Physical Properties of Oils a n d Mixtures of Oils

241
R.E. TIMMS, Kempas Edible Oil Sdn. Bhd., P.O. Box 75, Pasir Gudang, Johore, Malaysia
ABSTRACT
The physical properties of palm, palm kernel and coconut oils are
reviewed and compared and contrasted with the properties of other
oils and fats. More information is available for palm oil than for the
other two. The properties of mixtures of the oils also are con-
sidered, especially mixtures of palm and palm kernel oils in which a
euteetie interaction occurs,
Basic physical properties considered are density, specific heat,
heat of fusion and viscosity. Where appropriate, data is tabulated in
SI and Imperial unit~
Experimental methods used for determining melting points and
solid fat contents are discussed and the empirical nature of the re-
~l t s emphasized. Wiley melting points and Slip melting points, and
Solid Fat Content by NMR and Solid Fat Index by dilatometry, are
compared and comparative data given. For palm oil, detailed olein
and stearin information is presented.
T h e p h a s e behavi or a n d p o l y mo r p h i s m o f t h e t hr e e oils i s re-
vi ewed. Speci al a t t e n t i o n is gi ven t o t h e pos t - ha r de ni ng p h e n o me -
n o n i n pa l m oi l a n d t h e e f f e c t s o f di gl ycer i des a nd s t or age t i me o n
pha s e behavi or .
I NTRODUCTI ON
Physi cal pr oper t i es of an oi l or f at are of cri t i cal i mpor t a nc e
i n det er mi ni ng i t s use. Thi s is par t i cul ar l y t r ue of t he large
qua nt i t y and var i et y o f oi l s and f at s used in var i ous f or ms
as f ood. I ndeed, t he separ at e wor ds " oi l " and " f a t " occur
in mos t l anguages and show t hat one f undament al physi cal
p r o p e r t y - wh e t h e r t he f at is l i qui d at ambi ent t emper at ur es
- h a s been r ecogni zed f r om t he ear l i est t i mes as of gr eat
i mpor t ance.
A f a t is a mat er i al t ha t is c ompos e d of an i nt i ma t e mi x-
t ur e of l i qui d and sol i d phases whose mai n cons t i t uent s are
t r i gl ycer i des. The physi cal st at e o f a f at ma y vary f r om a
l i qui d t o a vi scous f l ui d t o a pl ast i c sol i d t o a br i t t l e sol i d.
The t hr ee oi l s pal m oi l (PO), pal m ker nel oi l (PK) and
c oc onut oi l (CN), t oge t he r wi t h t hei r commer ci al l y avail-
abl e f r act i ons, span t he whol e range of physi cal st at es. Fur -
t her mor e, al t hough t he y are cal l ed oils, pr es umabl y because
t he y are mos t l y l i qui d at t he a mbi e nt t r opi cal t emper at ur es
wher e t he y are pr oduced, t he y are mos t l y sol i d and t r eat ed
as f at s in t he mor e t e mpe r a t e cl i mat es of t he maj or i ndus-
t r i al count r i es. These t wo f eat ur es make t hei r physi cal
pr oper t i es o f par t i cul ar i nt er est and have r esul t ed in t hei r
use m a wi de range of speci al appl i cat i ons (1).
I n t hi s paper I pr opos e t o consi der t he basi c physi cal
pr oper t i es, empi r i cal physi cal pr oper t i es and phase behavi or
and pol ymor phi s m. Thi s is not an exhaust i ve l i st but will
encompas s mos t of t he pr oper t i es whi ch ar e of i nt er est .
Mor e det ai l ed and ext ensi ve i nf or ma t i on can be f ound i n
vari ous revi ews and t e xt books (2-4).
BASI C PHYSI CAL PROPERTI ES
Density
The densi t y* of an oi l depends on i t s s aponi f i cat i on val ue
( mol ecul ar wei ght ), i odi ne val ue ( uns at ur at i on) , f r ee f a t t y
aci d cont ent , wat er c ont e nt and t emper at ur e. Appr oxi -
* I n t hi s di s cus s i on t h e t e r m d e n s i t y r ef er s t o t h e a p p a r e n t
d e n s i t y or we i ght b y vol ume, a s s u mi n g t h e oil i s wei ghed i n air.
Thi s is t h e mo s t us e f ul de f i ni t i on f or pr act i cal p u r p o s e s Th e abso-
l ut e density refers to the oil weighed in vacuum. The specific gravity
= (weight in air of volume of oil at a given temperature (T 2 )/(weight
in air of same volume of water at reference temperature (T 1 )) and
usually is written as sg T 1/ T 2 to indicate the particular tempera-
tures. If T 1 a n d T 2 are the same, they often are omitted. A full dis-
cussion of this topic is given in reference (5).
mat el y, dens i t y changes by (4, 5) +0.3 kg/ m 3 f or each uni t
i ncr ease i n s aponi f i cat i on val ue; +0. 14 kg/ m 3 f or each uni t
i ncrease in i odi ne val ue; - 0 . 6 8 kg/ m 3 f or each degree C
i ncrease in t e mpe r a t ur e ; - - 0. 2 kg/ m f or each 1% i ncrease in
f r ee f a t t y aci ds, and +0. 8 kg/ m 3 f or each 1% i ncrease in
wat er .
These cor r ect i ons r ef er onl y t o de t e r mi na t i ons at t he
usual a mbi e nt and measur i ng t emper at ur es , e.g. 20- 60 C.
Thus, f or pr act i cal pur poses t he t e mpe r a t ur e is t he mos t
i mpor t a nt vari abl e.
Dat a f or PO, PK and CN is l i mi t ed and is r e por t e d at a
var i et y of t emper at ur es , s omet i mes as dens i t y and some-
t i mes as speci fi c gr avi t y, so t ha t compar i s on is di f f i cul t : PO,
0. 891 g/ ml at 50 C (6), 0. 8919- 0. 8932 sg 50 C/ 25 C (7),
0. 8957- 0. 8766 kg/1 at 4 2 - 7 0 C (5); PK, 0. 860- 0. 873 sg
99 C/ 15. 5 C (4), 0. 9195- 0. 8913 kg/1 at 20. 60 C ( 5) ; CN,
0. 917- 0. 919 sg 25 C/ 1 5 . 5 C (4), 0. 869- 0. 874 sg 9 9 C /
15.5 C (4), 0. 9219- 0. 8934 kg/ l at 20- 60 C (5), 1. 12-7. 06 x
10 -4 T (g/ cm 3) over 30- 60C wher e T is t e mpe r a t ur e
in K (40).
