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Group Title: Study of essential oils occurring in the different organs and products of the citrus group in Florida
Title: A study of essential oils occurring in the different organs and products of the citrus group in Florida
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Full Citation
STANDARD VIEW MARC VIEW
Permanent Link: http://ufdc.ufl.edu/UF00055745/00001
 Material Information
Title: A study of essential oils occurring in the different organs and products of the citrus group in Florida
Physical Description: <35> p. : ; 28 cm.
Language: English
Creator: Huff, O. P ( Otis Pascal )
Publication Date: 1917
 Subjects
Subject: Citrus oils -- Florida   ( lcsh )
Essences and essential oils   ( lcsh )
Citrus fruits -- Florida   ( lcsh )
Chemistry thesis M.S   ( lcsh )
Dissertations, Academic -- Chemistry -- UF   ( lcsh )
Genre: bibliography   ( marcgt )
non-fiction   ( marcgt )
 Notes
Thesis: Thesis (M.S.) - University of Florida.
Bibliography: Includes bibliographical references (leaf <35>).
Statement of Responsibility: by O.P. Huff.
General Note: Typewritten copy.
 Record Information
Bibliographic ID: UF00055745
Volume ID: VID00001
Source Institution: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
Resource Identifier: aleph - 001027723
oclc - 18066582
notis - AFA9742

Table of Contents
    Front Cover
        Page i
    Title Page
        Page ii
    Table of Contents
        Page iii
    Main
        Page 1
        Page 2
        Page 3
        Page 4
        Page 5
        Page 6
        Page 7
        Page 8
        Page 9
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        Page 11
        Page 12
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        Page 15
        Page 16
        Page 17
        Page 18
        Page 19
        Page 20
        Page 21
        Page 22
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        Page 27
        Page 28
        Page 29
        Page 30
        Page 31
        Page 32
        Page 33
        Page 34
    Bibliography
        Page 35
Full Text
* ''" t"1'* '' -:'*
t 'E I &4'
- -t


STUDY


.OF


ESSENTIAL


ORGANS


OILS


AND


OCCURRING

PRODUCTS


OF


THE CITRUS


GROUP


FLORIDA


A-THESIS SUBMITTED TO THE COMMITTEE. ON GRADUATE


STUDIES


-FOR


THE DEGREE OF


J > l 1
. MASTER OF SCIENCE IN^.GhfflRtY>
*


a I -
I**. *. .
I* .
a I


4 >
0


UNIVERSITY


O. P


OF FLORIDA


HUFF


JUNE, 1917


I
I' *


I


THE










* K


Investigate ions


on the


Oils


Obtained


from


Citrus


Leaves


Seed,


tuady


Conneoti on


Essential

Citrus G


with


Oils


rroup


Flor ida


with


Espe.o ial


Reference


Theif


Chemical


and


Physi al


Properties.
















C 0


T


N T


Introduction

Definition


General


Charaoteristios


Preparation


Oils


Expression

Distillation

Extraoti on

Analysis

Conolusions

Bibliography


HI
















IN


TROD


UC


T I 0 N


the


ohoioe


this


problem


study


several


factors


were


taken


into


consideration.


Since


the


author


believed


that


this


problem


must


solved


detail


the


future


need


make


no apology


the


appearance


present


work


which


ha s


attempted


lay


bare


some


facts


connection


with


this


subject.


This


subject


seemed


an especially


sul table


applicat ions


problem


Florida


are


evident,


and


only


production


a question


the


various


time


when


-pro duo ts


practical


connect on


with


citrus


fruit


raising will


receive


attention.


writer


felt


that


such


results


as might t


obtain d


would


some


value


aiding


those


may


undertake


investigate


the


matter


farther


writer


trusts


that


thia


thesis


may


serve


awaken


some


interest


subject


and


make


clear


some


points


chemical


value


those


who


are


interested


further work


on this


problem.


-a


t


ni ~ ~ ~ ~ *r a -a -a'4 4' V I.Aa a


WT A Wft 1


~AIIA


Av 4-V k


1 4 44" A


vn ^K


II


IA

















improved

believed


any great


that mechanical


extent.


devices


Furthermore


could


used


author

exclusively


production


these


oitrus


oils..


With


present


and now


present


these


results

s the w


views


in mind,


of his


ork


writer has


investigations as


endeavored


best


Graduate Committee


could,


to act


they


deem


best.


The work was


laboratories a


scholastic


year


carried


University


chemical


of Florida during the


of 1916-17.


The


writer undertook this study at


suggestion


of Dr.


many


Flint,


suggestions


whom he


and much


feels greatly


advice


indebted


pursuit


investigation.


