December, 1931 I N D U S T R I A L A N D ENGINEERING CHEMISTRY 1421

peratures, some of the results being shown graphically in
Figure 2. It is seen that for various combinations of fuel,
temperature, and humidity, the difference in gross and net
heating values per kilogram of water formed may be any-
thing from 0 to 595 Gal. per kg. (0 to 1070 B. t. u. per pound).
Thermodynamic Proof of Difference
In making the foregoing computations it was observed
that the difference between gross and net heating values,
at constant pressure, per pound of water vapor condensed
was equal to the latent heat of water a t the final tempera-
ture. The proof that this is true is as follows:
It has already been shown
HYPOTK f TICA
that the difference b e t w e e n
gross and net heating values is
equal to the difference between
heat of saturated vapor at constant pressure for this range
is about constant, and the decrease in i will be equal to
dQ = di = cP ( t c - ti)
since dQ = d i for a constant-pressure process.
It remains to be proved that the end of the hypothetical
path is a t B. The water vapor a t B is at a low pressure
corresponding to the temperature t l , whereas at the end
of the hypothetical path the pressure corresponds to that
at t,. However, the product of PV for both cases is prac-
tically the same, owing to the low pressures involved, which
makes the value of i the same and fixes the end of the hy-
pothetical path a t B. Then since the d i , following any path
between two points, must be the same,
- j’, = cp (tc - tl) + TI

the decrease in thermodynamic when r is the latent heat a t tl, and also represents di from
potential, i, for the actual path B to C. Rearranging the expression, we have
and the decrease for the hypo-
thetical path. In the actual (;‘A - i’c) - c p (tc - tl) = 11

I EKrQnpv
1 cooling piocess the water vapor
the left side being by definition the difference between the
Figure 3-T-E Diagram for
becomes saturated a t A (Fig-
Water Vapor ure 3). An infinitesimal drop gross and net heating values. This has been checked and
in temperature will cause an in- found true for various conditions, so that the following
finitesimal mass of vapor to condense and in so doing move general rule can be accepted: The difference between the
across the diagram to D. Further cooling will cause more va- gross and net heating values of a fuel burned a t constant
por to condense and cause the liquid already a t D to be cooled. atmospheric pressure is equal to the weight of water vapor
The f i s t particle cooling will follow the path A-D-C; the actually condensed multiplied by the latent heat of steam
last particle will follow the path B-C. However, since i a t the initial temperature of the mixture, which is also the
is a point function temperature to which the products are cooled.
di = i n A- i’,
Literature Cited
regardless of the path.
For the purely hypothetical process of cooling the vapor (1) Goodenough, ’‘Principles of Thermodynamics,” pp. 294-1, Henry Holt
1927.
from t, to tl without condensing, which is a constant-pres- (2) Goodenough and Felbeck, Univ. of Ill. Eng. Expt. Sta., BuU. 180,
sure process, any path may be drawn. However, the specific 138 (1924).

Chemical Composition of Avocado Seed’

LeRoy S. Weatherby and D. Glenn Sorber
CHEMICAL
LABORATORY, OF SOUTHERN
UNIVERSITY Los ANGELES.CALIF.
CALIFORNIA,

R E C E N T years the Quantitative determinations have been made of the Very early in the history of

