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Master's Theses Student Research
Spring 1972
A spectrophotometric study of the reactionbetween benzoyl peroxide and N, N-dimethyl-P-phenylenediamineBertha Cosby King
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Recommended CitationKing, Bertha Cosby, "A spectrophotometric study of the reaction between benzoyl peroxide and N, N-dimethyl-P-phenylenediamine"(1972). Master's Theses. Paper 359.
A SPECTROPHOTOMETRIC STUDY
OF THE REACTION BETWEEN
BENZOYL PEROXIDE AND N,N-DIMETHYL-P-PHENYLENEDIAMINE
BY
BERTHA COSBY KING
A THESIS S~8MITTED TO THE GRADUATE FACULTY .. OF THE UNIVERSITY OF RICHMOND
IN CANDIDACY FOR THE DEGREE OF
MA8TER OF SCIENCE IN CHEMISTRY
JUNE 1972
UBRARf
UM1VE:RSITY OF RICHMONv J'Ol~!~JIA
APPROVED:
ACKNOWLEDGMENT
With the completion of this work, I wish to express
my sincerest thanks to Dr. w. Allan Powell for his per
sonal interest and guidance throughout this project.
I wish to express my appreciation to Dr. J. Stanton
. Pierce, whose wiae counsel and contagious enthusiam
helped in the completion of this wbrk.
I would like to thank the other members of the de
partment for their patience and encouragement •
. Finally, I want to thank my family for their sup
port and cooperation.
TABLE OF CONTENTS
' . INTRODUCTION •
HISTORICAL,., .•.•
• •
• • •
• •
• •
• • • • • • • •
• • • • • • ... • • • • •
• •
• •
• •
• •
• • •
• • •
Page \ l
4 I. Organic Peroxides. • • • • • • • • • • • • • • • • • 4
A., Classification and Stability • • • • • • • • • • 4
B. Methods of Analysis •• • • • • • • • • ••• • • 5
1. Volumetric • • • • • • • • • • • • • • • • • 6
2. Polarographic, infrared, and chromato-
,. 8 graphic • • • • • • • • • • • • • • • · • • • • " ..
3. Colorimetric • • • • • • • • • • • • • • • • 10
4 .. The spectrophotometric method using N,N
dimethyl~p-phenylenediamine sulfate. .. • • • 15 II. Oxidation of Amines •••• ~ • • • • •
A. Formation of Free Radicals • • • •
• • • • • • •
• • • • • • •
23
24 B. Reactions of N,N-Dimethyl-p-phenylenediamine • • 28
c. Formation 'or Wurster• s Red • • • • • • • • • • •
EXPERIMENTAL • • • • • • • • • • • • • • • • • • • • • • • •
I. Reagents
II.· Apparatus
• • • • • . . .. • • • • • • • • • • • • • •
• \ • 0 . .. . . . . • • • • • • • • • • •
III. Preparation of Solutions and General Procedure •• • • IV. Data and Results •••••• • • • • • • • • • • • • •
" I
A. A Study of the Effect .of Variables on Dugan's ,; I .
Method •• • • • • • • • • • • • • • • • • • • ,,
B • N, N-D~methy.1-p-phenylenediamine Sulfate in
Methanol. • • • • • • • • o •••• 0 ••.••
• •
• •
29
36
36
37
38
40
40
43
v.
S~ARY.
APPENDIX
Page· c. N,N-Dimethyl-p-phenylenediamine·Sulfate in ,
,,•:I ..,_.:; .
• Water •••••• • • • • • • • • • • • • • • . • .. 46
D. N,N-Dimethyl-p-phenylenediamine Sulfate in
Acetone •• • • • • • • • • • • • • • • • • . ... . E. Separation of the Colored Reaction Product •••
" .
F. Reaction of the Amine with Bromine and Ferric
Ions •• • • • • • • • • • • . .• '. . . . G. P~vel~pment of a Method for the Determination
of Peroxides Substituting Pyridine for Benzene •
Discussion •••• • • • • 8 '. • • • • • • • • • • •
A.
B.
c.
' . Identification of Wurster's Red ••••••••
Identification of p,p'-Bis(dimethylamino)-
azobenzene • • • • • • • • • • • • • • • • • • '
Further Analysis of the Spectra •• • • • • • • •
•
•
•
D. The Modification of Dugan~s Method •••••••
~ • • • 0 • • • • • • • • • • • • • • • • • • • • •
eeeeee•eoeeoe~OGeee•oe•e•e
···. ··"
49
49
.51 ..
51
57
57
59 64
66
68
69
BIBLIOGRAPHY . . . .. . . (. '
• • • • • • •. '. ·. • • . • • • • • . • • • • 132 ,, AUTOBIOGRAPHY. • • • • • • • •• ·~· •• 0 ••••••••• 138 ,,
. I
(1)
INTRODUCTION
A special need for methods to determine low concen-
trations of organic peroxides originated because of their
hazardous and harmful effects, Even the small amounts of
organio peroxide~ formed by autoxidation in ethers exposed ...
to air make the ethers highly explosive and unsuitable for
use as anesthesia or laboratory solvents. The formation of
organic peroxides in fats and oils causes rancid'ity. They
have been named as pollutants, and some of them are known
to have detrimental.physiological eff~cts (47).