The mos t compr ehensi ve s t udy of t he dens i t y of pal m
oi l has been made by PORI M (8). Cr ude and RBD pal m oi l
and ol ei n were s t udi ed over t he t e mpe r a t ur e range 25-75 C.
St at i st i cal anal ysi s of t he dat a showed no si gni f i cant di f f er -
ence bet ween t he var i ous oils, and t he dens i t y coul d be
expr essed as dens i t y ( g/ ml ) = 0. 9244 - 0. 00067 T, wher e T
is t he t e mpe r a t ur e in degrees Celsius. Typi cal Mal aysi an
cr ude pal m oi l has a moi s t ur e c ont e nt o f 0. 25% and f r ee
f a t t y aci d c ont e nt of 3%. Thus, t he di f f er ence in dens i t y
bet ween RBD and cr ude oi l s woul d be e xpe c t e d t o be onl y
0. 0004 g/ ml , and t hi s smal l di f f er ence was not s t at i s t i cal l y
si gni f i cant c ompa r e d wi t h exper i ment al er r or and nat ur al
var i abi l i t y of t he var i ous oils st udi ed.
For r ef er ence pur poses t he avai l abl e dat a has been re-
f er r ed t o c o mmo n t emper at ur es and uni t s usi ng a t emper a-
t ur e coef f i ci ent o f - 0 . 6 8 kg/ m 3 and conver si ons bet ween
speci fi c gr avi t y and dens i t y as given by Cocks and van Rede
(5) ( Tabl e I).
Densi t i es of t r i gl ycer i des in t he sol i d st at e are appr oxi -
ma t e l y 10% gr eat er t han in t he l i qui d st at e. Thus, on mel t -
ing, expans i on occur s whi ch is t he pr i nci pl e o f t he di l at o-
met r i c me t h o d f or det er mi ni ng sol i d f at c ont e nt (9).
Specific Heat
Much dat a has been r e por t e d on speci fi c heat s of oi l s and
fat s, but none refers speci f i cal l y t o PO, PK or CN (4, 7).
I n t he sol i d st at e t her e is l i t t l e change i n t he speci fi c heat
as t he mol ecul ar wei ght varies, but t her e is an i ncr ease in
speci fi c heat wi t h i ncrease in i odi ne val ue ( unsat ur at i on) .
I n t he l i qui d st at e speci fi c heat i ncreases sl i ght l y wi t h
TABLE I
Deami t i es o f Pal m, Pal m Kernd and Coconut Oi l s
Te mp e r a t u r e PO PK CN
C F k g / m 3 l b/ f t s k g / m 3 l b/ f t ~ k g / m s l b / f t s
50 122 891 55. 6 898 56. 1 901 56. 2
75 167 874 54. 6 881 55. 0 884 55. 2
100 212 857 53. 5 864 53. 9 867 54. 1
200 392 789 49. 3 796 49. 7 799 49. 9
JAOCS, Vol. 62, no. 2 (February 1985)
242
R.E. TIMMS
molecular weight, but decreases slightly with iodine value.
Overall, there is little variation among the natural oils and
fats. For practical purposes the specific heats of liquid oils
and fats, including PO, may be taken as:
0.47 + 0. 00073T kcal/kg
where T is the t emperat ure in degrees Celsius. Note: 1 Btu/
lb = 0.252 kcal/kg. There is no data available for PK and
CN, but the above equation is probabl y satisfactory for
practical purposes since the variation of specific heat with
molecular weight is small.
He a t o f Fusi on
Although there is much published data on heats of fusion
of pure triglycerides (10), there is only limited data on the
heats of fusion of natural oils and fats. Recent work at
PORIM (11) has provided useful data on the heats of fusion
of PO, PK and CN, as shown in Table II. These values
should be compared with milk fat (12) 17.7-22.3 kcals/kg,
fully hardened milk fat (12), 24-31 kcal/kg, and cocoa
but t er (13) in the/3' pol ymorph, 26-29 kcal/kg. As usually
measured, heats of fusion are an empirical physical prop-
ert y dependent on the thermal pre-t reat ment or tempering
given to the oil. The tempering procedure applied in the
PORIM study would be expected to t ransform all the
sample to the /5' pol ymorph, but this was not checked
independently.
Vi scosi t y
Oils and fats show t he flow behavior of true Newtonian
liquids. Near the melting point non-Newtonian behavior
may occur due to the presence of fat crystals. The viscosi-
ties of natural oils and fats do not differ greatly (4,40).
Viscosity increases with molecular weight but decreases
with increasing unsaturation and temperature. The viscosity
of an oil decreases by approxi mat el y 30% for each 10 C rise
in temperature.
Frying increases t he viscosity of oils (14), and recently a
viscosity test has been proposed for screening used frying
oils (15). A viscosity of 45 cP at 50 C has been proposed as
the maxi mum permissible for a used frying oil. For this test
to be applied it is i mport ant to know the viscosity of
freshly refined oils. Table III gives our recently determined
data. By this criterion, the viscosity of an oil would approx-
imately double before it would be rejected.
Blends of palm and palm kernel oils also were studied.
Although blends of laurie and non-laurie oils are not
normally used for frying, such blends show interesting and
potentially useful eutectic effects (1,16). I t was of interest
to see if the interactions between the laurie and non-laurie
oil also affect the viscosity. In Figure 1, viscosity and solid
fat cont ent (SFC) data are shown for blends of palm oil and
palm kernel oil and palm olein and palm kernel oil. At all
compositions t he viscosity of the blend is lower than the
viscosity expected by linear interpolation (dashed line), but
the effect is unrelated to the eutectic interaction as shown
by t he SFC curves.
E M P I R I C A L P H Y S I C A L P R O P E R T I E S
Mel t i ng Po i n t
Since fats are mixtures of many compounds, t hey exhibit a
broad melting range rat her t han a clearly defined melting
temperature. The melting poi nt of a fat is thus an empirical
propert y related t o t he experimental met hod of determina-
tion and not a basi~ physical propert y, like the melting
poi nt of a pure compound. The t wo commonest met hods
TABLE II
Heats of Fusi on of Palm, Palm Kernel and Coconut Oils (11)
AHf (kcal/kg)
RBD PO 22.6
RBD PK 29.7
RBD CN 26.0
Fully hardened PK 31.6
Fully hardened CN 31.2
Inst rument : Perkin-Elmer DSC-2. Tempering procedure: 353K
(10 rain), cooled lOK/min to 293K and held 30 min, cooled 1OK/
rain to 223K and held 10 min. Measuring procedure: heated at
lOK/min to 353K, reference indium.