I large increase of avocado

production and the rapid
growth of the industry have
composition of the seed of the avocado (both Mexican
and Fuerte varieties), including moisture, ash, acidity,
nitrogen, protein, reducing sugars, sucrose, starch,
organic chemistry, Avequin
(9)in 1831 and Melsens (8)in
1839 found avocado seed to
s t i m u l a t e d search for by- pentosans, crude fiber, and ether extract. be the source of d - p e r s e i t .
products to utilize the culls. a-d-Mannoheptite was prepared from the seed and So far as is known, no mention
Avocado dehydration, pres- identified. was made of any of the other
ervation in freezing storage, A flour consisting largely of starch was prepared and constituents until 1920 when
c a n n i n g , use in ice cream, identified as amylum. a report (9) of various oil-
cocktail, m a y o n n a i s e , and yielding seeds was made by
sandwich spreads have been investigated (4). Methods of ex- the food-testing laboratory of the Surinam. This report
traction and refining, and possible uses of the oil are being states that the seed of Persea gratissima contains only 8 per
studied.2 All of these, however, have to do with the pulp, cent fat and 2 per cent saponin, to which the poisonous char-
while the seed, comprising from 8 to 25 per cent of the fruit, acter is ascribed. Jamieson et al, (7) found but 2.2 per cent
apparently has never been considered. I n attacking the oil in an air-dried crushed sample.
problem of preparing by-products from the seed, it was con-
Quantitative Determinations
sidered that a knowledge of the chemical composition would
properly serve as a basis. The seeds available for the work here reported were from
1 Received JUIY16, 1931. Presented before the Intersectional Meet- varieties Of Persea drymifolia Of the Mexican race of horticul-
ing of the American Chemical Society, in conjunction with the National ture, and the Fuerte was classed as a hybrid of p. drymifolia
Meeting of the American Association for the Advancement of Science,
Pasadena, Calif., June 19, 1931.
and p. americana of the ~ ~race (11). ~The varie- t ~
2 W o r k on the oil is being carried on in the laboratories of the University ties Of these two races are not separated into two
of Southern California. species, as some authorities list them all as belonging to P
1422 INDUSTIZIAL AiVD E N @'NEERING CHEMISTRY Val. 23, No. 12
omerieana,also known by some horticulturists as P. grutissiniu referred to Avequin (2). This was not verified, as only the
GIirtn (10). determination of total acid soluble in cold water, as directed in
After removing tlie outer hard brown coats, which were thetentativemethod{Z),wasfollowed. Tho acidity,calculated
discarded, the large white seeds were passed through a Russwin as the number of cubic centimeters of 1 N sodium hydroxide
food chopper three times, using a nut butter cutter. The required to neutralize the water extract from 1 gram of seed,
material was then thoroughly mixed, and portions for the gave, for the Mexican varieties, an average of 0.30 cc. or
various determinations weighed out in duplicate. 0.64 cc. reduced to moisture-free basis, and 0.32 ec. and 0.65 cc.
The methods of analysis of the Association of Official (moisture-Freebasis) for the Fuerte.
Agricultural Chemists ( 1 ) were used for all quantitative work. Table I is a summary of results that can be classed as purely
Most of the methods selectcd were from those giveii for the quantitative composition data.
analysis of feeding stuffs, as the ground material seemed to
Tabie I-Composlrion of Avocado Seed
resemble this group more than any other. MexienN VhRIBTIBS FUSRTB VAPIBTIB8
Ether extract was determined by niearis of tho ofiicial Moirtuir. % 53.61 52.14 51.36 50.56 49.01
direct method, extractiiigin a Sorhlet for 113hours.
1 24 ... 1.34
c
2.98 ... 2.70
0.33 ... 0.39
0.92 ... 0.79
2.38 ... 2.43
5.72 ... 4.95
2.58 .., 1.60
.. 5.40 ... 3.24
..
..
0.92
1.91
...
...
0.61
1.23
3.50 2.21
7.31 ... 4.47
27.54 2 9 . 00
57.21 50.87
1.78 ... 1.64
3.62 ... 3.33 ..
.. 2.15 ... 2.04 ..
.. 4.50 ... 4.12
Figure I-&Perself 01 Ir-d-MannOheptlfe 3.78 4.14 ... ... 3.66
from Avoeado Seed. 250 x 9.08 8.66 ... ... 7.28