As organic. peroxides are oxidants and sources of free •,
radicals, within recent years they have been used commer-
cially as initiators and catalysts in polymerization, as
bleaches, as disinfectants, and as fuel additives. In
addition, they are intermediates in certain oxidation pro
cesses for the production of alcohols and phenols (34).
In these 'processes the amount of unused peroxide requires
determination. For example, as polymeri~ation catalysts
in the synthesis of rubber or plastics, organic peroxides
may remain in the finished product, which is often used in
rood packaging, thus allowing peroxide migration into food.
With the variation in the techn<5logy of their applications~
(2)
many n~w p~rox~des are being synthesized. As more is known
of their cnemistry and behavior, they will have wider use,
requiring·. simple, rapid, reliable methods of .determination.
N,N-Dimethyl-p-phenylenediamine sulfate has been used "
in a quantitative .spectrophotometric determination for sev
eral types. of. organic peroxides •. This method was developed
by Dugan :(12), using' benzoyl,and lauroyl peroxides in ben•
zene. A mixture ·of water. ,arid methanol was used as the sol-
vent for .the amine sulfate •. The method was later extended
to include' the.detection of traces of peroxides in ethers . .
and of other ~pacific peroxides {13, 14).
This .. mit thod needs modifies ti on. Al though the color
forms rapidly (with benzoyl peroxide maximu.~ formation oc
curs in approximately five minutes) and the standard curves
for the peroxides studied follow Beer's Law, color fading is
apparent. Absorbance.at the.specified wavelengths changes
rapidly,. making the time 'ror measuring the absorbancesori ti•·
cal. In. determini~g benzoyl peroxide, the absorbance is ap
proximately 70 percent of the maximum value and continues to
decrease after thirty minutes, the time allowed for color
development, by the Dugan method.
The formation of different colored products was observed
by Dugan at different pH values.' and in different solvents. .. .
Howev.er, no identificati.on of these products was made. Ac-
cording 'to' Dugan, the reaotan,ts were the amine sulfate and " I ' ',
( 3)
methanol, which formed a colored complex, and the reaction
was cats.lysed by a free radical mechanism. According to
Dugan, it involved the splitting off of -Ng~~ from the ben
zene ring. However, this seemed to be too drastic a reac
tion for occurrence at room temperature and an unusual reac-
tion for an aromatic tertiary amine.
The purpose of this research was to improve this method
of analysis and to determine better conditions for the meRs~··
urement of color b'y studying the separate effects of the
solvents used, and the effect of pH, the amine concentration,
and the order of addition of reagents. The' purpose also was
to learn more about the reaction that occurs and to identify,
if possible, one or more of the colored products.
(4)
HISTORICAL
I. Organic Peroxides
A. Classification and Stability
Organic peroxides are characterized by an -0-0- linkage. ~
Martin (34) divides them in~o six types.
Type Example Analog
1) Hydroperoxide · C2H5ooH C2H50H
2) Dialkyl (also diaryl) c2H5ooc2H5 c2H5oc2H5
3) Peroxyacid (or ~er-acid) CH3C~QooH CH3C~QOH
4) Peroxy ester CH3c~QOOC(CH3 )3 . 0 CH3C~-OC(GH3))
5) Diacyl (also diaroyl) . CH3C" ... Oooc~2cH3 CH3C~Qoc~QCH3
6) Peroxy derivatives of H
<e:._xO aldehydes and ketones - 0 OH
Other examples of peroxide linkage are found in polymers formed
from conjugated olefins plus oxygen, for example, ,_
+
x trans annular peroxides of terpenes ~·· sterols, and polynuclear aro
matic hydrocarbons, for example,· · -6- ,cH3 CH3 0-0 CH 'CH .
3
(5)
and polyalkylidene peroxides, for example, the dimeric and tri~ I
meric acetone peroxides such ~s
Ozonides also have a peroxide linkage.
Organic peroxides have a wide range of stability, This class
of compounds as a whole should be treated with respect because.
ce:Dtain perr.&ides ·decG.'llpose violently when exposed to heat or
shock. N~vertheless, all organic peroxides are not dangerous as
was shown in a study by Noller and Bolton (47). They may have 11
half lives, which vary from one second to over twenty years at
50 degrees centigrade (36). Peroxides with high oxygen content
are most likely to be unstable and are extremely dangerous if the
ratio of hytlrogen .to oxygen or carbon to oxygen is three (or \
less) to one. Organic. peroxides are most stable in neutral or
slightly acidic aqueous solutions.
