D S C E O

C P D
A C E M R M A E

1
P

Place about 10 mL of the oil in a dry test tube of 18-20

mm. diameter. Cool in water or in a suitable freezing
mixture, the temperature of which should be about 5 Safrole Content Congealing Point
degrees lower than the supposed congealing point of the
liquid. To initiate congelation, rub the inner walls of the 100% +11.0°C
tube with a thermometer, or add a small amount of the 90% +7.5°C
substance previously solidified by excessive freezing. The
thermometer should be rubbed quickly up and down in the 80% +4.6°C
mixture in order to cause a rapid congelation throughout,
with its subsequent liberation of heat. The temperature 70% +1.7°C
should be read frequently; at first the rise of temperature 60% -1.3°C
is rapid, but soon approaches a constant value for a brief
interval of time. This value is taken as the congealing point
of the oil. The process described above should be repeated
several times to assure obtaining the true congealing point.

Determine the congealing point of the sassafras oil, and estimate the safrole content from the adjacent
table, it will give values of the safrole content with an accuracy of about 2% if the congealing point is
above 2°C.

The congealing point offers a distinct advantage over the melting point and the
titer, in the case of mixtures, such as essential oils. In determining the
congealing point, the oil is supercooled so that, upon congelation, immediate
C P crystallization with liberation of heat occurs. This results in a rapid rise of
O O temperature, which soon approaches a constant value and remains at this
S V temperature for a period of time. This point is known as the "congealing point."
S C 2
With increasing percentage of crystalline material in an oil, the congealing point
will approach a maximum. Hence, this physical property is a good criterion of
Safrole the percentage of such material. The congealing point is important in the
Congealing
Content evaluation of anise, sassafras and fennel oils, as well as oil of Ocotea cymbarum.
Point
(weight%)

69.1% 2.4°C The thermometer used should be calibrated in 0.1°C units and should be
accurately standardized. A thermometer covering the range of -5°C to +50°C is
73.3% 3.7°C
satisfactory for most determinations. Before the oil is tested, it should be
76% 4.4°C thoroughly dried with sodium sulfate since the presence of small amounts of
water will often materially lower the congealing point. In the case of sassafras
79% 5.2°C oils, it is well to initiate the congelation by the addition of a small piece of solid
safrole since sassafras oil can be congealed only with great difficuly if no "seed"
82% 6.1°C
is used. For a more exact determination of the congealing point, the test tube
85% 6.9°C containing the supercooled oil may be insulated by means of an air jacket. This
is frequently of particular importance when determining congealing points which
86% 7.2°C are much below room temperature, as, for example, the congealing point of
euclayptus (sic) oils. Gildemeister and Hoffmann recommend the use of the
87% 7.5°C Beckman apparatus, frequently used for the determination of molecular weights
88% 7.8°C by the lowering of the freezing point. The use of a larger sample (up to 100 mL)
may make the congealing point sharper. This method has an accuracy of 0.7%
89% 8.0°C according to the paper2.
90% 8.3°C

91% 8.6°C
C A S
92% 8.8°C O O C 2

93% 9.2°C Congealing Safrole content Safrole content

Oil
94% 9.4°C Point (from table) (Hg analysis)

95% 9.7°C A 8.7°C 91.4% 92.1%

96% 10.0°C B 7.2°C 86.0% 85.4%

97% 10.3°C C 8.1°C 89.3% 88.6%

98% 10.6°C

99.5% 11.0°C

1. Guenther's "Essential Oils", Volume 1

2. Journal of Analytical Chemistry, Volume 20, Book 3, 1948 p.248-249