TABLE HI
Viscosity (cP) of Various Oils
Temperat ure (C)
Oil 20 25 30 35 40 45 50 b
Palm >100 a >100 a >100 a 96.3 a 40.4 33.3 27
Palm olein 85.3 69.2 56.3 43.4 38.6 32.6 26.5
Palm kernel >100 a >100 a 44.0 35.6 30.0 25.4 21
Coconut >100 a 48.1 39.8 32.9 27.4 23.3 1.9
Soybean 63.6 51.6 43.1 36.8 31.7 26.8 22.5
aTurbulent, non-Newtonian flow occurred.
bBy extrapolation, log(viscosity) vs. T.
35 - ] 50
VISCOSITY ~ N~ ' ' . . / 40
(cP) at 45C "" - 30
. - 20
= x ' x ~ . . . - i 0
25 I I I I " ~ : 0
2 0 4 0 6 0 8 0 1 0 0
% PK
SFC (%)
at 20 ("
3s F - so
v,scos,rY ~ . / SFC ('/.)
(~P)=kSCl " ~ . / at 20C
I /
3 0 r " % - . . _ 2o
I f " - . . . " - . - '
0 20 40 60 80 100
% PK
FIG. 1. Viscosity and Solid Fat Content of bl ends of Palm Oil and
Palm Kernel OR, top, and Palm Olein and Palm Kernel Oil, bot t om.
JAOCS, Vol. 62, no. 2 (February 1 985)
243
PHYSICAL PROPERTIES AND MIXTURES OF OILS
for determining the melting poi nt (MP) of a fat are:
Slip Melting Point-The t emperat ure at which fat in a
capillary t ube placed in water becomes soft enough to slip
or rise up t he tube. Also called open t ube MP, rising poi nt
or softening poi nt and exemplified by AOCS Method
Cc 3-25.
Wiley Melting Point-The t emperat ure at which a disc of
fat becomes spherical when heated in an alcohol-water
mixture. AOCS Method Cc 2-38.
The Wiley MP is very popular in the USA, but little used
elsewhere. The Slip MP is used commonl y in Europe and
has been adopt ed in Malaysia as the preferred met hod for
palm and palm kernel oil. Comparative values for Slip and
Wiley MP' s are shown in Table IV. Wiley MP's frequent l y
are several degrees higher than Slip MP's. In the Slip MP test
the fat slips in t he capillary t ube when about 5% solid fat is
present. In t he Wiley MP test the f at is sufficiently fluid to
form a sphere onl y when the fat is almost fully liquid with
about 1% solid fat still present.
Because there are substantial differences in MP' s deter-
mined by different methods, it is i mport ant to distinguish
carefully between the methods. Too often, papers in t he
literature or at conferences refer simply to Melting Point.
TABLE IV
Comparison of Slip (AOCS Cc 3-25) and Wiley
(AOCS Cc 2-28) Melting Points
Slip MP Wiley MP
C F C F
RBD palm oil 36.3 97.3 41.9 107,4
RBD palm olein 22.8 73.0 25.8 78.4
RBD palm stearin 54.0 129.2 54.4 129.9
RBD palm kernel oil 27.6 81.7 32.1 89.8
NBD palm kernel stearin 32.0 89.6 34.2 93.6
RBD coconut oil 24.1 75.4 26.0 78.8
Hydrogenated palm kernel oil 40.0 104.0 45.1 113,2
Hydrogenated coconut oil 35.6 96.1 41.7 107.1
Hydrogenated palm oil 50.4 122.7 50.8 123.4
Cocoa butter substitute
based on hydrogenated
PK stearin 35.9 96.6 38.8 101.8
In Figure 2, Slip and Wiley MP' s of blends of palm and
palm kernel oils are compared. The substantially different
shape of the two curves indicates t hat caution should be
used in converting f r om one MP t o the ot her by any "rul e
of t humb" met hod. Figure 2 also clearly demonstrates the
empirical nature of the MP determination as discussed
above.
There is little information available on the natural varia-
tion of coconut oil. In our experience, Malaysian coconut
oil has a Slip MP of 23.5-25.5 C. Ranges of 23-26 C (17)
and 20-28 C (18) have been given in the literature for the
natural variation, but the latter range is not found in com-
mercial samples.
Much more information is available for palm oil, olein
and stearin and for palm kernel oil (Table V). The results
from my own company (KEO) refer to weekly composi t e
samples collected over a 12-month period. All means from
235
5
W
IE
3O
2 5
0
m
%/
i 1 I I
20 /.0 SO 80 t00
% PALM KERNEL OIL
FIG. 2. Comparison of Slip and Wiley Melting Points for blends of
Palm and Palm Kernel Oils.
TABLE V
Variation of Slip Melting Point (C) of Palm Oil,
Palm Olein, Palm Stearin and Palm Kernel Oil
Source No. of
Oil of data samples Mean Range
Crude palm kernel PORIM (39) 118 27.3 25.9-28.0
Crude palm oil PORIM (37) 102 36.0 32.3-39.0
Crude palm oil MARDI (37) 215 34.2 30.8-37.6
Crude palm oil KEO (36) 300 35.6 33.6-37.2
RBD palm oil KEO (36) 36 36.1 34.0-39.0
Crude & RBD palm olein a
Crude palm olei9 a
RBD palm olein o
Crude & RBD palrq stearin a
Crude palm stearin o
PORIM (38) 193 21.6 19.4-23.5
KEO (36) 40 20.3 17.2-26.1
KEO (36) 35 21.5 19.O-23.0
PORIM (38) 150 - 44.5-56.2
KEO (36) 29 52.6 51.2-54.2
aAll fractionation processeg
bDetergent fractionation only.
JAOCS, Vol. 62, no. 2 (February 1985)
2 4 4
R. E. TI MMS
this study are weighted according to the tonnage. For
crude palm oil the KEO results agree closely with the
PORIM results, suggesting that the MARDI results are too
low. For palm olein, the KEO and PORIM results are
similar again. For palm stearin, the PORIM survey covered
all the fractionation processes used in Malaysia. The result
is a very wide spread of MP's. The KEO results refer only to
stearins produced by detergent fractionation and therefore
show a narrower variation, with results at the upper end of
the PORIM range.
In the PORIM and MARDI surveys, no systematic
differences in MP (or other properties) were found between
crude PO from different parts of Malaysia. In the KEO
study, over 90% of the oils studied originated in Johore.
The close agreement between the KEO and the PORIM data
confirms PORIM's conclusions of little regional variation
for Malaysian PO. Furthermore, except for one small parcel
of PO from Sabah, there was no significant difference in the
MP's or the iodine values of oils received from 10 major
suppliers in the KEO study. This is further confirmation
that Malaysian crude palm oil is a very uniform product.
