH?
• We measure oil and NaOH by weight, not by molecules
Saponification

Saponification

• Oil + 3 NaOH = Glycerol + 3 Soap

• Each molecule of oil requires 3 molecules of NaOH
• What happens if you provide only 2 molecules of NaOH?
• What happens if you provide 4 molecules of NaOH?
• We measure oil and NaOH by weight, not by molecules
• Each gram of oil should require a specific weight of NaOH for
complete saponification
Saponification Value

Saponification Value
Theoretical saponification value of glyceryl tristearate:

1 mol Oil 3 mol KOH 56 g KOH

µ ¶µ ¶µ ¶
? g KOH = 1000 g Oil
890 g Oil 1 mol Oil 1 mol KOH
= 189 ppt KOH

Experimental saponification value of tallow: 190-200 ppt

Saponification Value

Saponification Value
Theoretical sodium saponification value of glyceryl tristearate:

1 mol Oil 3 mol NaOH 40 g NaOH

µ ¶µ ¶µ ¶
? g NaOH = 1000 g Oil
890 g Oil 1 mol Oil 1 mol NaOH
= 135 ppt NaOH

Experimental sodium saponification value of tallow: 135-143 ppt

Saponification Value

Saponification Value

• SV = weight (mg) of KOH needed to saponify 1 g of oil

• SSV = weight (mg) of NaOH needed to saponify 1 g of oil
• AR = weight (mg) of alkali actually used to saponify 1 g of oil
Saponification Value

Saponification Value

• SV = weight (mg) of KOH needed to saponify 1 g of oil

• SSV = weight (mg) of NaOH needed to saponify 1 g of oil
• AR = weight (mg) of alkali actually used to saponify 1 g of oil
• SV of Delight is 211.5 ppt KOH
• SSV of Delight is 150.8 ppt NaOH
Saponification Value

Saponification Value

• SV = weight (mg) of KOH needed to saponify 1 g of oil

• SSV = weight (mg) of NaOH needed to saponify 1 g of oil
• AR = weight (mg) of alkali actually used to saponify 1 g of oil
• SV of Delight is 211.5 ppt KOH
• SSV of Delight is 150.8 ppt NaOH
• Since Lye is 500 ppt NaOH, we have used an AR of 144 ppt
NaOH
• Why?
Lye Discounting

Lye Discounting
Total Alkali (ppt NaOH)

Total Alkali (ppt NaOH)

1 Day Old 11 Weeks Old

6 6
4 4
2 2
0 0

140 144 148 152 156 140 144 148 152 156
Alkali Ratio (ppt NaOH) Alkali Ratio (ppt NaOH)
Checking In

Checking In
What are the temperature and consistency of your soap?
Measurable quantities

Measurable Quantities

• Finished soap
• Total alkali
• Moisture content
• Hardness
Measurable quantities

Measurable Quantities

• Finished soap
• Total alkali
• Moisture content
• Hardness

• Raw materials
• Saponification value
• Lye concentration
• Free fatty acid
Free Fatty Acid

Free Fatty Acid

• Real-world oils may contain “free” fatty acid

• How can we measure it?
Titration

Titration
Titration

Titration

• Add 50 mL ethanol to Erlenmeyer flask

• Add 4-5 drops 1% phenolphthalein
• Add 4.18 ppt KOH until solution is faintly pink
• Solution is now “neutral”
Weighing Analytically

Weighing Analytically

• Place coconut oil bottle on balance

• Press tare button
• Transfer 30-40 drops of oil to Erlenmeyer flask
• Replace oil bottle on balance and read weight
Gravimetric Titration

Gravimetric Titration

• Place 4.18 ppt KOH bottle on balance

• Press tare button
• Add KOH to Erlenmeyer flask until faintly pink
• Replace KOH bottle on balance and read weight
Acid Value

Acid Value
YY.YY g Std 4.ZZ g KOH
µ ¶µ ¶
? g KOH = 1000 g Oil
1.XX g Oil 1000 g Std
YY.YY
µ ¶
= 4.ZZ ppt KOH
1.XX

• What is the Acid Value of your oil?

Acid Value

Acid Value
YY.YY g Std 4.ZZ g KOH
µ ¶µ ¶
? g KOH = 1000 g Oil
1.XX g Oil 1000 g Std
YY.YY
µ ¶
= 4.ZZ ppt KOH
1.XX

• What is the Acid Value of your oil?