Station


also


University


indebted


of Florida


Experiment


majority of


samples


which


were


procured


from


horticultural


grounds.


Definition


an Essential


Oil


a a -


- a a -.


fIlan amu a a a a S a am a


*


m. A


















and


that


volatile


this


without


definition must


decomposition.


further states


be accepted within


ordinary


limitations


which


are


laid


down


by the common acceptation


of the


words,


no restricted


definition


is either


advantageous


possible.


Allen*


defines an


essential


proximate


principles


occuring


in nature


ready


"ormed,


or as


gluco'ides,


which


by the


action


water


or enzymes


readily undergo


decomi.osition


in to


essential


oils


one


or more


bodies.


General


citrus


Characteristics


oils produced


Citrus


thi s


Oils.


investigation


were


found


possess a


strong characteristic


odor,


and a


pungent


taste.


They were


found


be liquids


ordinary


temperatures,


and


were


practically insoluble


in water,


though


traces


which


went


into


solution rendered


strongly


odoriferous.


These


oils


are


soluble


in most all


organic


solvent s,


such


alcohol,


-chloroform


, petroleum


ether,


acetone


and


benzene.


They were


fou nd


to be


nearly


I















Me th o ds


used


the Preparation


these


Citrus Oils.


The following processes were


used in


preparation


these


citrus


oils,


namely expression?


steam distillation,


extraction.


Expression,


process


preparing the


by mechanical


pressure


squeezing


containing


substance


by hand,was


found


applicable


only


preparation


citrus


from


peel


orange.


samples


citrus


expressed


from


peel


sour and


sweet


oranges were


prepared


author


by hand


exp ressi on


following ma nner:


fruit was


peeled


hand,


either


cutting in half


crosswise


sections and


scooping out


pulp or


stripping the


peel


in longitudinal


sections.


peel


was


then inverted and


squeezed


over a


clean


dry


sponge.


As a


result.


oells were


ruptured and


a mixture


oil and


other


liquids


were


shot out


a fine


spray.


When


sponge


had


become


saturated,


was


squeexed

















Preparation of


Sour and Sweet


Orange


Peel


Oil


by Mechanical Pressure.


sweet


and


sour


orange


peel


prepared


by the mechanical


device


explain d


below


, produces a


quality


expressed

method has


oil

oil.

been


that


although


used


regarded superior to


only


any advanta


recently that

ge. Where 1


hand

this

.abor


oheap,


in Italy


the hand method


still


used,


in countries


where


labor


high


other methods must


used.


following plan &nd


apparatus


as worked


by S.


Hood produces a


quality of


peel


that


regarded as superior


press used in


expressed


this method


by hand.


consi


heavy wooden


frame,


a wooden


drum fitted with


a perforated


brass cylinder and


heavy screw


for applying the


pressure.


About


twenty pounds


finely


ground


peel


placed


in a


canvass sack


drum.


made


Pressure


duck


is applied


and


sack placed


by means


a heavy


wooden


screw.


Before


pressing,


peel


mixed with approximately


- a a


a


A


uWn toT


A -- ~ I -I 'q 1 .


A


,, 1 ILL *~ ~r num nmr CL Y


'I


Jr


| ft, n r~l


b IT


















Ihe


pressed


cake


then distilled


with


water


and


a small


quantity of


secured.


separatory funnel


usually


employed


separation


from


water.


product


secured


this


manne r


consists


an oil-like,


thick


emulsion and


difficult


separate.


It resists


fixation must


oentrifuving


be used


such


hence


other


passing


methods


throuprh


puri-


infusorial


earth and


subsequent


filtering under


different


pressures,


disadvantage


of this


process


that


operation


entirely too


Hood


slow.


following process


purifying the


peel


recommended


oil.


All

aratory funnel


the

an d


water possible

the emulsion


is removed


warmed


on a water


sep-

r bath.


this


is added


a two


per


cent


solution of


gelatine


and


whole


added


tannin.


thoroughly


one-third


stirred.


volume


The mixture


this


a ten


brought


into a


warm


cent


state


solution


solution


coagulation


and


released.


This


regarded


very pure.
















distillation


shortly y


defined


process


procuring


passing


steam


into


vessel


containing


bearing


substance


and


collecting


distillate.


author


found


this


process


ap liable


procuring


from


leaf.


The


foll owing


method


was


devised


author


preparation


leaf


leaves


were


collected


any


from


convenient


tender


method.


shoots


namely,


tree


sausage


and


mill.


ground


Then


they


was


were


fitted


placed


a pipe


suitable


conveying


vessel


steam


into


generated


this


from


vessel


a suitable


source.


