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Masters Theses 1896 - February 2014 Dissertations and Theses

1914

The composition and feeding value of cocoa shells

G. Scott Fowler
University of Massachusetts Amherst

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February 2014. Paper 1221.
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3iaDbb 0D1S SbflE 7

The Composition and Feeding Value

of Cocoa Shells

G. Scott Fowler
 MASSACHUSETTS
STATE COLLEGE

DATE DUE

UNIVERSITY OF MASSACHUSETTS
LIBRARY

PHYS
SCI
Lp

$268
1914
Phy, F785 ice
A
hesis
 THESIS

FOR THE QCGREE OF

or SCIENCE.

AGRICUUTURAL COLLfcUB,

by

o. scott rcvuoi.

, kASSACHIlStfTTS

1914.
547. 6>3

CHEMISTRY
coupQsrrioH and f£*dihg value

COCOA SHELLS.
 .

VALUE OF COCOA

G. Scott Fowler, B. 5c.

Introduction

Cocoa shslls are the covering of the eeede of a tropical tree

known as Theobrona Cacao, which belonge to the general order Buttoneriaceae.

This tree may be found throughout the tropics, and is extensively cultivated

for its seeds. These seeds are comraonly called cocoa beans, froa the kernel

of which the cocoa and chocolate of commerce are manufactured. The seede ere

ovate in shape, about the sise of an ordinary green kidney bean, and covered

with a thin, red or grey-brown, friable shell or husk.

Information procured from The Salter Baker Company by Professor

V. P. Brooks of the Massachusetts Agricultural Experiment Station, regarding

the annual product ion of shells in the United states givee us some idea of

the world product. Profeeeor Brooke was informed that approximately 6, TOO

tone were produced each year.

Op to the present time most of these shells have been burned , or

otherwise destroyed, ae they have been considered of little value. S<

however, have been ueed as bedding and as food for cattle and shsep.

Purpose of Thesis

The object of thie theeie ie to gain soms further knowledge of the

food constituents of thess shells, and to investigate their digestibility

with the caffein alone or the eaffoin and theobromin together extracted from

them, and comparing the factors obtained with those of untreated shells.
 Igpsriaental Results,

Z. Complete Analysis.

In considering the analysis of thsss shells, first sns finds

considerable data recorded froa analyse 6 mads on various brands froa

different localities. A suaaary of the data compiled by Kenig and other

analysts is given In the following table. Thess results have been re-

calculated to a moisturs frse basis in order that they may be

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II. Nitrogen Constituent .

(a) Alkaloids. — In determining the two principle alkaloids

present, theobromin and caffein, the Official Mothode were modifiod by

using ealoiusi hydroxide in place of magnesium oxide. The purpose of this

substitution was to obtain a substance that could be used in solution so

that the reel due after extraction might be free from an excess of alkali,

thus allowing it to be fed and ite digestibility determined. Three to

five-gram saaplss were used instead of ten-, a lines filter instead of a

Buchner funnel; a tinfoil dish instead of a H •Hoffmsister Sohalohen' or

other suitable glaes dish," and a Soxhlet fat extractor in place of a Tollens,

Johnson or Wiley extractor. The filter paper, used in separating ths bensene

solution of caffein from tho insoluble theobrorain, was extracted with

chloroform into the original flask that contained the mixed alkaloids. The

filter paper may thus be eliminated. This disposal of the paper loaves no

chance of possible reduction of the silver nitrate when heated in the presence

of ammonia. The complete method used is as follows:

Boil from 3 to 5 grams of the ground sample for one-half hour with

250 oc. saturated solution of calcium hydroxide in a 500 cc. Krlenmeyor flack.

Filter through a linen filter, with the aid of suction, and wash once or

twice with hot water. Transfer the material to the same flaek and boil again

for fifteen minutes with 250 cc. calcium hydroxide, then filter and wash as

before. Combine the filtrate, »nd evaporate to dryness in a small tinfoil

dish on the steam bath. Dry this residue at 100° C. from 8 to 12 hours.

Crush the tinfoil dish containing the residue, and place in a Soxhlet*

extraction cartridge. Extract with chloroform in a Soxhlet' s fat extractor

for 8 hours. Heat the flask containing the extract until free from
 7

chloroform, add 50 cc. of anhydrous bentene, and allow to stand over

night at room temperature. Filter and wash thoroughly with bent ana

into a tarod crystallising diah. Dry and waigh thia residue aa oaf fain.