In the KEO study, no significant correlation was found
between MP's and iodine values for crude palm oils. This
somewhat surprising result is attributed to (a) the effect
of free fatty acids, (b) the possible effects of the introduc-
tion of the weevil, (c) a trend increase in the MP over the
year studied (see below), (d) lack of homogeneity in a
supplier's tank coupled with blending practices to keep the
FFA of delivered oil below 5%. It should be noted that the
period under study, from June 1982 to June 1983, was a
period of tremendous change in Malaysian crude PO pro-
duction and supply due to the combined effects of the
introduction of the weevil and of the weather.
Although, as noted, Malaysian crude palm oil varies over
a narrow range of properties, day to day and week to week
fluctuations can be large and cover the whole range ob-
served. In Figure 3 the variations of MP of crude PO re-
ceived at KEO over the year studied are shown. Each point
refers to the weighted mean MP for a week's deliveries of
oil. A substantial part of the daily and weekly variation is
due to inhomogeneity in a supplier's tank. After several
weeks of storage, which happens all too frequently, stearin
crystals sink to the bottom of the tank and the first oil to
be pumped out is enriched in stearin and has a higher
melting point.
Apart from these daily and weekly flucttmtions there
was a statistically significant upward trend in MP during
the period. The trend regression line is shown in Figure 3.
The trend line slope was 0.9 C rise per yr, and the average
MP in the second six mo was 0.6 C higher than in the first
six mo. This increase may have been due to the combined
effects of the weevil and the weather. There is some evi-
dence that a higher MP for Malaysian PO has persisted,
leading to lower yields of palm olein on fractionation.
When palm stearins are considered, a relationship be-
tween MP and iodine value becomes clear. Results for palm
oil and palm stearin are shown in Figure 4. PORIM has
proposed using this relationship to assist in distinguishing
between palm oil and stearin and to detect adulteration of
PO with palm stearin.
The results in Table V and other results by PORIM and
other workers show that MP's rise on refining.
Sol i d Fat Cont ent s
The solid fat content (SFC) of a fat at a given temperature
has until recent years been determined mainly by dilato-
merry (5,9).
European practice has been to use dilatations them-
selves in units of mm 3 per 25 g: American practice has been
3 , [
37
36
5
Y
a. 35
3/.
10 2o 30 40 50
WEEK ( Beginning 1st June 1982)
FI G. 3. Var i at i on o f Sllp Mel t i ng Po i n t f or c r u d e Pal m Oi l r ecei ved
o v e r a y e a r ; we e k l y - c o mp o s i t e anal ys es .
i 44
4O
It,
~ e
i t " " " " ' - . : . . ~ ! ? . .
[
I
I
.%
"~.. P A L M O I L S
32 I
%
!
24
24 28 32 36 40 44 48 52 56
IODINE VALUE
FI G. 4. Re l a t i ons hi p b e t we e n Slip Mel t i ng Po i n t a n d I odi ne Val ue
f o r Pal m St ear i n a n d Pal m Oi l s a mpl e s ( t a ke n f r om r ef . 38).
to divide this dilation by 25 to give a "solid fat index"
(SFI), which all too frequently is confused with the actual
percentage of solid fat present. The American procedure
assumes that all fats have the same total melting dilation
(TMD), that it is 2500 mm3/25 g, and that its variation
with temperature can be ignored. All these assumptions
have long been known to be incorrect (9). In addition,
American tempering practice was designed especially for
hardened oils and includes a tempering at 80 F (26.7 C),
This tempering procedure tends to lower the solid fat
content at temperatures below 80 F and raise it above 80 F.
It is generally unsuitable for PO, PK and CN and has not
been adopted widely in Malaysia. Furthermore, the use of a
TMD of 2500 means that SFI' s for PO and PK based fats
often are only about 80% of the true solid fat content and
JAOCS, Vol . 62, no. 2 ( Febr uar y 1985)
245
PHYSICAL PROPERTIES AND MIXTURES OF OILS
even the hardest PK-based cocoa but t er substitutes, with
actual solid fat cont ent s above 90%, do not show SFC' s
above about 75%.
In the last 10 yr, nuclear magnetic resonance spectrom-
etry (NMR) has been used widely for the det ermi nat i on of
SFC (19-23). The NMR met hod is quicker, more precise
and closer to the absolute solid fat cont ent than dilato-
merry. Laboratory i nst rument s suitable for rout i ne use in
TEMPERATURE ( F )
50 70 80 92 100
100 I ~ I ~ w
8 0
6O
%
/,0
20
0 I ! i ....... I , , I
10 20 25 30 35
TEMPERATURE ( C )
FIG. 5. Comparison of Sol i d Fa t I n d e x b y di l at ome t r y (SFI),
Sol i d Fa t I nde x b y NMR ( SFI ( N) ) and Sol i d Fa t Co nt e nt b y NMR
(sFc).
O~ . ~ " ~ x - - - - - x SFI
I ~ ' ~ ' ~ " % H S F I ( N }
~" " %~' ~0% o.-- --. 0 S FC
~" . . . . ~ ~ ~' " ~%~ HYDROGENATED
- " ~ ' , , ' ~ . ~ PALM KERNEL OIL
O-.
L % % % xXXx~X~
,%
!
t,0
factory product i on and quality control became available in
the early 1970' s. In Europe, NMR has replaced dilatometry
almost entirely, but in North America the adoption of
NMR appears to have proceeded more slowly. In Malaysia,
dilatometry has never become well established. Research
institutes and refinery laboratories immediately adopted
the new technology. Indeed in my own laboratory we only
resort to dilatometry to provide results for potential
American customers.
All the results given below as SFC' s were obt ai ned by
NMR and used a "European" series tempering procedure as
adopted by PORIM and used widely in Malaysia (0 C for
90 min, then 30 min at each measuring temperature, 10 C,
20 C, 25 C, etc.).
Figure 5 shows typical results for PK and hydrogenated
PK comparing SFI, SFC by NMR and an SFI/NMR proce-
dure in which the tempering was as SFI (AOCS Cd 10-57)
but measurement was by NMR. At temperatures above
26.7 C there is little difference between the three methods,
but at lower temperatures the differences are substantial.
In Table VI SFC data for PK and PO products is given. It
should be compared with the MP data in Table V. As with
the MP, refining increases the SFC of palm oil and frac-
tions. This is due partly to the removal of free fatty acids,
since adding back fatty acid distillate lowers the SFC' s
(Fig. 6). However, in some cases it appears that other
changes due to refining are important, such as some re-
arrangement of the triglycerides or removal of phospho-
tipids and monoglycerides, since we find that adding back
the fat t y acid distillate does not fully account for the
change on refining.