The


oil


volatile


zed


readily


with


steam


and


passes


into


a condenser,


fitted


into


a flask


attache d


a water


pump.


oil


together


with


water


was


collected


flask


and


then


mixture


was


placed


a separatory


funnel


where


water


was8


tapped


and


left


behind.


was


filtered


several


times


through


osaoined


charcoal


order


take


impurities.


author


considered


pure.















i ., i aeing


some


solvent


that


would.


extract


only


possible.


seeds


evenly


water


investigation:


were


were


treated


They


permitted


were


dry


following


thoroughly


a certain


washed


manner

with


extent,


then


ground&


means


a sausage


mill,


and


plac


petroleum


etheir,


which


they


were


allowed


stand


for


a period


oft U ine,


usually


from


days,


a tightly


stoppered


bottt te.


solvent


was


then


poured


and


seed


pres seed


order


procure


solvent.


was


found


advi-isable


filter


this


liquid


through


a cloth.


solv.vent


was


then


placed


a wide


mouthed


flask


and


immersed


ins a water


bath


connected


a condenser.


bath


was a heated

boi:.lea fre


gently


ely.


until


The


solvent


liquid

passed


contained


over


a low


flask


temperature


and 1 left


byI-produots


behind.


extracted


was


solvent


contaminated


needed


with


further


pur:ifloation.


was


first


separated


means


sepsoaratory


funnel,


still


contained


some


impurities.


then


placed


a water


bath


heated


further


, and















after


had


been


freed


from


the


solvent.


was


stalline


a melting


substance.


point


needle-


degrees


shaped


a spe


crystals


cifi


possessed


gravity


1.01014


15.5


distilled


degrees


water


, potassium


This

hydrate


substance


was


sodium


insoluble


hydrate


dissolved


immediately


chloroform.


substance


was


organic


hara


cter,


upon


heetin


a matra


charged.


author


classed


as a ctrbjh:ydrate


for


pounded


Owing


color


lack


reach


this


tions


and


crystalline


supplements.


material


large


enough


quantity


author


was


unable


classify


substance


further.


Analysis


Citrus


Essential


Oils.


Before


a quantitative


anal


these


citrus


oils,as


produced


author,


could


made,


was


found


necesaazy


make


a qualitative


examination.


author


found


upon


qualitative


analysis


these


citrus


oils


that


following g


constituents


were


present.


from


the


sweet


sour


orange


peel


was









been


ie st iga ted


Parry


and


the


author


re sult


were


aooord


with


his


The


from


orange


leaves


showed


upon


examination


compose d


following


onstituent


. namely;


I monene,


linalol,


linalyl


aoe


tate


, gerani


geranyl


acetate,


sesqui terpenes.


The


author


found


upon


examination


seed


that


was


composed


foll owing


constituents.


namely


linolyl


acetate


, limonene,


gerttni


and


small


aces


others.


first


thing


that


was


done


making


quantitative


examination


esse


ntial


oils


was


determine


theit


specific


c gravities.


this


purpose


hydrometers


were


useless.


Results


as accurate


as possible


are


necessary


and


since


hydrometers


are


only


rox


imate


other


methods


must


used.


Picnometers


had


their


disadvantages


only


a small


quantityy


was


available,


and


too,


they


seldom


contain n


exact


quan


that


they


are


supposed


contain.


h sample


author


les:


than


lOoo


and


hen


neither


picnometer


or hydrometer


could


used.


this


determination


an instrument


called


"Springel


Tube"


was


used


This


was


made


from


a small


capillary


tube


. _


* -


,.~ ~ -r 9- n A a n n .


na Ier S


Snan4 44 a


a rtA


I an nA


*1 tn


xKM


w\> A


_ -


m


nR p


a ,


CA


Y















graduated


by this


on each arm in oxorder to maintain a standard


instrument


volume


even less


could


used


with


good re:esults,


for the


liquid


tube


immediately


assumed tijthe


temperature


distilled


water


which


was


imeo ors ed.


specific


gr vi ties of these


oils


could be


placed at


a definite


sta anbdar d for


there


are many


details


taken into


consideration on.


For


instance,


different


climates*


and


soils


giver u mnch variation


specific


gravities


, henoe,


these Bsttandards


were


taken


within


certain


limits.


specific


geivvity of these citrus


oils were


found


range


from


.84S t to


.899.


results


obtained ,


table


below were found by using the


"Sprengel


first


by weighing the


weighing with an


equal


tb *oe with a,


vo' lune


volume


of water


then


applying the


formula:


It. of oil at
Wt. of water at


* nOhaml4nF ar P\ o + anl I 04 1u


16.5 C
15 .5.C


4D -- r Ir n


fronom


Tube"^


1n m















Table Showing Specific Gravity


of Citrus Essential


Oils.