• Why did we get different values?
Free Fatty Acid

Free Fatty Acid

• Free Lauric Acid = 3.570 AV

• What is the Free Lauric Acid content of your oil?
Free Fatty Acid

Free Fatty Acid

• Free Lauric Acid = 3.570 AV

• What is the Free Lauric Acid content of your oil?
• Which oil would saponify quicker?
Extended Investigations

Extended Investigations

• Dreaded Orange Spots

Extended Investigations

Extended Investigations

• Dreaded Orange Spots

• Seizing
Extended Investigations

Extended Investigations

• Dreaded Orange Spots

• Seizing
• Superfatting vs Discounting
Extended Investigations

Extended Investigations

• Dreaded Orange Spots

• Seizing
• Superfatting vs Discounting
• The Water “Discount”
Lye Concentration

Lye Concentration

• What is the normal, correct, or standard lye concentration?

Lye Concentration

Lye Concentration

• What is the normal, correct, or standard lye concentration?

• Ann Bramson, Soap: Making it, Enjoying it (1972)
25-27%, 26% average
Lye Concentration

Lye Concentration

• What is the normal, correct, or standard lye concentration?

• Ann Bramson, Soap: Making it, Enjoying it (1972)
25-27%, 26% average
• Susan Cavitch, The Soapmaker’s Companion (1997)
26-29%, 27% average
Lye Concentration

Lye Concentration

• What is the normal, correct, or standard lye concentration?

• Ann Bramson, Soap: Making it, Enjoying it (1972)
25-27%, 26% average
• Susan Cavitch, The Soapmaker’s Companion (1997)
26-29%, 27% average
• Robert McDaniel, Essentially Soap (2000)
33-38%, 34% average
Lye Concentration

Lye Concentration

• What is the normal, correct, or standard lye concentration?

• Ann Bramson, Soap: Making it, Enjoying it (1972)
25-27%, 26% average
• Susan Cavitch, The Soapmaker’s Companion (1997)
26-29%, 27% average
• Robert McDaniel, Essentially Soap (2000)
33-38%, 34% average
• Anne Watson, Smart Soapmaking (2007)
30-37%, 33% average
The Soap Formula

The Soap Formula

• Lye = 50.00% NaOH, 50.00% distilled water

• Coconut1000Lye348
Coconut1000Lye348Aq174
Coconut1000Lye348Aq348
The Soap Formula

The Soap Formula

• Lye = 50.00% NaOH, 50.00% distilled water

• Coconut1000Lye348 (50.00% NaOH “Low-Water”)
Coconut1000Lye348Aq174 (33.33% NaOH “Medium-Water”)
Coconut1000Lye348Aq348 (25.00% NaOH “High-Water”)
Processing Soap

Processing Soap

• 100 g oil + water + lye into 500 mL plastic bottle

• Shaken 15 sec on a paint shaker
• Gently swirled until trace
• Poured into an Upland experimental mold
• Incubated at 140◦F for 4 hours
Questions

Questions

• What do we want to know?

Questions

Questions

• What do we want to know?

• Does the initial water portion affect the final moisture content?
• Does it affect the curing time?
• Does it effect the hardness of the soap?
• Is there a danger of separation?
What Can We Measure?

What Can We Measure?

• Moisture content of soap over time

• Hardness of soap over time

• Alkalinity of soap over time

• Separation of soap
What Can We Measure?

What Can We Measure?

• Moisture content of soap over time

Initially from formula, follow weight loss over time
• Hardness of soap over time

• Alkalinity of soap over time

• Separation of soap
What Can We Measure?

What Can We Measure?

• Moisture content of soap over time

Initially from formula, follow weight loss over time
• Hardness of soap over time
Soil penetrometer
• Alkalinity of soap over time

• Separation of soap
What Can We Measure?

What Can We Measure?

• Moisture content of soap over time

Initially from formula, follow weight loss over time
• Hardness of soap over time
Soil penetrometer
• Alkalinity of soap over time
Titration with 5 ppt citric acid
• Separation of soap
What Can We Measure?

What Can We Measure?

• Moisture content of soap over time

Initially from formula, follow weight loss over time
• Hardness of soap over time
Soil penetrometer
• Alkalinity of soap over time
Titration with 5 ppt citric acid
• Separation of soap
Hardness of top and bottom of bar
Alkalinity of top and bottom of bar
Moisture

Moisture

• Coconut1000Lye348Aq348
• Total weight 1696 g
• Water weight (174 + 348) = 522 g
• Initial moisture = (522/1696) = 0.308 = 30.8% = 308 ppt
Moisture

Moisture

• Coconut1000Lye348Aq348
• Total weight 1696 g
• Water weight (174 + 348) = 522 g
• Initial moisture = (522/1696) = 0.308 = 30.8% = 308 ppt
• Initial bar weight 141.32 g; Final weight 113.17 g
• Weight loss (28.15/141.32) = 0.199 = 19.9% = 199 ppt
• Final moisture = 308 - 199 = 109 ppt
Penetrometer

Penetrometer

Smaller foot used for hard soaps.