Dry tha flask containing the first residua (also the filter) until frss

from beniene, then free the filter from any theobromin which may be

pressnt by extraction with chloroform into the original flask. Dry the

flask until frss from chloroform, and add 100 es. distilled water, 2 to 3

drops of ammonium hydroxids and an excess of N 20 silver nitrate solution.

Digsst this on a steam bath until free from ammonia, adding water if

necessary. Filter hot through quantitative paper, and wash thoroughly with

hot water. Acidify washings containing the excess of silver nitrate with

a fsw drops nitric acid, which is frse from dissolved oxides of nitrogsn.

Titrate with N 10 lium sulphocyanits solution, using fsrric

sulphats as an indicator. From the silver nitrate taken up by the theo-

bromin the psr cent of theobromin can be calculated. The results obtained

for oaf f sin and theobromin are as follows:

Caff sin Determinations.

weigm •sight •oight •sight Psr cant

Caffsia a Dish Dish Caffein Sampls Caffsia

19.0301 19.0242 .0059 2.7 .218

23.4436 23.4379 .0057 2.7 .211

17.5200 17.5145 .0055 a. .203

20.8287 20.8229 .0058 2.7 .214

20.6982 20.6921 .0061 2.7 .225

Average .214
 . .

Thoobromin Determinations.

Equivalent
10 00. AgNO s Thsobromin
Equivalent minus to 1 oo. Wsight
NH^SCN AgNO, Sxesss AgNO, N 20 AgNOj Thsobromin Sample Thoobromin
CO. 00. 00. grams grant grams Per oont

4.45 8.722 1.28 .01802 .023085 2.7 .854

4.50 8.820 1.18 .01802 .021263 2.7 .787

4.35 8.526 1.47 .01802 .086489 3.7 .981

4.45 8.722 1.28 .01802 .023065 3.7 .854

4.55 8.920 1.08 01802 .019461 3.7 .721

Average .1339

(b) Nitrogen in the Residue.—Two series of determinations were

made to compare the nitrogen contained in the residue when magnesium oxide

was used, and that obtained when calcium hydroxide was used. The data obtained

are ae follows:
 sium Oxide Method.

Nitrogen
Equivalent
, Equivalent Titer to 1 ee.
N 2 HCi M 10 NaQH Difference 1/10 NaQH Nitrogen Nitrogen
oe oc CO. ee. grexw. grame Per cent

10 25 14.22 10.78 .00274 .029537 1.639

10 35 14.40 10.60 .00274 .029044 1.611

10 25 14.15 10.85 .00274 .029722 1.643

10 25 14.20 10.80 .00274 .029592 1.642

10 25 14.12 10.88 .00274 .029811 1.654

Average 1.637

Calcium Hydroxide Method

Nitrogen
Equivalent
Equivalent Titer to 1 ce.
N 2 HC1 N 10 NaCXi NaOH Difference N 10 NaQH Nitrogen Nitrogen
ee. oc ee. co. grame Per cent

25 36.50 16.5 20.00 .0015 .03000 1.

25 36.50 16.6 19.90 .0015 .02985 1.656

36.50 16.8 19.70 .0015 .02955 1.638

36.50 17.2 19.30 .0015 .02891 1.606

36.50 16.7 19.80 .0015 .02970 1.648

Average 1.641

Average of both mot node 1.699

Theee determinations show that either method will give equally gcod

results, the amount of nitrogen in the residue being practically the

a in both eaeee.
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 10

III. Fat Constanta.

The chsmioal and phyaioal constant a of tho fat wars also studisd,

and ths following tabla will show a comparison betwssn than and tho as givsn

in Lswkowitch, "Technology and Analysis of Oils and Fats'*, Vol. IX, page 480,

for "Cocoa Buttsr." Ths averags of five parallel determinations is givsn in

the caae of the chsmioal constants.

Saponifi-
Molting Angls of cation Insoluble Yolatils Iodine
Sp. Q, Point Refraction Numbsr Acids Acids Absorption

Cocoa Shsll
Fat .941 30-34 1.469 192. 11 95.56 .30 33

Cocoa Buttsr .970 28-33 1.466 191.8-194 94.59 .38 34.3-37

Thsss constants are so close that ons would not bs justified In saying that ths

two wars different, as ths same sample, or like samples, will vary as much

depending on age and exposure. The fat was prepared by extracting with benssno,

washing with hot water, and filtering through fine grade filter paper.