NAME OF


OIL


AT 15.5 C


FOUND BY


Sour Orange Peel


.848


Author


Sour


Orange


Seed


.8995


Sour


Hybrid


Orange Leaf Oil


Orange Peel


.848


.851


Lemon Peel


Oil*


.850


.860


........ Other


Determinations....................


Grapefruit Peel


.840


- .855


Hood


i;eroli


Oil


.850


- .890


Parry


Lime Peel


.870


- .875


Laboratory


sample not made


by the


author.


The Melting and


Solidifying Points


These


citrus


oils


possessed


property


becoming solid


temperatures


lightlyy


below


ordintr


by a


determination


these


p-oints


author


believes


that


purity of


an o


this group may


judged


a certain


extent.


e melting point


solidifying points


- a


1 A















liquifaction


occurs.


solidifying


point


just


reverse


former.


results


shown


tabi


below


were


served


the


following


method


vised


author


0 The


was


placed


small


tube


was


inserted


ermometer,


the


tube


immer


their


ethe


was


rapidly


evapora


ted


a stream


air


temper&


ture


were


observed.


Table


Showing


Points


the
Vario


Solidifying
us Citrus 0


and
ils.


Melting


KIND


OIL


SOLIDIFYING


POINT


MELTING


POINT


Sour


Orangee


Peel


0 0


Sweet


Orange


Peel


-2 G


0 C


Sour


Orange


Leaf


-2 C


0 C


Sour


Orange


Seed


. -3


0 C


$. @. .. .. @


.. Other


Determinations


Neroli


Parry)


0 C


Boiling


Point


Citrus


Oils.


A a~ +awnI n 044 A


whk4 nh


The


+A jMwm^^o ^n WA


PT


||l 1 A


n'P rCI~

















manner:


convenient


volume of


oil


was


taken


pla


a flask


having


a capacity~'o:f


5Boo.


flask


was


then


partially


immersed


a paraaffi1n


bath


thermometer


inserted


flask.


Sufftic


lent


heat


was


applied


maintain


boiling.,


and


tat


boiling


began


was


observed.


fol owing


result t


show


temperature


observed:


Name


Oil


H Boi


linga


Point


Sour

Sour


Sour 0

Sweet

Hybrid


Orange

Orange


rang e I

OranPe

Orange


Peel


174


Seed


172


,oaf


175


Peel


173


Peel


174


......................Other


Neroli


Alien)*


178


*0ommeroial


Distilling


OrganiLAo nalys


PoLi nts of


Allen,


Citrus


Vol.


Oilse.


T Determinations............















order


to determine


cent


that


passes


over


between certain


temperatures,


author devised


following method:


A weighed


quantity


was


placed


in a


flask


immersed


in a


paraffin


bath,


flask,


being connected


a small


receiver


which


was


pr evi ou sly


weighed and


attached


to a


water pump


in order


create


vaccuum.


various s


temperatures


were


observed upon


distilling and


flask


containing the


distillate


was


weighed


between


certain


temperatures and


per


cents


calculated.


value


fractional


distillation


could


not 'be


over-estimated,


by determining the


specific


gravity


optical


rotation


f the


various


fractions,


much


time


was


saved and


useful


results


obtained


determining the


purity of


these


oils.


Table Showing Per Cents of Citru
Distilled Between Definite Ten
Per Cent of Residue.


.s Essential
Lperatures and


Oils


that


Kind


Between Degrees
of Oil of Temperature


Per Cent
Distilled


Per Cent
Residue


Sweet


Orange Peel


173


- 175


I












Tabi


Continued


Kind


Between Degrees
of Temperature


Oil


Per


Cent


Distilled


Per Cent
Residue


Sour


Orange


Leaf


175
177
185


-- 177


185
188


account


very


limited


amount


samples,


accurate


results


could


be obt


gained


only


three


oases


noted


above.


Solubility


Citrus


Oils


solubility*


citrus


this


determination


termed


amount


alcohol


known


strength


required


complete


solution


a known


volume


oil.


This


test


used


test


essential


oils


was


found


play


an important


part


determining


approximately


purity


citrus


oils.


alcohols


used


this


termination


were


such


a nature


that


they


were


as accurate


their


per


cent


as possible


and


oils


used


were


relatively


pure.


strengths


alcohols


employed


these


determinations


were


eighty-five


per


dent,


ninety


per


cent


and


ninety-fi


per


oent.


this


determination


a volume















Table


cording


Solubility


Data


Obseerv ed


of Various CitrunS Oils.


