measurement and application of equivalent alkane carbon number
TRANSCRIPT
Measurement and Application of Equivalent Alkane Carbon Number of Fragrance Oils
AOCS Meeting – May, 2014D.R. Scheuing, Erika Szekeres Clorox
Outline
Introduce the Fragrance Problem
Relate the Problem to Hydrophilic-Lipophilic
Difference (HLD) and Equivalent Alkane Carbon Number (EACN)
Introduce a Practical Approach to the Problem
Example and Watch-Outs
The Good News -
Chemically Complex Modern Fragrances Drive Consumer Preference
The Bad News -
Chemically Complex Modern Fragrances Drive Consumer Preference
Multiple Fragrances Needed !
Lemon 1.5% Surfactant
Lavender 1.7% Surfactant
Watery Fresh 1.2% Surfactant
Spring Blooms 1.3% Surfactant
4 Fragrances Need 4 Different Minimum Surfactant LevelsOne Answer = 4 Different FormulationsAnother Answer = Use 1.7% Surfactant For All
Or – Rank the Fragrances in Terms of Polarity with a Simple Method Design One Robust Formulation for All Fragrances Understand that Wide Range in Polarities Will Drive Costs
Classic Fish Diagram Shows the Formulation Problem – in terms of Temperature
Surfactant concentration
Tem
pe
ratu
re
w/o micelle+
excess water
o/w micelle+
excess oil
bicontinuous3 phase
Single phase
w
oil
oil
oil
water
w
oil
Product
Non-ionic surfactant
HLD View of the Problem – What is the Range of Fragrance HLD?
Surfactant concentration
HL
D
(oil
po
lari
ty)
2 phase
2 phase
3 phase
Polar fragrance oil
Hydrophobic fragrance oil
Single phase
(-)
(+)
𝑪𝒔
HLD = hydrophilic-lipophilic differenceVaried via oil polarity variation
A Wider Range of Fragrance HLD Requires Higher Concentration of a Given Surfactant – Costs Are Increased
Surfactant concentration
HL
D
(oil
po
lari
ty)
2 phase
2 phase
3 phase Single phase
(-)
(+)
𝑪𝒔 𝑪𝒔
Hydrophobic fragrance oil
Polar fragrance oil
Even Worse for Cost – Selection of the Wrong Surfactant Package for the Range of Fragrances
Surfactant concentration
HL
D
(oil
po
lari
ty)
2 phase
2 phase
3 phase
Single phase
(-)
(+)
𝑪𝒔 𝑪𝒔
Surfactant is too hydrophobic for this range of HLD – Higher Concentration Required
Polar fragrance oil
Hydrophobic fragrance oil
Rank Fragrance Oil Polarities Via EACN Measurement
Use the HLD equation for anionic surfactant
0=ln (𝑺∗ )−𝑘 ∙𝑬𝑨𝑪𝑵+𝐶𝑐
𝐻𝐿𝐷=ln (𝑆 )−𝑘 ∙𝑬𝑨𝑪𝑵+𝐶𝑐−𝑎𝑇 ∙ (𝑇 −25 )+ 𝑓 ( 𝐴)
HLD (reflects overall formulation hydrophobicity):
• Electrolyte (S) – vary this experimentally• Oil polarity (EACN) - unknown• Surfactant head/tail (k and Cc) – these are known• Temperature (T) – fix this at 25C• Alcohol – f(A) don’t add alcohol
Experimentally determine S* at which optimum formulation is achievedHLD = 0
Calculate EACN
𝐸𝐴𝐶𝑁=ln (𝑆∗ )+𝐶𝑐
𝑘
Salt scan on the SOW phase map
Surfactant concentration, wt%
Na
Cl w
t%
w/o micelle+
excess water
o/w micelle+
excess oil
bicontinuous
3 phase
Single phase
HLD =0S*
Anionic surfactant
Salt scan in the test tubes with SDHS surfactant and Limonene
2.687
3.714
4.740
5.718
6.744
7.770
8.797
9.823
10.850
11.827
12.854
13.880
0%10%20%30%40%50%60%70%80%90%
100%
Relative phase volumes
Excess water Microemulsion Excess oil
aq. NaCl %R
ela
tiv
e p
ha
se
vo
lum
e
2 3 4 5 6 7 8 9 10 11 12 13 140
1
2
3
4
5
Volume of oil and water in the mi-croemulsion phase
WaterOIL
NaCl %
Vo
lum
e, m
l
S*
S* = 7% EACN = 6.05
The more positive the EACN the
more hydrophobic the oil
SDHS= sodium dihexyl sulfosuccinate
Water/oil volume ratio = 1
Adaptation to Fragrance Oil Ranking
Problem• Fragrance oils are quite polar