Titration

Titration

How many grams of acid required to titrate a given weight of

soap?
Total Alkali

Total Alkali
Y.YY g Acid 5 g H3Cit
µ ¶µ ¶
? g NaOH = 1000 g Soap
¶ µ g Soap 1000
1.XX ¶ µ g Acid
1 mol H3Cit 3 mol NaOH 40.00 g NaOH
µ ¶

µ g H3¶Cit 1 mol H3Cit

192.12 1 mol NaOH
Y.YY
= 3.123 ppt NaOH
1.XX
Palm Oil

Palm Oil

• Low, Medium, and High Water soaps

• Identical in other respects
• Moisture and hardness measured weekly for 60 days
• Alkalinity measured at beginning and end
Palm Oil

Palm Oil
Batch Code Moisture/ppt Alkali/ppt NaOH
KMD2007.12.27 Initial Final Initial Final
Top Bottom Top Bottom
A Palm1000 Lye286 111 54 1.8 4.9 0.3 0.9
B Palm1000 Lye286Aq143 200 60 1.8 1.4 -1.7 -0.2
C Palm1000 Lye286Aq286 273 74 0.5 0.3 -1.7 -0.1

Moisture Hardness
300 A 10
B
C

kg/scm
200
ppt

5
100

0 0
0 30 60 0 30 60
Days Days
Coconut Oil

Coconut Oil
Batch Code Moisture/ppt Alkali/ppt NaOH
KMD2008.1.8 Initial Final Initial Final
Top Bottom Top Bottom
D Coconut1000Lye348 129 41 0.4 0.5 -0.6 -0.3
E Coconut1000Lye348 Aq174 229 88 -0.1 -0.2 -1.7 -1.0
F Coconut1000Lye348 Aq348 308 109 0.1 0.2 -1.8 -0.4

Moisture Hardness
300 D 10
E
F

kg/scm
200
ppt

5
100

0 0
0 30 60 0 30 60
Days Days
Olive Oil

Olive Oil

• Medium and high water soaps separated

• What can I do to accelerate trace?
Olive Oil

Olive Oil

• Medium and high water soaps separated.

• What can I do to accelerate trace? Add clove oil.
Olive Oil

Olive Oil
Batch Code Moisture/ppt Alkali/ppt NaOH
KMD2008 Initial Final Initial Final
Top Bottom Top Bottom
1.7A Olive1000Lye264 104 36 0.3 0.2 -3.2 -0.4
3.5A Olive990 Clove10 Lye259 103 43 -0.4 -0.7 -0.7 -0.7
3.5B Olive990 Clove10 Lye259 Aq130 187 61 -0.4 -0.4 -0.8 -0.7
3.5C Olive990 Clove10 Lye260 Aq260 256 67 -0.7 6.2 -1.1 -0.2

Moisture Hardness
300 1.7A 10
3.5A
3.5B

kg/scm
200
3.5C
ppt

5
100

0 0
0 30 60 0 30 60
Days Days
Delight

Delight

• Delight = Olive390Palm280Coconut280Castor50
Delight

Delight
Batch Code Moisture/ppt Alkali/ppt NaOH
KMD2008.2.17 Initial Final Initial Final
Top Bottom Top Bottom
A Delight1000Lye288 112 48 -0.2 0.2 -1.0 -0.4
B Delight1000Lye288 Aq144 201 89 -0.4 0.3 -3.1 -0.9
C Delight1000Lye288 Aq288 274 104 -0.9 0.9 -3.7 -1.3

Moisture Hardness
300 A 10
B
C

kg/scm
200
ppt

5
100

0 0
0 30 60 0 30 60
Days Days
Delight

Gel Phase

• Delight1000Lye288Aq50
Tmax 151◦F after 180 minutes
Never reached gel phase
Total alkali: 1.3 ppt (top), -0.2 ppt (bottom)
Delight

Gel Phase

• Delight1000Lye288Aq50
Tmax 151◦F after 180 minutes
Never reached gel phase
Total alkali: 1.3 ppt (top), -0.2 ppt (bottom)
• Delight1000Lye288Aq100
Tmax 156◦F after 165 minutes
“Very dry vaseline” at 145◦F after 210 minutes
Total alkali: 0.5 ppt (top), 0.1 ppt (bottom)
Delight