There is no published data on the variation of the SFC
of coconut oil. From experience at my own company,
typical Malaysian CN has SFC at 10 C, 68-72%; at 20 C,
32-40%, at 25 C, 0-3%.
P H A S E B E H A V I O R A N D P O L Y M O R P H I S M
The phase behavior of fats (including palm, palm kernel
and coconut oils) has been reviewed recently (2). This
review should be referred to for more detailed information.
P a l m O i l
Palm oil is uni que among vegetable oils because of its high
saturated acid cont ent with a significant amount (10-16%)
of saturated acids at the 2-position of its triglycerides. In
TABLE VI
Solid Fa t Co n t e n t (% b y NMR) o f Palm Oil, Palm Olein, Palm St eari n and Palm Ke r n d Oil
Temperature (C)
Source
of data 10 20 25 30 35 40
45 50
Crude palm kernel oil PORIM (39) 67.6 40.1 17.1 0
Crude palm oil PORIM (37) 48.5
Crude palm oil MARDI (37) 49.6
Crude palm oil KEO (36) 49.2
RBD + NBD palm oil PORIM (37) 50.3
RBD palm oil KEO (36) 53.1
Crude palm olein PORIM (38) 33.6
Crude palm olein KEO (36) 36.9
RBD + NBD palm olein PORIM (38) 37.0
RBD palm olein KEO (36) 37.6
Crude palm stearin PORI M (38) 54.2-
91.1
Crude palm stearin KEO (36) 76.8
21.8 13.4 9.3 6.6 4.2 -- --
22.5 13.5 9.2 6.6 4.0 -- --
21.5 13.8 7.9 4.5 2.1 0.7 O.1
23.2 13.7 8.5 5.8 3.5 -- --
24.7 15.5 9.1 5.7 2.0 1.1 0.1
3.2 . . . . . .
1.8 0 . 2 0 . . . .
5.9 . . . . . .
4.5 0.9 0.3 0 -- -- --
31.3-- 20.2-- 16.4-- 12.5-- 7.4-- 2.7-- 0--
87.4 81.9 73.5 65.0 56.6 48.6 39.7
68.0 61.2 50.3 42.6 35.7 29.3 19.0
JAOCS, Vol . 62, no. 2 ( Febr uar y 1985)
246
R.E. TIMMS
A
r~
:E
z
$
I - -
z
Lu
p .
z
0
o
LL
E3
- - I
4 8
Z,';
/.6
Z.5
/*3
42
/.1
40
3 9
~ F C a t 1 0 ~
1 9
18
17
" ~ S F C at 20C
I I I I I I I
0 1 2 3 /. 5 6 7
% PALM FATTY ACID DISTILLATE ADDED {FFA85%)
FIG. 6. E f f e c t o f p a l m o i l f a t t y a c i d d i s t i l l a t e o n t h e S o l i d F a t Co n -
t e n t of RBD Pahn Oil.
consequence, PO consi st s of t hr ee mai n t ype s o f t r i gl ycer -
i de: t r i s at ur at ed ( mai nl y PPP), di s at ur at ed ( mai nl y POP)
and monos a t ur a t e d ( mai nl y POO), PO al so cont ai ns appr e-
ci abl e amount s of di gl ycer i des (5-8%) and f r ee f a t t y aci ds
( 24- 25) , whi ch can have a subst ant i al ef f ect on i t s physi cal
pr oper t i es.
Under nor mal a mbi e nt condi t i ons ( 20- 30 C), PO appear s
as a het er ogeneous sl ur r y o f cr yst al s ( mai nl y PPP + POP) i n
a l i qui d oi l ( mai nl y POO + POP) (26, 27). The s epar at i on of
t hese phases is t he basis of t he l arge-scal e f r act i onat i on
processes appl i ed t o PO. These f r act i onat i on pr ocesses are
r el at i vel y easy t o oper at e, because t he phases ar e mor e
di s t i nct t han in ot he r fat s. I f t he f r act i onat i on pr ocess uses
a sol vent , t hr ee f r act i ons r oughl y cor r es pondi ng t o t he
t hr ee mai n t ype s of t r i gl ycer i de ma y easi l y be separ at ed.
A mos t usef ul and compr ehensi ve s t udy of t he phase
behavi or of PO has been r e por t e d by Per smar k, Mel i n and
Sr~hl (28). I n unf r act i onat ed PO t hr ee pol ymor phs were
f ound:
22 C
liquid = #~ - 2
I I I 3 7 C ]
i
- 1 5 C 5-7 C
f
#2 (sub-e) ; e - 2 + #'3 -- 2
- 5 to - 1 0 C
( - - --*,~ cooling, ~ heating)
Similar polymorphic behavior was found by Riiner (29)
and by Berger and Wright (30). For practical purposes,
when PO is used for margarines and shortenings and most
ot her food uses, only the c~-2 and #'1-2 polymorphs are
JAOCS, Vol. 62, no. 2 (February 1985)
important. An important consideration here is that the time
for the ~ polymorph to transform to/3' (i.e. the ~ lifetime)
is unusually long in PO, which has been shown t o be due t o
the high level of diglycerides (28-31).
It is recognized that crystallization and development of
an equilibrium SFC and hardness is relatively slow in PO
compared to other oils, especially hardened oils, with
similar MP. This phenomenon is called post-hardening and
is a serious disadvantage in some applications of PO. The
cause of post-hardening is not fully understood, but it is
related to the peculiar triglyceride and phase composition
of PO and to the presence of high levels of diglycerides.
The rate of crystallization and polymorphic transformation
in PO has been studied using differential scanning calorim-
etry and microscopy and a theoretical treatment developed
(32, 33).
As well as affecting the rates of crystaUization and poly-
morphic transformation, diglycerides also affect the equi-
librium solid fat contents (30,31). However, at the average
level of diglycerides found in our study of Malaysian PO,
6.3%, the results of Berger and Wright (Fig. 7) showed no
substantial effect. However, when the oil was stored for a
long time there was a clear effect of diglycerides on the rate
of crystaUization, even at the levels normally found in PO
(Fig. 8). (In fact, the oils used by Berger and Wright had
o
~_ 3 0 o - - o - - - Palrnoil B
0 o " - (I.V.:51.7)
O x
\
u~ Palm OiL A ~ "~,,
{ l . V . =55-6 ) ~ "
1 0 I I
0 1 0 2 O
"/. D~GLYCERIDES
1 0 0 % 7RIGLYCERIDES
FIG. 7. Solid F a t C o n t e n t after 10 days at 21 C o f mi x t u r e s o f
re~. ycerides a n d diglycerides isolated from Palm Oil (taken from
3 0 ) .