• The Winsor I-III-II phase sequence might be impossible to find
Solution• Run salt scan with fragrance oil/limonene mixture rather than with
pure fragrance oil and determine the EACN of the oil mixture;
• Run a limonene salt scan control to determine limonene EACN
• Use linear mixing rule by volume to calculate fragrance oil EACN from oil mixture EACN and limonene EACN data
Salt scan with fragrance/limonene mixture
2 3 4 5 6 7 8 9 10 11 12 13 140
0.51
1.52
2.53
3.54
4.55
Volume of oil and water in the microemulsion phase
NaCl %V
olu
me
, ml
2.687
3.714
4.740
5.718
6.744
7.770
8.797
9.823
10.850
11.827
12.854
13.880
0%10%20%30%40%50%60%70%80%90%
100%
Relative phase volumes
Excess water Microemulsion Excess oil
aq. NaCl t%
Re
lati
ve
ph
as
e v
olu
me
S* oil mixture = 4.8%EACN fragrance = - 5.05
S* mix calculate EACN mix using HLD calculate EACN fragrance with linear mixing rule
Oil mixture = 0.2 vol fraction fragrance/limonene mixture
Watch-outs
Limonene oxidation – polar shift possible
Run SDHS +limonene control scan
SDHS solution from Aldrich seems reproducible
Ester hydrolysis/residual alcohol ?
Room temperature is usually good enough
Use water/oil ratio = 1
Always add fragrance oil at 0.2 volume fraction
Calculated fragrance EACN depends on mixing ratio !
Oil mixture EACN is a nonlinear function of mixing ratio
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1-4
-2
0
2
4
6
8
Limonene + fragrance oil mixture, 10% SDHS, salinity scan using NaCl
Fragrance oil volume fraction
EACN
of o
il m
ixtu
re
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1-14
-12
-10
-8
-6
-4
-2
0
EACN of fragrance oil calculated using linear mixing rule
Fragrance oil volume fraction
EACN
of p
ure
frag
ranc
e
Stick to a fixed 0.2 volume fraction for all EACN measurements
Measured EACN of Fragrances and Solvents
-14 -12 -11 -10 -9 -8 -6 -5 -4 -3 0 1 50
1
2
3
4
5
6
7
8
9
10
Typical fragrance EACN values
Fragrance EACN value
Fre
qu
en
cy
solvent 1 solvent 2 solvent 3 solvent 4 solvent 5-28
-26
-24
-22
-20
-18
-16
-14
-12
-10
Solvent EACN values
Example - Individual Fragrance Components
Nerol – 97% from Acros
EACN measured with current approach = -21.9
Linalool – 97% from Acros
EACN measured with current approach = -14.5
Empirical Formula = C10H18O
Summary
Complex Modern Fragrances Exhibit a Wide Range of Polarity
Formulation Costs Can Be Driven By Range of Polarity – Equivalent to a Range in HLD
Ranking of Fragrance Polarities Via EACN Drives Rapid Formulation Optimization
Simple Approach – Measure EACN of Limonene/Fragrance Oil Mixtures to Rank Fragrances
Rankings Will Be Correct – Even if the Measured EACNs are Not the Real Ones
Approach Is Practical – And Could Drive Inter-Lab Collaboration
Thanks !
AOCS – S&D Division
Clorox
And –
You – The Audience and Consumer !
References
The EACN scale for oil classification revisited thanks to fish diagramsJournal of Colloid and Interface Science 312 (2007) 98–107S. Queste, J.L. Salager, R. Strey, J.M. Aubry
Classification of terpene oils using the fish diagrams and the EquivalentAlkane Carbon (EACN) scaleColloids and Surfaces A: Physicochem. Eng. Aspects 338 (2009) 142–147Francois Bouton, Morgan Durand, Véronique Nardello-Rataj, Marie Serry, Jean-Marie Aubry
A Two-State Model for Selective Solubilization of Benzene-Limonene Mixtures in Sodium Dihexyl Sulfosuccinate MicroemulsionsLangmuir 2004, 20, 6560-6569 Erika Szekeres, Edgar Acosta, David A. Sabatini, Jeffrey H. Harwell