Name


Sweet


of Oil


Degre e of Solubility


Orange Peel


SolDub e in 7 volumes
905 a aoohol.


Sour Orange Leaf Oil


So0iub 2e


in 2 volumes


90'^ a loohol.


Sour Orange


Peel


Sol0lub le


7 volumes


90L alcohol.


Sour Orange


Seed


Selflub le in 3 volumes
.8a a-loohol.


Determination ons ........


of Neroli


Allen)


Sol tub le in 2
90 d a-loohol.


volume s


Determination


of A i1> ohol in


Citrus Otiils.


Alcohol


in essential


oils


"thLis


group was


detected


gradually


adding dry powder redL calcium chloride


a given


volume


oil,


agitatinrg a-nd


heating in a


water


bath


between


each


addition.


Merere


traces


alcohol


rendered


first


portion


calcium o hLoride


pasty,


but


upon


the addition


of more


calcium


chlorerida the


salts


dissolved


............. ........Other
















convenient to convert them into an acetic ester by an


excess of acetic anhydride,


asinP sodium acetate to absorb


the water formed in


the reaction.


The resultant ester was


then saponified and


the alcohol present was calculated from


the amount of alkali


actual


entering into the reaction.


determination of alcohol it is often


For an


necessary


make a supplementary determination of the esters present.

According to Allen* the following method may be followed in


A weight of five grams of the sample was placed


a strong botti


centimeters and

of :NaOH in alcoh


having the capacity of about a thousand cabic

to thi3 was added 30 co of a normal solution

ol. The bottle was then securely closed


and kept in a water bath of boiling water


one hour.


After cooling,


the bottle was opened and


the contents


titrated in the bottle with semi-normal H1C acid,


-.sing


phenolphthalein for an indicator.


The per cent


free


alcohol as expressed in menthol in the


form


ester.-


Was


found by the following formula:

Menthol% = 15.6(30


- Amount of Acid)


ample


detail:














Table


Showing


Per
Citrus


Cents


Essential


ohola


Oils


Found


Name


Oil


Cent


Menthol


Sour


Sour

Sweet


Orange


Orange

Orange


Peel


Leaf


Peel


3.8


Tangerine


Peel


1.1


Sour


Orange


Seed


3.5


Iodine


Absorptive


Power


Another


metho d


differentiation


based


chemical


constitution


these


citrus


oils


was


determina-


tioun


amount


iodine


taken


under


conditions


tended


insure


format ion


additive


compound s


only.


This


a test


resorted


tests


was


deter-


mined


according


Hubb*


as follows


Add


grams


&HgCl


co ethyl


alcohol.


Another


solution


containing


grams


iodine


Co.


same


alcohol


was


made.


were


mixed


left


standing


12 hours


before


using.


Before


after


using,


A. -A~A -- t ~ ~ t e.L~ .1A-


*V ^ *


__ _L .. A -


J ~ )


I~ ~


L


II,


J *















Then


1 gram of the


oil and 10


chloroform


were


taken.


They were mixed


in a


well


stoppered


bottle


with


20 oc


standard


iodo-merourio


chloride


solution


and if the


solution was


the mixture


clerm, 10


had


become


oc more


decolorized


chloroform were


or nearly


added,

or 10 Oc


more


iodide


brown after


solution


standing


was added.


2 hours.


liquid


Then 10


was


15 cc


quite

a 10%


solution


of EI


were


added


mixture.


free


iodine


was


then


determined


titrating


contents with


sodium


thio3ulphite.


A blank experiment


was


carried


side


sida e


with


difference


reading


burrttes onon


first and


second


blank


test


gave


number


titrating

equivalent


solution


used.


iodine and


This was


cent


then

oil.


calculated

Starch


into itste

was used fl at


the reaction.


Table


tame


Showing the Io
of Essential


of Oils


dine
Citr


Absorptive
us Oils.


Iodine Absorptive


Power


Power


in Grrsme


Sweet Orange Peel
Sour Orange Peel


346 344 341
341 389 313
















Aoid


Value


acid


value*


an oil


shows


what


extent


an oil


acids


has


formed


other


undergone


hydrolysis,


subsequently


words


represents


the

the


amount


process

number


ozidized


hydrolysis.

milligrams


potassium


hydroxi de


required


saturate


free


acid


gram


oil'*.


gram


citrus


was


mixed


with


ethyl


alcohol


titrated


with


alcoholic


standard


alkali


using


Phenol-


phthale in


as an indicator.


manner


which


acid


value


this


group


oils


this


was


expressed
expreS8ed in


group


bears


terms


a relation


anhydrou a


citric


citric


acid.


acid,


Hence,


was


expressed


number


grams


anhydrous


citrio


acid


contained


one


citrus


oil.


relation


shown


following


equation


3SaOH


C G607Nae3


3120


S*nnwna-nI al


Oranni n


Anal van


Allsan


Vol. TI.Pt.