A
~ t , O
_ T R I G L Y C E R I D E S - - ~ " e - - e - - e . " e e -
U J / i t s w - -
E .,,.e "A) ~ ORIGINAL OIL
( ~ 2 0 [ ~ e ~ o ~ O ~ O ~ ~ ' ' e ~
( ~ ~ " ' e ' * e 2 O % DIGLYCERIDES IN TRIGLCERIDE$
lot l I I I
S t 0 l S 2 0
D A Y S S T O R A G E A T 2 1 C
FIG. 8. E f f e c t o f d i g i y c e r i d e s o n t h e r a t e o f c r y ~ a l l i z a t i o n o f palm
o i l tri~ycerides (taken from reL 30). Sample worked in mini-rotator
e--a--o, Sample crystallized in NMR r o b e
247
PHYSICAL PROPERTIES AND MIXTURES OF OILS
unusually low amount s of diglycerides, 3.7% and 5.4%, one
oil being expressed directly from the fruit in the l aborat ory
and the other a specially selected, Lot ox, palm oil).
The results in Figure 8 also show t hat the final level of
SFC and the rate at which it is attained are substantially
affected by the crystallization method. Other oils do show
a similar effect, but it seems t o be particularly pronounced
in PO.
Recent results from PORIM also show the post-harden-
ing effect clearly and its strong dependence on the met hod
of crystallization and the amount of working given to the
sample (Fig. 9).
One practical consequence of the post-hardening of PO
is shown in Figure 10, where the creaming power of a palm-
based margarine is shown to be strongly dependent on stor-
age time.
The rate of crystallization can be increased and the post-
hardening probl em largely eliminated by interesterification.
Pa l m K e r n e l a n d C o c o n u t O i l s
These t wo laurie oils contain mainly saturated triglycerides,
with the medi um chain acids laurie and myristic predomi-
nating. The result is a very compl ex mi xt ure of triglycerides
with properties changing onl y slightly with f at t y acid chain
length from one triglyceride t o the next, e.g. LMM, LMP,
MMP and MMM. Both oils behave like a single phase and,
although bot h can be fractionated, there is no clearcut
phase separation as is found with PO. The pol ymorphi sm is
correspondingly simple with a ~'-2 pol ymor ph occurring
under almost all circumstances. An c~ phase can be obtained
onl y by rapid cooling, and it easily transforms t o the stable
~' pol ymor ph (29). I t is possible t hat a/3 phase develops
after several mont hs (34). Hydrogenated PK and CN and
their stearins show similar behavior. All laurie fats crystal-
lize rapidly (35), which makes t hem ideally suited for con-
fect i onery coatings and molded compound chocolate
products.
M i x t u r e s o f P a l m , P a l m K e r n e l a n d C o c o n u t O i l s
Because of molecular size differences, PO and the t wo
laurie oils are incompatible with each other and form
leOO
~ 1 2 0 0
w
o _ z ,ooo
t -
Ug 8 O O
Z
uJ
O.
6 O O
400
WORKING UNIT AT 800 RP.
200 .... I I I I I I
0 & 8 12 lS 20 2/~
STORAGE T I M E ( DAYS)
FIG. 9. Penetration of RBD Palm Oil o n s t o r a g e a t 20 C (taken from
ref. 11).
eutectic mixtures (1,16). The eutectic interaction is clearly
shown by the mi ni ma in the SFC and Slip MP curves in
Figures 1 and 2.
Figure 11 shows a response surface diagram of the SFC
of blends of palm stearin, palm olein and palm kernel oil.
The eutectic interaction is indicated by the maxi mum in
t he iso-SFC lines, and it can be used t o advantage in t he
blending of fats for many food uses. Formerl y, laurie oils
were used extensively in margarines. Now they are little
,,=,
O
13..
O
Z
~E
<
r,,,,
o
1 " 5 - -
/ i b ' ~ " ~ STORED tN WAREHOUSE
STORED AT 20 C " ~
i.3
1-2 I l , I
O 7 I / , 30
STORAGE TIME {DAYS)
FIG. 10. Creaming power of margarine o n s t o r a g e ( Cr e a mi n g p o w e r
= specific volume of standard batter after 6 rain whipping under test
conditions).
50
40
Z
30
<
LU
U3
~ 20
10
t 0 20 30 40 50
% PALM KERNEL OLEIN
FIG. 11. S o l i d F a t C o n t e n t a t 10 C f o r b l e n d s of palm stearin, palm
kernel olein and palm oi l . R e s p o n s e curves calculated by multiple
regression f r o m b l e n d s p r e p a r e d a t 5-10% intervals (taken from
ref. 1).
JAOCS, V01.62, no. 2 (February 1985)
248
R.E. TIMMS
used due to their high prices relative to non-lauric oils.
I t has been suggested t hat the eutectic interaction be
used to advantage in the blending of oils for frying (16).
Blends of PO and lauric oils were found to have lower MP's
and bet t er cold stability t han the base oils. However, al-
though the lower MP is potentially useful, blends of lauric
and nonqauric oils are not usually recommended for frying
because of excessive foaming.
Blends of PO and palm stearin and palm olein and palm
stearin are used for shortenings, especially in Malaysia.
However, even though atl the component s originate from
PO it should not be expect ed t hat the physical properties of
the blends are linearly related to the properties of the com-
ponents. In t heory, a logarithmic curve is expected (9). A
curve is observed in practice, as shown in Figure 12.
/
z ,,
~ z
W - /
IE /
/
m /
l
l
1
l
l
I
l
/
l
/
0 20 40 60 80 100
*/. PALM STEARIN
F I G. 1 2 . Sl i p Me l t i ng P o i n t s o f b l e n d s o f Palm Olein and Palm
St eari n.
ACKNOWLEDGMENTS
I am grat eful t o E. M. Gob, F. H. Foo, N. C. Wong and t hei r st af f
f or experi ment al work, and t o F.C.H. Oh (PORIM) for det ermi ni ng
heat s of fusion.
REFERENCES
1. Timms, R. E. , Fat s for t he Fut ure, t he proceedings of t he
I nt er nat i onal Conference on Oils, Fat s & Waxes, edi t ed by
Brooker, S.G., A. Renwick, S,F. Hannam and L. Eyres, Duro-
mar k Publishing, Auckland, New Zealand, 1963, pp. 25-28,
2. Timms, R.E., Prog. Lipid Res. 23: 1 (1984).
3. Meara, M.L., Physical Properties of Oils and Fats, Scientific
and Technical SurveysNo. 110, Leat herhead Food R A (1978).