The results of the first weighing of the ether extract from the 0.70 0.91 1.00 0.99 1.10
1.70 1.90 2.07 2.w 2.21
seeds of the Mexican varieties, calciilated to percentage, gave
7.76 ... 9.25
an average of 0.80. This decreased with successive drying 16.22 ... 18.71
periods until it reached 0.70 per cent. The second set of By the direct acid-hydrolysis method.
Mexicans showed irregular losses at first, as indicated by three
weighings during the first 3.5 hours, whereas the loss was Tannin is present, as indicated by qualitative tests which
slight and uniform during the second drying period of 3.5 Haas and Hill (G) have taken from Trimble. The water
hours. The results, after drying for 7 hours, checked at 1.00 extract (washings from the starch determination of the
per cent. An addit.ional 20 hours in the oven a t 100' C . Mexican varieties) gave, with ferric chloride, green color and
brought the percentage down to 0.82. The extract from the precipitate; lime water, light pink precipitate, becoming red
Fuerte seeds was esdimated a t 1.10 per cent, which an addi-
tiopal drying of 20 hours lowered to 1.00 per cent. This
continued loss on drying seems to indicate that either the
ether extract is somewhat volatile, or decomposition takes
place a t this temperature.
The extract was a light-brown sticky gummy mass not
easily soluble in anhydrous ether, even though extract4 witti
it. An attempt was made to secure its refractive index at
different temperatures, but the results were far from satis-
factory. No reading of any kind could be secured of the
extract much below 35" C., whereas tlie oil from tlie piilp was
liquid at ordinary temperature, and readings could he taken
at 20" C.
So far as t.hey have been compared, the ext,ract of the seed
has none of the characteristics of tlie oil from the pulp.
Others have assumed i t to he an oil or fat; as the report on the
oil-yielding seeds of Dutch Guiana (ii), previously mentioned, Figwe 2-Avocado-Seed
Granuies. 250 x
Starch
says, the seeds contain 8 per cent fat and the fiesh of the fruit
only 5 per cent fat. Jamieson et al. ( 7 ) ,who were working with and brown; bromine water, yellow precipitate, becoming
Fuerte avocados, found that "the large seed of the frnit brown. Theae reactions, according to Trimhle, are character-
contains very little oil; an air-dried crushed sample of the istic of tannins containing 5Cb60 per cent carbon. This group
seed contained only 2.2 per cent of oil." This checks very includes tanning of osk hark, kino, canaigre ratanhia, and
closely with the 2 and 2.21 per cent of extract obtained from catechu.
the Fuerte seed, as will be noted in the summary of analytical Investigations Relative to Composition and By-Products
data. No evidence is given, however, to support the as-
sumption that the substance is an oil. Other kinds of investigations relative to cornpsition and
Wehmer (12) listed malic acid as occurring in tile seed and by-products were carried on; while none of these solve the
 ... .., . .. . ...... .
December. 1931 INDUSTRIAL A N D ENGINE8EING CHBiWIS'TR1'
problem of finding uses for the seed, they do give further in-
sight into the nature of the material studied.
In tho first set of determinations, ten seeds of the Mexican
race (varieties of about average size) were selected. Thcy
weighed 276.95 grams and their coats 6.12 grams or 2.22 per
cent.
The seeds have about the same consistency as chestnuts and
can be chewed quite as easily. They have a very bitter as-
tringent taste which roasting fails to destroy and which
persists to some extent even after grinding aiid boiling. It is
entirely removed, however, by extracting with 80 per cent
alcohol.
Within a few minutes after the seeds were ground, they
turned a reddish bronn (very likely due to an oxidase) and
retained this color when dry. In trying to secure a ground
sample without this color, a portion of it was allowed to drop
direc.tly from the chopper into a saturated salt solution. This
remained white as long as it was below the surface of the solu-
tion, but as soon as it was exposed to the air to dry, the color
appeared even after having been in the solution for days.
Fiewe 3-Avollado-Seed Starch Grant81
with Crosaed Nichols Prisms. 250 x
During grinding and until dry, the seed material uf the
Mexicans gave off a strong anise-like odor. I n the Fuerte this
was much fainter. The leaves and bark of the trees possess
the same odor. According to Popeiioe (11) this odor in the
leaves is a distinguishing characteristic between P.dry9nijdiu
(Mexican) and P. ammicana (Guatemalan). It occurs in
the former but not the latter. Gildemeister and Hoffmann ( 5 )
describe this anise-like odor and the oil obtained from both
