Time and Temperature in

Soapmaking

Kevin M. Dunn

Spring 2009

$Revision: 1.1 $

1
Time and Temperature
Copyright © 2009 Kevin M. Dunn

Time and Temperature

• What is the “gel phase?”

• Why and when does it appear?
• Is it good or bad for my soap?

2
Acknowledgements

Acknowledgements

• Mike Lawson/Columbus Foods

• Hampden-Sydney College
• John Campbell (NMR)
• Andrew Basinger (Temp Profiles)
• Tyler Bowman (Temp Profiles)
• Drake Huzek (Kinetics)
• Billy Eskridge (Kinetics)
• Matt Huff (IR)
Acknowledgements

Acknowledgements

• Proctor and Gamble (DSC and XRD)

• Jody Aiken
• Steve Sealschott
• David Bohlen
• Kassy Pelzel
• Pauline Vu
Saponification

Saponification

• Oil + 3 NaOH = Glycerol + 3 Soap

• How much NaOH is needed?
Sodium Saponification Value

Sodium Saponification Value

1 Day Old
Total Alkali (ppt NaOH)

140 144 148 152 156

Alkali Ratio (ppt NaOH)
Delight

Delight

• Delight1000 = Olive390Palm280Coconut280Castor50
Delight

Delight

• Delight1000 = Olive390Palm280Coconut280Castor50
• Lye = 50.00% NaOH, 50.00% distilled water
• SSV of Delight is 150.8 ppt NaOH
Delight

Delight

• Delight1000 = Olive390Palm280Coconut280Castor50
• Lye = 50.00% NaOH, 50.00% distilled water
• SSV of Delight is 150.8 ppt NaOH
• Delight1000Lye288
Delight

Delight

• Delight1000 = Olive390Palm280Coconut280Castor50
• Lye = 50.00% NaOH, 50.00% distilled water
• SSV of Delight is 150.8 ppt NaOH
• Delight1000Lye288
• 144/150.8 = 0.955, 4.5% lye 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
More Lyes

More Lyes

• Lye = 50.00% NaOH, 50.00% distilled water

More Lyes

More Lyes

• Lye = 50.00% NaOH, 50.00% distilled water

• Delight1000Lye288Aq0 (50.00% NaOH Lye)
Delight1000Lye288Aq72 (41.67% NaOH Lye)
Delight1000Lye288Aq144 (33.33% NaOH Lye)
Delight1000Lye288Aq216 (29.16% NaOH Lye)
Delight1000Lye288Aq288 (25.00% NaOH Lye)
More Lyes

More Lyes

• Lye = 50.00% NaOH, 50.00% distilled water

• Delight1000Lye288Aq0 (11.18% Water)
Delight1000Lye288Aq72 (15.88% Water)
Delight1000Lye288Aq144 (20.11% Water)
Delight1000Lye288Aq216 (23.93% Water)
Delight1000Lye288Aq288 (27.41% Water)
More Lyes

More Lyes

• Lye = 50.00% NaOH, 50.00% distilled water

• Delight1000Lye288Aq0 (Low-Water)
Delight1000Lye288Aq72
Delight1000Lye288Aq144 (Medium-Water)
Delight1000Lye288Aq216
Delight1000Lye288Aq288 (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 a nest of styrofoam cups
• Temperature recorded every 15 min for 4 hours
Phases

Phases

• Ice, water, steam

Phases

Phases

• Ice, water, steam

• Ice, cream, ice cream
Phases

Phases

• Ice, water, steam

• Ice, cream, ice cream
• Gel, sol (Jello)
Phases

Phases

• Ice, water, steam

• Ice, cream, ice cream
• Gel, sol (Jello)
• Sugar, water, honey
Phases

Phases

• Ice, water, steam

• Ice, cream, ice cream
• Gel, sol (Jello)
• Sugar, water, honey
• Flour, water, gravy
Phases

Phases

• Ice, water, steam

• Ice, cream, ice cream
• Gel, sol (Jello)
• Sugar, water, honey
• Flour, water, gravy
• Soap is more complex than any of these.
Phase Diagrams

Phase Diagram
Phase Diagrams

Where We Work
Phase Diagrams

Delight

Delight/Water Phases
100
neat (gel) 200
Temperature / oC

Temperature / oF
80
solid + neat 160
60
120
40
80
20 solid
40
0
10 15 20 25 30
% Water
Time and Temperature

Time and Temperature

40oC Starting Temperature

100
200
Temperature / oC

Temperature / oF
80
160
60
120
40
80
20
High-Water 40
0
0 50 100 150 200
Time / min
Time and Temperature