4. Formo, M.W., in Bailey' s Indust ri al Oil and Fat s Products,
edi t ed by D. Swern, 4t h edn., J ohn Wiley & Sons, New York,
1979, pp. 177-232.
5. Cocks, LV. , and C. van Rede, Labor at or y Handbook f or Oil
and Fat Analysts, Academic Press, London and New York
(1966).
6. Cornelius, J.A., Prog. Chem. Fat s ot her Lipids 15:5 (1977).
7. Clark, P.E., C.R. Waldeland and R.P. Cross, Ind. Eng. Chem.
38: 350 (1946).
8. Chong, C.L., PORIM Repor t PO(58)83.
9, Hannewijk, J., A.J. Haighton and P.W. Hendrikse, in Analysis
and Charact eri zat i on o f Oils, Fat s and Fat Products, edi t ed
by H.A. Boekenoogen, Interscience, London, 1964, pp. 119-
182.
10. Timms, ILE., Chem. Phy~ Lipids 21: 113 (1978).
11. F.C.H. Oh, Unpubl i shed results, PORIM (1984).
12. Timms, R.E., Aust. J. Dairy Technol . 35: 47 (1980).
13. Wille, R. L, and E.S. Lut t on, JAOCS 43: 491 (1966).
14. Bracco, U., A. Di effenbacher and L Kolarovic, JAOCS 58: 6
(1981).
15. Battaglia, 1L, and J. Mitiska, Mitt. Gebi et e Lebensm. Hyg.
74: 156 (1983).
16. Archier, P., and C. Bouvron, Oldagineux 32: 8 (1977).
17. Rossell, J.B., in Food Indust ri es Manual, edi t ed by M.D,
Ranken, Leonard Hill, Glasgow and London, 1984, Ch. 5.
18, Pardun, H., Analyse der Nahrungsfette, Paul Parey, Berlin
and Hamburg (1976).
19. Madison, B. L, and R~C. Hill, JAOCS 55: 328 (1978).
20. Mills, B. L, and F.R. van de Voort , JAOCS 58: 776 (1981).
21. Van den Enden, J.C., A.J. Haighton, K. van Putte, LF. Ver-
maas and D. Waddington, Fet t e Seifen Ansrri chm. 80: 180
(1978).
22. Waddington, D., i n Fat s and Oils: Chemi st ry and Technol ogy,
edi t ed by Hamilton, R.J., and A, Bhati, Applied Science
Publishers, London, 1980, pp. 25-45.
23. Walker, R.C., andW. A. Bosin, JAOCS 48: 50( 1971) .
24. Jacobsberg~ B., and C.H. Oh, JAOCS 53: 609 (1976).
25. Goh, E.M., and R.E. Timms, JAOCS 62 (In press).
26. Deroanne, C., M. Severin and B. Wathelet, Lebensm: Wi ss
Technol. 9: 304 (1976).
27. Deroanne, C., J.P. Wat hel et and M. Severin, Rev. Franc. Corps
Gras 23: 27 (1976).
28. Persmark' U., K.A. Melin and P-O. St~hl, Riv. ItaL Sost. Grasse
53: 301 (1976).
29. Riiner, U., Lebensm.-Wis~ Technok 3: 101 (1970).
30. Berger, K.G., and W.B. Wright, Crystallization Behavior of
Palm Oil, present ed at ISF Conference, Marseilles, 1976.
31. Okiy, D.A., W.B. Wright, K.G. Berger and I.D. Mort on, J,
Sci. Fd. Agile. 29: 1061 (1978).
32. Kawamura, K., JAOCS 56: 753 (1979).
33. Kawamura, K., JAOCS 57: 48 (1980).
34. Noorden, A.C., Stl'sswaren Tech. Wirtsch. 26: 318 (1982).
35. Rossell, J.B., JAOCS 52: 505 (1975).
36. Thi s work.
37. Tan, B.K., and F.C.H. Oh, PORIM Technology, No. 3, May
(1981).
38. Tan, B.K., and F.C.H. Oh, Ibid., No. 4, May (1981).
39. Siew, W. L, and K.G. Berger, Ibid., No. 6, Sept. (1981).
40. Kubota, K., S. Kurishu and K. Suzuki, Ni ppon Shokuhi n
Kogyo Gakkaishi 29: 195 (1982).
JAOCS, Vol. 62, no. 2 (February 1985)
249
SESSION II DI SCUSSI ON
Session I i Discussion
The following questions, answers and comment s were pre-
sented during the informal discussion held at the conclusion
of the session.
Q.. When you meas ur e " c a r o t e n e " c o n t e n t , wh a t do you mean?
What anal yt i cal me t h o d was used?
Goh: Ca r ot e noi ds have t o be anal yzed b y c hr oma t ogr a phy and UV -
visible me a s ur e me nt .
Q.. Woul d y o u ki ndl y dwel l a l i t t l e f ur t he r on t he possi bl e ant i eancer
agent f ound in t he mi nor c ons t i t ue nt s of pal m oil? wh a t is i t
speci fi cal l y? wh a t are t h e pr os pe c t s so far~ What t ype s of cancer
are a f f e c t e d by t hi s / t hes e agentsP
Gob.- Ant i cancer agent s i n a pr ot ect i ve sense are possi bl e f r om car o-
t e ne s and pr ecur s or s o f car ot enes. Ther e are ma n y l ong t e r m and
s hor t t e r m e xpe r i me nt s bei ng carri ed o u t at PORI M f or pal m oil
and f or car ot ene ri ch f o o d s i n o t h e r count r i es.
Q: The t oc ophe r ol c ont e nt s i n PFAD wer e given as 150- 8500 p p m
in one o f your slides. Coul d you l et us know wh a t coul d be t he
causes o f such wi de var i at i on?
Goh: Toc ophe r ol s can be degr aded t her mal l y and b y oxi da t i on.
Obvi ousl y, gr eat care s houl d be exer ci sed dur i ng r ef i ni ng.
Comme nt , K. G. Berger: The r ef i ni ng pr oces s a f f e c t s t h e t oc opbe r ol
level t o a di f f e r e nt e x t e n t due t o a di f f e r e nt deodor i zer and t h e
wa y it was used, especi al l y t h e t emper at ur e. In t he St at es, hi gh
de odor i z a t i on t e mpe r a t ur e is used t o r emove t he pest i ci des, b u t
t hi s is n o t necessar y f or pal m oil.
Q: We have obs er ved in Hondur a s and Col ombi a t he f ol l owi ng, I f one
adds a l i t t l e 85% phos phor i c aci d t o a neut r al i zed bl eached pal m
oil and t he n cent r i f uges ( i n a l abor at or y) , a dar k pr eci pi t at e
f or ms . What ki nd o f mat er i al can t hi s be?