I.


080 o07















Table


findL


Showing the Amount
Aoid Contained in


of Oil


Anhydrou
oe CO of


AMhydrous Citrio


S


Citrio


Oil


Acid Per


Sour


Orange


Leaf


.16741


Grams


Sour


Orange


Peel


Sour


Orange


Seed


.001378


Sweet Orange Peel

......................Other


.002144"

Determinations...... ............


Jeroli


Parry)


.016707


Detection


Chloroform


This test


essential


used


oils,


in many


often


oases


case


analysis


that


neglected


this


nature.


primary


advantage


this


test


this group


oils was


determine whether


or not


these


citrus


oils


had


become


contaminated


with mineral


oils


or oils of


a different


nature.


This determination


was


carried


according to Allen


* by dissolving a conven-


ient


amount


oil in alcohol


warming with


sine


ii_ i

















of the


essential


oils


of thi s


group no


trace


chloroform


coul d


detected.


Optical


Activity


The


optical


activity of


these


oils


such


value


that


is regarded


1now


by all


authorities


indispensable.


its value


only


be properly esti-


mated


a very


careful


consideration


results


obtained.


As a


determination


of the


purity


optical


instrument,


(usually the refractometer),


was


of little


value .


The


chief


value


this


test was


found


to be


in a


careful


examination


various


fractions when the


was


distilled


under


reduced


pressure.


The


optical


activity*


various


fractions


will


determine


to a


large degree whether


or not


has


been


subjected


to adulteration.


For


example,


the


peeling


sweet


orange will


vary


to a consider-


able


degree when adulterants


are added.


For


ails


this


determination an


instrument


called


"Polarizer "**should


a















simple


in structure.


consisting


semicircular


plates


placed


juxtaposition,


ea .;h


out at right angle


its axis;


one


possessing


dextro and


the


other


leavo-rot


atory


power.


plates


are


some


thickness,


pro-


duc e


equal


rotations


opposite


directions.


incident


light


white


and


lights


different


refragibili8es


are


rotated


through


different


angles.


Henoe,


when


viewed


by an anaylysinp nicol,


waves


different


refragibilities


will


quenched


into


two halves,


and


they will


appear


different


colors.


When


principal


plane


of the


analyzer,


however,is parallel

complementary colors


direction


which


are


of the


quenched.


incident

suitable


on the

adjust-


ment


of the


thickness


plate,


brilliant


yellow will


quenched


, and


delicate


gray-violet


tint,


known as


tint


of passage appears when


both halves


have


same


color.


This point


zero


point


the apparatus and


easily


fixed,for


slightest


rotation


right


left


renders


one-half


field.


blue


and the


other red.


Having


instrument,


found


that when an


optically


active


substance


introduced


tint


disappears,


a -


1


m
















incident ray,


this


optical


examination,


au,.to., idiso vered


a new flame whi


h aided greatly


.


*


the.* e'ta'eri nat i on.
> >* i


. C


* .


flask was


flask.


fitted


was


up as fo

attached


allows


TwoKJ-jtes .wer4e \)ilgc~4'.in
3 3 ) *3 3 j I


to a ..ipe
to a g1^ Vipe,
g >8..


while


pipe


leading froM


flask was attached


burner.


flask


was partially


oduced.


filled


with water


flask was


calo


iromedia


ium carbide


closed


and


turned


on.


flame


was


lighted and


very


brilliant


light was


produced,


was


used


an advantage


over


ordinary


flame.


Table


Showing the Optical
Citrus Essential


Observation


Oils.


Name of Oil


Angle


of Rotation


Specific


Power


Rotaryf


Sour Orange Peel


+ 928


1.411


Sour Orange Leaf Oil


.4940


1.4563


Sour Orange


Sweet


Seed


Orange Peel


1.5114


+-96'


1.843


Determinations...............


S ..... Other














Determination


Esters


principle


on which


this


determination


was


based


fact


that


most


esters


are


decomposed


action


caustic


alkali.


milligrams


KOH


In other


required


words,


represents


saponify


esters


number


contained


one


gram


oil.


make


this


teat,acoording


Koettstorfer


from


five


grams


oil,


acc wording


ester


content,


were


weighed


placed


into


a flask


capable


holding


from


and


from


solution


oaustic


potash


alcohol


were


added.