Time and Temperature

40oC Starting Temperature

100
200
Temperature / oC

Temperature / oF
80
160
60
120
40
80
20
Medium-Water
High-Water 40
0
0 50 100 150 200
Time / min
Time and Temperature

Time and Temperature

40oC Starting Temperature

100
200
Temperature / oC

Temperature / oF
80
160
60
120
40
Low-Water 80
20
Medium-Water
High-Water 40
0
0 50 100 150 200
Time / min
Temperature Profiles

Delight

Aq0 (Low-Water)
100
200
solid
Temperature / oC

Temperature / oF
80
160
60
120
40
hot 80
20
warm
cold 40
0
0 50 100 150 200
Time / min
Temperature Profiles

Delight

Aq72
100
neat 200
solid
Temperature / oC

Temperature / oF
80
160
60
120
40
hot 80
20
warm
cold 40
0
0 50 100 150 200
Time / min
Temperature Profiles

Delight

Aq144 (Medium-Water)
100
200
Temperature / oC

Temperature / oF
80 neat
160
solid
60
120
40
hot 80
20
warm
cold 40
0
0 50 100 150 200
Time / min
Temperature Profiles

Delight

Aq216
100
200
Temperature / oC

Temperature / oF
80
160
60 neat
solid
120
40
hot 80
20
warm
cold 40
0
0 50 100 150 200
Time / min
Temperature Profiles

Delight

Aq288 (High-Water)
100
200
Temperature / oC

Temperature / oF
80
160
60 neat
solid
120
40
hot 80
20
warm
cold 40
0
0 50 100 150 200
Time / min
So What?

So What?

• Is there a difference between soaps that gelled and those that

did not?
So What?

So What?

• Is there a difference between soaps that gelled and those that

did not?
• Compare Aq288 soaps processed at different initial tempera-
tures.
So What?

So What?

• Is there a difference between soaps that gelled and those that

did not?
• Compare Aq288 soaps processed at different initial tempera-
tures.
• Soaps had the same consistency.
• Soaps had the same alkalinity.
• Soaps had the same hardness.
So What?

So What?

• Is there a difference between soaps that gelled and those that

did not?
• Compare Aq288 soaps processed at different initial tempera-
tures.
• Soaps had the same consistency.
• Soaps had the same alkalinity.
• Soaps had the same hardness.
• Soaps behaved differently when soaked in water.
Soap Soak Test

Soap Soak Test

Soap cylinders soaked in water for 18 hrs.

Soap Soak Test

Soap Soak Test: 0 hrs

Soap Soak Test

Soap Soak Test: 18 hrs

Soap Soak Test

Soap Soak Test

• Did soaps “survive” because they got hot?

• Did soaps “survive” because they gelled?
Soap Soak Test

Soap Soak Test

• Did soaps “survive” because they got hot?

• Did soaps “survive” because they gelled?
• We can compare hot soaps with different moisture content.
Soap Soak Test

Soap Soak Test: 18 hrs

Conclusions

Conclusions
The phase behavior of saponifying oil depends on:
Conclusions

Conclusions
The phase behavior of saponifying oil depends on:

• The size and shape of the mold. Large block molds retain more
heat than individual cavity molds.
Conclusions

Conclusions
The phase behavior of saponifying oil depends on:

• The size and shape of the mold. Large block molds retain more
heat than individual cavity molds.
• The initial temperature of the oil and lye. High initial temper-
atures increase the peak temperature.
Conclusions

Conclusions
The phase behavior of saponifying oil depends on:

• The size and shape of the mold. Large block molds retain more
heat than individual cavity molds.
• The initial temperature of the oil and lye. High initial temper-
atures increase the peak temperature.
• The water portion of the soap formula. Low-water soaps gel
only at high temperatures. High-water soaps gel at moderate
temperatures.
Conclusions

Conclusions
The phase behavior of saponifying oil depends on:

• The size and shape of the mold. Large block molds retain more
heat than individual cavity molds.
• The initial temperature of the oil and lye. High initial temper-
atures increase the peak temperature.
• The water portion of the soap formula. Low-water soaps gel
only at high temperatures. High-water soaps gel at moderate
temperatures.
• The oils used. Saturated fats saponify more quickly than un-
saturated ois and may increase peak temperature.
Conclusions

Conclusions
The phase behavior of saponifying oil depends on:

• The size and shape of the mold. Large block molds retain more
heat than individual cavity molds.
• The initial temperature of the oil and lye. High initial temper-
atures increase the peak temperature.
• The water portion of the soap formula. Low-water soaps gel
only at high temperatures. High-water soaps gel at moderate
temperatures.
• The oils used. Saturated fats saponify more quickly than un-
saturated ois and may increase peak temperature.
• Fragrances and additives. Fragrances and additives may in-
crease the speed of saponification and peak temperature.
So What is Neat Soap?