Gel Phase

• Delight1000Lye288Aq200
“Vaseline” with beads of oil at 151◦F after 195 minutes
Tmax 154◦F after 210 minutes
Total alkali: -0.2 ppt (top), 4.0 ppt (bottom)
Delight

Gel Phase

• Delight1000Lye288Aq200
“Vaseline” with beads of oil at 151◦F after 195 minutes
Tmax 154◦F after 210 minutes
Total alkali: -0.2 ppt (top), 4.0 ppt (bottom)
• Delight1000Lye288Aq250
Tmax 156◦F after 165 minutes
“Jello” with layer of oil at 156◦F after 180 minutes
Total alkali: -0.2 ppt (top), 8.7 ppt (bottom)
Conclusions

Conclusions

• I encountered no problems with lye concentrations up to 50%.

Conclusions

Conclusions

• I encountered no problems with lye concentrations up to 50%.

• High-water Olive and Delight soaps separated.
Conclusions

Conclusions

• I encountered no problems with lye concentrations up to 50%.

• High-water Olive and Delight soaps separated.
• More water delays trace.
Conclusions

Conclusions

• I encountered no problems with lye concentrations up to 50%.

• High-water Olive and Delight soaps separated.
• More water delays trace.
• Low-water soaps start out hard; medium- and high-water soaps
may or may not “catch up.”
Conclusions

Conclusions

• I encountered no problems with lye concentrations up to 50%.

• High-water Olive and Delight soaps separated.
• More water delays trace.
• Low-water soaps start out hard; medium- and high-water soaps
may or may not “catch up.”
• “Gel phase” was observed only for medium- and high-water
soaps. Since all soaps were fully saponified, gel phase is not es-
sential. In fact, when separation occurred, it always happened
during gel phase.
Conclusions

Conclusions

• I encountered no problems with lye concentrations up to 50%.

• High-water Olive and Delight soaps separated.
• More water delays trace.
• Low-water soaps start out hard; medium- and high-water soaps
may or may not “catch up.”
• “Gel phase” was observed only for medium- and high-water
soaps. Since all soaps were fully saponified, gel phase is not es-
sential. In fact, when separation occurred, it always happened
during gel phase.
• Saponification and curing are two separate processes.
Recommendations

Recommendations

• Decide on a standard lye concentration and always use that

when making soap.
Recommendations

Recommendations

• Decide on a standard lye concentration and always use that

when making soap.
• You can always add extra (water, milk, etc.) to delay trace or
decrease initial hardness.
Recommendations

Recommendations

• Decide on a standard lye concentration and always use that

when making soap.
• You can always add extra (water, milk, etc.) to delay trace or
decrease initial hardness.
• If oil separates from the soap, try decreasing the amount of (wa-
ter, milk, etc.).
Recommendations

Recommendations

• Decide on a standard lye concentration and always use that

when making soap.
• You can always add extra (water, milk, etc.) to delay trace or
decrease initial hardness.
• If oil separates from the soap, try decreasing the amount of (wa-
ter, milk, etc.).
• Be aware that soaps may continue to lose moisture, even after
60 days.
Recommendations

Recommendations

• Decide on a standard lye concentration and always use that

when making soap.
• You can always add extra (water, milk, etc.) to delay trace or
decrease initial hardness.
• If oil separates from the soap, try decreasing the amount of (wa-
ter, milk, etc.).
• Be aware that soaps may continue to lose moisture, even after
60 days.
• Make lye only from NaOH and water.
Checking In

Checking In
What are the temperature and consistency of your soap?
Summary

Why Am I Teaching You to Teach

Soapmaking?

• There is a market for soapmaking instruction

Summary

Why Am I Teaching You to Teach

Soapmaking?

• There is a market for soapmaking instruction

• Soapmaking can motivate gen-ed students
Summary

Why Am I Teaching You to Teach

Soapmaking?

• There is a market for soapmaking instruction

• Soapmaking can motivate gen-ed students
• Online soapmaking communities are fraught with MSU
Summary

Why Am I Teaching You to Teach

Soapmaking?

• There is a market for soapmaking instruction

• Soapmaking can motivate gen-ed students
• Online soapmaking communities are fraught with MSU
• I’m lonely
Summary

Organizations

• The Handcrafted Soap Makers Guild (www.SoapGuiild.org)

• The Saponifier (www.Saponifier.com)
• Scientific Soapmaking (www.ScientificSoapmaking.com)