IV. Carbohydrates.

A special study of ths particular carbohydrates in the cocoa shslls

was mads, and the important ones dstsrminsd. Traces of reducing sugars, sue rose,

and also starch, were found. Pentosans and galaotans wars present in considerable

quantities. The galaotans were determined by the mucic acid method) ths

pentosans by precipitating as phloroglucid and calculating from Krobor' s tablss

for changing furfural to pentosans. Ths percentages obtainsd are the average

of five determinations except in the caee of the galaotans and pentosans where

the average of ten is givsn.

 "

11

Reducing sugar 9.085 per cent

Sucrose 0.029 f*

Soluble starch 1.420 a

Insoluble rtarch 0.614

Gelactans 7.340

Pentosans 8.290

Others net determined 41.102

Nitrogen free extraet 58.88

All netbods used may be found in "Official Methods.

f. Digestibility.

Tbs second part of this thesis deals with the digestibility of

the eoeoa shells, both in the unaltered state and with certain compounds

extracted from them.

(a) Preparation of Materials. —(1)

The first attempt to obtain an

extracted product was as follows: A quantity of shells was extracted with

warm, dry bensene by allowing then to stand for several days, and then

filtering on a Buchner filter, and washing with bensene. The extracted

material was dried, thoroughly nixed, ground and nixed again. Zt analysed

as follows:
 .

12

Extracted Shell* Unextractod Shells

rithar extract 1.15 per cent 5.22 per cent

Ash 9.45 » 8.94

Fibre 13.04 15.67 a

Protein 10.99 10.24

Theobromin 1.16 .84 M

Caffein — •
.21 it

N. free extract 64.21 58.88 M

Total 100.00 100.00

As these analyses shoved not only a decrease in the fat, but

also a relative increase in the theob renin content, the material was not

considered worthy of further investigation.

(2) A second material was prepared by treating with a cold

saturated solution of calcium hydroxide. Upon the basis of the analytical

methods for the estimation of the caffein and theobromine this treatment

should remove these two alkaloids and also neutralise the acidity, making

the shells more palatable.

The shells, in sufficient quantity to carry on a digestion

experiment, were boated on a steam bath with a saturated solution of calcium

hydroxide for about five hours in 800 ee. beakers. The proportion of

shells to calcium hydroxide solution was one to four. These shells were

drained through cheese cloth, and treated with more calcium hydroxide

solution without heat. This washing process was continued until the sheik

remained slightly alkaline. The residue was drained end dried. Calcium
 .

hydroxide eolution was added to the washings until a considerable quantity

of extract Batter was precipitated out. This precipitate wae filtered,

dried and added to that first obtained. The compound residue wae thoroughly

nixed, ground, nixed again and sampled.

(b) Feeding Experiment Two sheep and the apparatus used in

digestion experiments by ths tSassachusette \gricultural Experiment Station

were placed at my disposal to carry out this investigation.

In a few words the manipulation of the experiment is this:

A basal ration, calculated to just maintain the animal at an equilibrium is

fed each day for a period of fourteen days. About half of each ration is

fed in the morning, and the other half at night, an near twelve hours apart

as possible. The faeces are collected for the laut seven days of ths period

weighed and a tenth portion dried over night at 100 C. These tenth portions

are allowed to stand for a week that they nay attain the sane moiature con-

tent as ths air. They are weighed, and the air-dry matter calculated in the

whole portion. The sun of these whole portions gives the total manure

excreted in the seven days. The seven, tenth portions are united, ground,

passed through a millimeter sieve, thoroughly mixed and analysed. All

calculation are made on the average of the seven daye or on the amount fed,

and excreted in the faeces in a single day.

The basal ration in this experiment consisted of 150 grans of the

analysed, extracted shell- residues with 650 grans English hay and ISO grans

Gluten feed. The analyees of the hay and gluten feed, their digestibility

cosffioiente when fed together and the digestibility coefficients of the

untreated shells were obtained from the records of the Uaasachusette

Agricultural Experiment Station.