This


strength


should


normal.


whole


was


then


boiled


under


a reflux


condenser


an hour.


was


the n


diluted


with


water


and


excess


potash


was


estimated


titratinr


with


semi-normal


sulphuri c


acid,


using


phenolphthalein


indicator.


determine


amount


potash


originally


employed,


was


perform


a blank


experiment


with


same


amount


potash


solution,


merel


y omitting


oil.


difference


titration


gave


the


amount


potash


used


decomposition


esters


determination


V- a


he amount


used


Vw


a -.e a


neutralization


of free


Dotash

















Table


Showing the Per Cent


Essential


Citrus


of Esters


Oils


Name


of Oil


Per Cant


of Ester


Sour


Orange Leaf


- 60


Sweet


Orange


Peel


Trace


Sour


Orange Peel


race


Sour


Orange


Seed


- 18


Tangerine Peel


race


of Methyl


Ester


......................Other


Determinations..


of Neroli


(Parry


& Allen)


- 20


Determination


Aldehydes -and


Ketones


The essential


oils


this


group


contain


small


cents


cldyhydes and ketones a


comparison


other


essential


oils.


important


This


one


this


test


regarded


group


oils.


by the

For


author

details


process


Thieland


Stange*


following method


About


may


used


citrus


according


were


- q -


I a


n ,- -


c a ait


a an ra1 4 A/


o n i tn M


.l.i I /filfl 1 lr M -i V* 1 M1


oanA4 rnm


Mrlrn


T














was


neutralized


with aoetic acid


(strength


until


a red


coloration


1 longer


appeared


upon


further


heating.


The


was .brought


into


graduated


neck


flask


filling the


flask


the graduated


hot water.


neck


From


flask


per


volume


cents


aldeh--des and


letones


were


calculated.


Table


Showing Per
Essential


Cent


Citrus


Aldehydes
Oils


Name


of Oil


Per


Cent


Aldehydes


Sweet Orange


Peel


Oil


Sour

Sour


Orange

Orange


Peel

Seed


Oil


2.67

.96


Oil


Sour


Orange Leaf Uil


1.10


.... ... .... ..............Other


Determinations............


Oil


e rol i


(Parry)


1.46


Effect of
and Iodine


Sulphuric
on Citrus


Acid, fIit
Essential


rio Ac
Oils.


early


investigations of


peel


above


tests


were


no t


taken


into


consideration.


*Ofl


lid
















on essential


oils.


citrus


oils


this inve


tigation


were


found


be entirely


changed


by treatment with strong


acids


such


iodine.


as concentrated H S

The following result


04and

s were


concentrated HI03,


observed


and


this


investigation;


Upon


the addition


concentrated sulphuric acid


a small


quantity


these


oils


there was marked chanFe.


oils


were


turned


dark


red and


a characteristic


odor


produced.


acid and


a brown


Likewise

color was


oils were


produced


treated


with


with nitric


evolution


a characteristic


odor.


While


investigate tinr


action


upon


other


essential


oils there


was


entirely


different


color


produced.


Upon


addition


iodine


these


oils a


rapid


reaction


took


place


with


evolution


flames,


turning yellow and,


upon heating,


turning red,


hence,


these


tests may


used


a certain


extent


in differentiating


the classes


essential


oils.


The Methoxyl Number of Citrus
Essential Oils
















Concentrated


hydriodio


avoid


and


receiving


alkyl


iodide


formed4in a


solution


silver


nitrate.


Proa


we ight


silver


iodide


produoed


that


alkyl


radeial


oan


oaloulated,


since


silver


iodide


oerre spends


CH 0.


determination


Methoxyl


number


method


devised


Benedikt


and


Graulanet


was


carried


as follows:


Prom


grams


oil


were


pao*ed


a flask


having


a oapao-


ity


and


treated


with


oonoentrated


hpydriodie


avoid,


(sp.


1.90).


flask


was


heated


bath

it.


of

The


bulb s,

tilled


paraffin

alkl i


the


first


water.


carbonate


and


or glyoerin,


odide

of i


and


a current


d passed


hinh


was


third


arsenious


'CO0


through


empty,


oontaine& a


oxide.


bulb


was


a eerie


second

solution

S were a


passed
8 of


contained


potass


surrounded


thro


dis-

ina

with


water


which


heat


was


neoseary


determination


was


0quit
quite


After


free


passing


fro


bulbs,


dydriodio


akyll


avoid


iodide,


iodine


was


which


absorb-


a flask


containing


oo of


a 40$


squious


solution


o0 of


*5%


aloohol.


a precaut ion,














eoolation


with


oo of


alcohol.


solutions


after


the.


tion


were


mixed,


diluted


with


distilled


water,


aoidulat-


b6 d with H303,


silver


iodide


filtered


off


and


we ightd.