So What is Neat Soap?

Neat soap is a lamellar lyotropic liquid crystalline phase of soap
and water.
So What is Neat Soap?

So What is Neat Soap?

Neat soap is a lamellar lyotropic liquid crystalline phase of soap
and water.

• Liquid crystalline: the molecules are free to move past one an-
other, as in a liquid; they are arranged in ordered patterns, as
in a solid crystal.
So What is Neat Soap?

So What is Neat Soap?

Neat soap is a lamellar lyotropic liquid crystalline phase of soap
and water.

• Liquid crystalline: the molecules are free to move past one an-
other, as in a liquid; they are arranged in ordered patterns, as
in a solid crystal.
• Lyotropic: the liquid crystal contains at least two kinds of
molecule and its properties depend on the concentrations.
So What is Neat Soap?

So What is Neat Soap?

Neat soap is a lamellar lyotropic liquid crystalline phase of soap
and water.

• Liquid crystalline: the molecules are free to move past one an-
other, as in a liquid; they are arranged in ordered patterns, as
in a solid crystal.
• Lyotropic: the liquid crystal contains at least two kinds of
molecule and its properties depend on the concentrations.
• Lamellar: the two kinds of molecules are arranged in sheets.
So What is Neat Soap?

So What is Neat Soap?

Neat soap is a lamellar lyotropic liquid crystalline phase of soap
and water.

• Liquid crystalline: the molecules are free to move past one an-
other, as in a liquid; they are arranged in ordered patterns, as
in a solid crystal.
• Lyotropic: the liquid crystal contains at least two kinds of
molecule and its properties depend on the concentrations.
• Lamellar: the two kinds of molecules are arranged in sheets.
• So.. What are the two kinds of molecules and why do they be-
have this way?
Oil, Lye and and Soap

Oil and Lye

Oil, Lye and and Soap

One Soap
Oil, Lye and and Soap

Two Soaps
Oil, Lye and and Soap

Three Soaps and a Glycerin

Oil, Lye and and Soap

Soap and Water

Nerds and Cheerleaders

Soap Micelle

Soap Micelle
Soap Micelle

Soap Micelle
Soap Micelle

Soap Micelle

Animation: (http://cavemanchemistry.com/graphics/Micelle.gif)
Neat Soap

Neat Soap
Neat Soap

Neat Soap
Neat Soap

Neat Soap

Animation: (http://cavemanchemistry.com/graphics/Neat.gif)
Solid Soap

Solid Soap

Animation: (http://cavemanchemistry.com/graphics/SolidSoap.
gif)
Conclusions

Conclusions

• When soap dissolves in water, the molecules form micelles, with

a fatty interior. Dirt, grease, and other fatty materials dissolve
in the fatty interior of the micelles.
Conclusions

Conclusions

• When soap dissolves in water, the molecules form micelles, with

a fatty interior. Dirt, grease, and other fatty materials dissolve
in the fatty interior of the micelles.
• Neat soap is a lamellar lyotropic liquid crystalline phase of soap
and water.
Conclusions

Conclusions

• When soap dissolves in water, the molecules form micelles, with

a fatty interior. Dirt, grease, and other fatty materials dissolve
in the fatty interior of the micelles.
• Neat soap is a lamellar lyotropic liquid crystalline phase of soap
and water.
• The structure of solid soap is similar to that of neat soap, but
the fatty tails of the soap molecules are “frozen” in a crystal
lattice.
Recommendations

Recommendations

• If you want a non-gelling soap to gel, increase the water portion

and/or the starting temperature.
Recommendations

Recommendations

• If you want a non-gelling soap to gel, increase the water portion

and/or the starting temperature.
• If you want to prevent a gelling soap from doing so, decrease
the water portion and/or the starting temperature.
Recommendations

Recommendations

• If you want a non-gelling soap to gel, increase the water portion

and/or the starting temperature.
• If you want to prevent a gelling soap from doing so, decrease
the water portion and/or the starting temperature.
• Gelled soap is neither better nor worse than non-gelled soap,
but it is subtly different in its water-absorbing properties.
Summary

Questions
Questions?
Summary

Scientific Soapmaking

• The textbook for the course you wish you had taken in high
school.
• To be completed this summer.
• Available now in draft form: ScientificSoapmaking.com.
Summary

References

• “Structure of the Liquid Crystal Phases of the Soap-Water Sys-

tem: Middle Soap and Neat Soap,” Luzzati, Mustacchi, and Sk-
oulios, Nature Sept 21, 1957.
• “Solid Soap Phases,” Ferguson, Rosevear, and Stillman, Ind.
Eng. Chem., 35(9), 1938.