+ Thie filtrate wae evaporated to dryness at 100°C., and extracted with dry
chloroform. Thie removed the caffein and theobronin which were subsequently
separated with bensene, caffein being soluble and theobronin insoluble.
 14

• I.

Analyse* of Hay, Gluten, Extracted Sheila and Faeeea of

Sheep V and VI.

Extracted faeces
Shells Hay Gluten Sheep Y Sheep YI

Moisture 7.7C 2.75 8.13 5.64 5.38

Dry natter 92.30 97.25 91.87 94.36 94.62

Total in oach caee 100 per cent.

Compos It ion of Dry Hatter .

Extracted
Sheila Hay Gluten Sheep Y Sheep TI

Protein 14.59 8.29 27.91 13.25 13.88

26.89 6.01 .95 10.63 10.11

Fibre 18.46 31.55 9.32 27.36 25.51

Fat 4.79 2.68 4.94 2.91 2.84

Nitrogen free
extract 35.27 51.47 56.86 45.85 47.66

Table II .

Digestibility Coefficients of Combined Hay and Gluten.

Dry natter Fibre

42 Fat

Protein 67 Nitrogen
free extrsct 70
 Table III.

Const ituents of Rations Fed Sheep ? and VI.

Amount of Nutrients in Dry Mattor Fed

Far coat Amount Dry nitrogen
Material Moisture Fad Matter Ash Protein Fiber Fat free ext.

11.4 650 g. 575.90 34.61 47.74 181.69 15.43 296.43

Gluten 9.3 150 g 136.05 1.29 37.99 12.68 6.72 77.37

7.7 150 g. 138.45 37.22 20.20 25.56 6.63 48.84

Total 850.40 73.12 105.93 219.93 28.78 422.64

Table 17.

Determination of Digestion Coefficients of Shells

Sheep V.

Amount of Rutrients in Dry Matter Fed

Dry Nitrogen
Matter Ash Frotsin Fiber Fat free ext.

Total amount eont 850.40 73.12 105.! 219.93 28.78 422.64

Minns constituents
in 372.349 manure* 351.34 37.34 46.55 96.12 10.22 161.11
Gives amount
ay, Gluten, Shells digested 499.06 35.78 59.38 123.81 18.56 261.53
Minus sen mut
Hay .Gluten digested2 477.01 15.08 57.43 132.17 12.40 261.66
Gives amount
Shells digested 22.05 20.70 1.95 6.16
Per sent shells digested9 15.90 55.61 9.65 92.91
 16

Sheep VI.

Amount of .'utriontc in Dry Katter Ked

Dry Nitrogen
Matter Aah Protein Fiber Fat free ext.

Total amount consumed 850.40 73.12 105.93 219.93 28.78 422.64

Uinua constituents
la 359.80 gma. manure 1 340.44 34.42 47.25 86.84 9.66 162.27
Givaa anount
Hay .Glut en, Sheila digested 509.96 38.70 58.68 133.09 19.12 260.37
Minus amount „
hey, Glut on digested 477.01 15.08 57.43 132.17 12.40 261.66
Givaa amount
Shells digested , 32.95 23.62 1.25 .92 6.72 !
Par cant abolla digested 23.79 63.46 6.18 3.60 101.05

Average of Sheep V and Sheep YI

Coefficient of
Per cent digested Digestibility

Dry matter 19.84 20

A ah 55.54 59

Protein 7.91 8

Fibre —
Fat 96.98 97

Nitrogen free extract

 .

IT

Table f

Digestibility Coefficients Compared

Original Sholle Extracted Sheila

Dry Matter 57 20

Ash 14 59

Protein 11 8

Fibre 51

Fat 100 97

Nitrogen free extract 73

References to Table If.

1. Average amount per day of air-dry faeeee for the seven-day

period.

2. Obtained by Multiplying the sua of the same nutrient in

hay and gluten by its digestibility coefficient.

3. Obtained by dividing the amount of each nutrient digested

by the amount of each nutrient fed in the 150 grame cocoa shells.

Conclusions .

The treatment used, namely extraction with lime water, has not

increased the digestibility of the shells, but rather materially decreased

it. On the basis of the dry matter digested the extracted shells would be

only one-third ae valuable as the unextracted shells, but when one considers

the negative value of the aeh which constitutes nearly all the total dry

matter digested, theee extracted shells are valueless except for the fat,

the digestibility of which is not changed.