Itiplying


weight


found


factor


.132


which


I** qu


51
2%g


equivalent


Table


Showing


methoxyl


Methoxyl


was


Number


found.


Citrus


Eseential


Oils.


MSum


Methoxyl


Number


Swsv et


Orange


feel


.13068


Soar


Orange


Peel


.12145


Somr


Orange


Leaf


.09010


Orange

n Peel*


Seed


.08791


.19890


Adulterationa


Oitrus


oila


liable


adulterat ion


and


' uenal


adulterant a


found


substances


suah


as turpentime


fixed


oils.(1)


cheaper


essential


oils


oltrue


plants


often


mixed


with


the


more


expensive


ones.


*oioel


frequently used


and


obhloroform has


at times


SeMar





I
















aoetio


esters


glycerin


ester


containing


oils.


difficult


secrete


these


adulterations,


for


upon


determin-


ing


optical


activity


specific


gravity


vari ous


fraction,


suoh


adulterants


oan


detected.


For


example,


the


sour


degrees,


but


orange


peel


possessed


addition


an optical


ethyl


alcohol


activity


rafrao-


tive


power


was


muoh


altered.


Not


only


did


these


adulterants


affect


optical


activity


oil,


but


there


may


some


change


speoifie


gravity


the


oil


adulterated.


change


detection


speoifio


adulterants


gravities


these


could


not


essential


oils,


used

for


for

upon


nixti


oil


with


substances


proper


speoifio


gravity,


which


oould


easily


made


from


pentine


no change


oould


detected.


This,


0ou0se,


makes


hard


detect


an adulter-


ant


from


a physical


nation.


Again,


adulterat ion


these


citrus


oils


caused


a marked


variation


solubility,


For


example;


sour


oragne


peel


was


found


soluble


seven


volume s


ninety


tina_


I lI


cent


aolubilltv


alcohol,


was


but


upon


deareased


addition


the


-I Y


other


turpen-


hand.


per


I















the


main


purpose


for


this


adulteration


rests


the


fuCot


that


cheaper


grades


used


com-


bination


4.ith


higher


grades


with


a result


bringing


cheaper


oils


into


a first


olass


market t.


This


also


produces


a greater


quantity


first


class


being


mixed


with


cheaper


oils


used


as adulterants.


CONCLUS


ON.


from


investigation,


account


which


author


has


set


forth


herein,


found


that


citrus


oils


have


been


investigated


only


a limited


extent.


methods


previously


used


production


these e


oils


very


or


crude.


Furthermore,


these


citrus


oils


can


prepared


me -


ohanioal


meth


exclusively.


oils


produced


from


leaf


and


seed


can


produced


distillation


extraction.


These


oils


possess


qualities


which


author


believes


will


place


them


soap,


drug


and


perfume


industry.


new


compound


a carbohydrates


was


found


production


seed


oil.


new


for


optioal


exauinati on


these


oils


was


disoov-


ered.


The


oil


sour


and


sweet


orange


peel


investigated


-


a -


- a at a a! a a Sb a a a9 ~A At a a a a a S -- S a 4t~ a


may


,A,,,lr,


Du Ar


lI II AIA"


L A a


AI


AI
















impose illBdle


to deteot


anl


phy


teal


change.


fracotion-


ati l


adult riabate


d oils,


found


that


examining


the


varioun


fraot lone


by tdheA


optical


teat


that


an adulterated


oould


detected.










IB


IOGR


Chemistry


Essential


Oil.


. Parry


Oitras


fruits


Their


Culture.


Oitra


an4


Essential


Oile.


.****sO......... Sohimel


Praodution


Sweet


Orange


1O1


...........3.0Q.Hood,


S.D.


Organio


Ohe


stry..


rotial


Ohemieal


Organio


Technology..


Artiales


Analysi ...


....................... *Lwowitoh


. Chase


Chase


'he


Chemistry


Plant


Products.


Hill


lnaustrial


stry


S. .. .. ..Rodger


Journal
Toel 8.


Industrial
T8. 1916


Engineering


istry


Analy si of

Deteotion of


PuDre
Pre


and


Medioinem.


Organic


Compounds.


.......Mnllikin


Organic


Chemistry.


Inftutr ial


istry ....


.........................Norria


0 *


Organio

World's


ari


their


Chemistry....


Prduoti on


Produeta..


Citrus


fruite


* 0.


& Kiplint


Wallsohlaeger


Teahniale


thode


ioal


Analyfse...


.* Seune


& Keane


14w#0


............E.


-4


... ...... ......E.


...........Hume


........................oewell


.............Allen


...........Raa8


...........Nelson


.. ............ horpe


. .................... Perkine




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