Gob: The t hi ng t o n o t e is t ha t col l oi dal i mpur i t i es ar e dest abi l i zed
and can be pr eci pi t at ed. As t o c ompos i t i on o f t h e cent r i f uged
pr oduc t , one nor mal l y f i nds i nor gani c i mpur i t i es ( Fe, Ca, Mg,
PO~, et c. ) as well as or gani c i mpur i t i es (cellulase, phenol i c
mat er i al s, et c. ) .
Q: Is t oc ophe r ol de t e r mi na t i on by t he DPPH Me t hod sui t abl e f or
de odor i z e d oil? I f n o t , why?
Goh: The DPPH me t h o d meas ur es t h e t ot al a mount o f r educi ng
s ubs t ances in t h e oil. It t he r e f or e may n o t i ndi cat e t he t r ue level
o f t oc ophe r ol s and t oc ot r i e nol s in pal m oil in vi ew o f t h e f act
t ha t pal m oil cont ai ns a numbe r of u n k n o wn s ubs t ances and also
t he possi bi l i t y o f t he f or ma t i on o f r educi ng s ubs t ances dur i ng
t h e r ef i ni ng pr ocess.
Q: The SFI and SFC da t a f or pal m oil and pal m oil f r act i ons ar e
ver y di f f e r e nt f r om each ot he r . Si nce i n f or mul a t i on SFI is a ver y
i mp o r t a n t pa r a me t e r one woul d l i ke t o have compar abl e r esul t s.
The AOCS SFI me t h o d s t at es t ha t i t is valid onl y f or f at s havi ng
an SFI o f l ess t han 50 at 10 C, a nd mo s t pal m oi l f r act i ons have
SFI over 50 at 10 C. Is t her e a modi f i e d SFI me t h o d f or pal m oil?
I f so, pl ease give det ai l s. What da t a are mo s t r epr es ent at i ve o f
sol i d c o n t e n t at 40 C, SFI or SFC? Al so, is t he r e any cor r el at i on
al ready est abl i shed b e t we e n SFI and SFC? Pl ease c o mme n t .
Ti mms : Fi r st , as far as I know t her e is no modi f i e d me t h o d f or f at s
wi t h SFI above 50. We and ot he r peopl e j us t use t he me t h o d as
gi ven. Second, SFC b y NMR is cl oser t o t he abs ol ut e c o n t e n t o f
sol i d t ha n SFI , as expl ai ned in my t al k. Dat a o n SFI and SFC by
NMR have been gi ven in J AOCS b y Madi son and Hill, and ot her s .
Dat a o n di l a r ome t r y and SFC have be e n gi ven b y wor ke r s f r om
Uni l ever in Fe t t e , Sei f en, Ans t r i chmi t t eL ( Det ai l ed r ef er ences
and c o mme n t s are gi ven in my r e c e nt revi ew in Progress in Li pi d
Resear ch. )
Q: In your sl i de s howi ng var i at i on in slip mel t i ng poi nt s , di d you
i nvest i gat e i f t he l ower mel t i ng poi nt s wer e due t o l ack o f st abi l -
i zat i on on a c c o u n t o f hi ghe r F F A or di gl ycer i des (DG)?
Ti mms : No, we di d n o t i nvest i gat e i f l ower mel t i ng poi nt s (MPs)
wer e due t o t ack o f st abi l i zat i on due t o hi gher FFA and DG.
However , i t is n o t l i kel y because t he r e was no st at i st i cal cor r e-
l at i on b e t we e n DG and MP or FFA and MP, and we f i nd t ha t
4 hr s st abi l i zat i on is adequat e f or pal m oi l ; we used 16 hr s as
r e c o mme n d e d by PORI M.
Comme nt , Dr . M. S. A. Kheiri~ Ther e is a cor r el at i on b e t we e n C4s
and mel t i ng poi nt .
Q: The vi scosi t y f i gur es y o u s how are u p t o 50 C onl y. At t hi s t em-
per at ur e pal m oil will still have s ome " me mo r y " o f i t s cr yst al l i ne
st at e. Vi scosi t y is i mp o r t a n t f or t he dr ai nage o f f r i ed f oods , and
is assessed at 100 C or hi gher f or t hi s pur pos e . Do you have any
fi gures?
Ti mms : All our 50 C dat a was obt ai ned o n oi l s pr evi ousl y he a t e d t o
80 C, so no i nt er nal me mo r y shoul d per si st . We have n o t mea-
sur ed vi scosi t y at 100 C becaus e o f t h e danger o f oxi da t i on.
However , r esul t s up t o 80 C have s hown t h a t t h e t heor et i cal l og
(vi scosi t y) vs. 1/ T r el at i ons hi p i s obs er ved and so t h e r esul t s coul d
be ext r apol at ed t o 100 C.
Q: Has t he speaker any vi ews on t he di f f e r e nt NMR appr oaches
a dopt e d by Pr axi s and BrukerP Has h e any vi ew on t he r e c e nt l y
publ i s hed AOCS me t h o d f or SFC by pNMR?
Timms~ Ther e are t hr e e i ns t r ume nt s f or NMR me a s ur e me nt : Pr axi s -
pul se; Ne wp o r t - c ont i nuous wave; and Br a k e r - pul se. Bot h t he
Pr axi s and t h e Ne wp o r t meas ur e onl y t he l i qui d f a t signal. Ther e-
f or e, t h e sampl e has t o be wei ghed, a r ef er ence oi l has t o be used
and t he SFC r esul t is obt a i ne d onl y at t h e end of a seri es o f
r eadi ngs at di f f e r e nt t e mpe r a t ur e s . Thi s is t he so-cal l ed i ndi r ect
me t h o d . The Bruker meas ur es b o t h solid and l i qui d f at signals.
Ther ef or e, t her e is no need t o wei gh t he sampl e, and t h e SFC
r e mi t is avai l abl e i mmedi at el y. Thi s is t h e di r e c t me t h o d and has
been devel oped wi t h and a d o p t e d b y Uni l ever in Eur ope . The
di r ect me t h o d us es an a ppr oxi ma t i on in t h e cal cul at i on, b u t f or
pr act i cal pur pos e s t hi s doe s n o t pr oduc e si gni f i cant er r or s. In
any case t he Br uker al so ma y be used f or i ndi r ect me a s ur e me nt s .
The AOCS t ent at i ve me t h o d f or " S F I " b y NMR r ef er s onl y t o
t h e use o f t h e Praxi s i ns t r ume nt .
JAOCS, Vol. 62, no. 2 (February t 985)