the leaves and b a r k "In addition to small amounts of
anethole, methglchicol =%Is found as its principle constituent,
the first known natural occurrence of this substance. The
presence of methylchavicol was established by its conversion
into anethole and oxidation to homoanisic acid."
Two hundred grams of the ground seeds were steam-distilled
with water. The distillate, caught in an oil bottle, possessed
give rise to the anise-like odor of the &ds, since they ha-& been
found in both the bark and leaves, and since the same odor is
common to all three.
Nearly 2 kg. of seeds were ground in the same manner as for
analysis, air-dried. and placed into two cloth bags that fitted
into l.&liter beakers. Eighty per cent alcohol was poured
over each and heated to boiling on a steam bath. The solution
was then filtered into a Miter Erlenmeyer Bask which w a s placed
on an electric hat date. and the alcohol was distilled back onto
the bags in the beaker;. After this process was repeated once
or twice, the flask full of the clear dark reddish brown extract
was allowed to stand overnight, and in some cases several days,
after which, small round whjte masses of crystals precipitated
out. The precipitate was collected on a filter paper. washed
two or three times with 80 per cent alcohol, and put aside to dry.
1423
The precipitate examined under the rnicroscope wits found
to be made up of fine needle-like crystals, some of them arrang-
ing themselves in fan-shaped masses. When crystallized on
a microscopic slide, they proved to be rhombic crystals,
crystallizing in tufts usually at 90" to each other. Thefirst
melting point obtained was 184" C. and, after one recrystalliea-
tion, was increased to 187" C.
The crystals proved to be rl-perseit or ad-mannoheptite, a
heptahydroxy alcohol first found by Avequin (Z) in 1831 in
avocado seed (Figure 1).
The optical rotation of 0.8 gram of the material of the first
crystallization in 10 cc. of saturated borax solution in a I-dm.
tube gave, as an average of six readings, +1.18" Ventzke
sugar scale (corrected), or +0.41° angular rotation D. I n
discussing the identity of d-manno1:eptit.e and perseit, R r o m e
(3) says that Fischer and Passmore found the rotation of syn-
tlietic d-mannoheptite to be +0.3S0 (0.4 gram of the substance
in 5 cc. saturated borax solution in a 1-dm. tube), and natural
perseit 0.39'.
The brown extract remaining after the perseit crystals vere
filtered out was coneentrated by distilling off the alcohol to a
low point and continuing evaporation in an evaporation dish
on the steam bath. When nearly a11 the alcohol had been
removed, a thick sticky gummy dark-brown mass floated on
the remaining water. This was collected and found to be
difficultly soluble in water. I t possessed a very bitter as-
tringent taste and formed a gummy coating on the tongne
and teeth, which persisted for some time.
Some of the ground-seed material, prepared in the same way
as for analysis, was spread out on large sheets of paper and
dricd. It contained a considerable portion of very fine light-
brown powder. This Aour was separated by sifting through a
sieve of 100 mesh. The flour was found by examination under
a microscope to consist largely of pcar-shaped starch grains,
whicii gave the characteristic cross with polarized light and
was turned blue by iodine, thus identifying it as common
starch, amylum (Figures 2 and 3).
Couclusions
Avocado seed is made up largely of water, starch, sugar,
protein, with but a small amount of crude fiber. There is a
possibility of its use as a food product or feeding stuff,though
the small amount of bitter-astringcnt principle present might
have to be rcmoved.
Perseit might figure as a by-product if a use for it could be
found.
There remains in the neighborhood of 16 to 18 per cent
material (moisture-free basis) to be determined quantitatively.
This includes perseit, tanning, pectic substances, gums, and
possibly glucosides, a bitter principle, and other unidentified
compounds.
Literature Cited
(1) Asrodation Official Agri~ultural Chemistts, Methods of Analydn,
. .
(3) Brownr."A Handbook ofS,rgar Analysls,('Chapmao and Hall, London,
1913.
(4) Cruen~and Harrold. Calif. Avocado Aasoc., Ann. ReDI., 1911, 34.
( 5 ) Gildemdsfei a d HoBmano, "The volatile oils." p. 478, Wlley, 1916.
..
I B i Haas and Hill. "Introduction to the Chemistry of Plant Product%"
p. 206, Longmirnr, 1913.
(7) Jarnierun, Baughman.and Hann. Oil ond Pat Ind., 6, 202-7 (1928).
( 8 ) Melsm~,Ann. chim. oh%. IBS% 109.
(9) O l i r n Veflen, No. 30. 387 (1820).
(IO) Pope, Hawaii Agr. Expt. Sa., Bull. 61, 3 (1821).
(11) Popenoe, "Maniial of Tropical sod Subtropical Fz'ruit~.1(Maemillan.
1920.
(12) Wehmer, "Die PRanrenstto(fe;' Gustao-Fircher. Jena. 1911