B. · Methods of Ana'lysis'
The usual methods of oxidation-reduction analysis have been
applied to"organic peroxide's' 1 (35). These include the· reduction
of the peroxide linkage. All methods, however, are not applica
ble to all peroxides. In the reduction reaction of peroxides,
there is a wide range 'of' ;r~acti vi ty not predictable from their
structures, Moreover, the relative reactivities among reducing
agents are not consistent. In application, many of the usual
'methods of analysis must b'e 'modified due to s'llub~li ty problems.
(6)
The reduction of the peroxide linkage is followed by ti tra\ .. •
tion or a colorimetric estimation. These titrations are all in-
direct. It is the oxidized reducing agent or the excess reducing
agent that is titrated. In the case where eerie ions are used
to oxidize hydrogen peroxide or hydroperoxides (37), the excess
oxidizing agent is titrated. Titration endpoints are determined
visually using indicators, potentiometrically, amperometrically,
or with "dead-stop" techniques. Colorimetric methods can be a·p-,. '
plied in the case of a colored oxidation product. If the reduc
ing agent is colored, the excess may be estimated colorimetrical
ly.
1. Volumetric
Martin (37) describes four volumetric methods, which are io
dometric, stannous ion reduction, arsenious oxide r·eduction, and
eerie ammonium sulfate oxidation. The iodometric method is
thought to be the most convenient, precise, and accurate method
for samples containing more than 0.05 milliequivalents of perox
ides if they are easily reduced~ For smaller amounts, colorimet-
ric methods are· more sensitive. For example, this wes found to
be true in c~~paring the iodometric method with the ferrothiocy
anate color'imetric method when determining peroxides in marga•
rines and edible oils {10). According to Martin, the best iodo
metric procedure is that of Wagner, Smith, and Peters (37). The
usual sources of error for this method are loss of iodine by side
reactions,. volatilization,, and incomplete reaction, along with,
(7)
the addition of iodine to double bonds if present. • • The advantage of the stannous ion reduction method is that
it can be used in the presence of sulfur or conjugated olefinic
compounds.· Materials reduced by the stannous ion interfere.
This method will not tolerate aldehydes, thioethers or primary
alcohols. The procedure is that excess stannous ions are ti
trated with ferric or iodine solutions, or an excess of ferric
ions is added, and the resulting ferrous ions are titrated with
pota~sium dichromate.
In the arsenious oxide reduction method, referred to as the
method of Siggia (37), the excess arsenious oxide is titrated
with iodine solution.
The eerie ammonium sulfate oxidation method (37) can be ap
plied to hydrogen peroxide and some hydroperoxides, in which case
the eerie ion is the s_tronger oxidizing agent. This oxidation is
followed by an iodometric procedure· to determine excess eerie
ions.
An additional method, referred to by Mair and Graupner. (33),
is that of reduction using titanous chloride. I
A double titration method was used to determine benzoyl per
oxide in carbon tetrachloride in the presence of free chlorine
(55, 56) •. The total amount of peroxide and chlorine was deter
mined iodometrically with thiosulfate, the amount of chlorine by
titration with methyl orange in acid, and the amount of benzoyl
peroxide calculated by differen~~· The amount of organic perox
ide was also calculated by' difference in an aqueous solution con-. I· l •11
{8)
taining aldehydes and hydrogen peroxide in addition to the or-\ I
ganic peroxide (46). The total peroxide concentration was de- ·
termined iodometrically, hydrogen peroxide was determined photo-++ metrically after reaction with acidic TiO , and silver oxide
was used to oxidize the aldehyde (RCHO to RCOOAg) followed by
titration with potassium thiocyanate. A special method, involv
ing separate determinations of hydrogen peroxide, peracids and
total peroxide (3), was also devised to determine the peroxid& .. .. compounds which are products of furfural oxidation.
Dialkyl and diacyl peroxides were determined in the presence
of hydroperoxides {48) by their reaction with aniline. Dialkyl
peroxides reacted with the liberation of water, which was titrat
ed with Fischer's reagent. For·diacyl peroxides, the amount of
aniline used was measured.
In the determination of peroxides used in the polymerization
of styrene, to eliminate the necessity of maintaining an inert
atmosphere, a complexonietric method was developed in which fer•o ·
rous ammonium sulfate was oxidized, and the resulting ferr_ic ions
were titrated with ethylenediaminetetraacetic acid (61).
2. Polarographic, infrared and chromatographic
For determining a wide variety of. peroxides, polarographic
methods are the most valuable. Ove.r the normal polarographic po-
tential region, only one peroxide, di-tert-butyl, is known to be
non-reducible (41). The reductions are two electron~reactions
in which the bond between the two oxygens is broken and hydroxyl
groups are formed. Mixtures .can be analysed i:t' the halt-wave
(9)
potehtials are different by at least ,0.4 volts, with the current
directly proportional to the peroxide concentration. In using •
this method, calibration is necessary for each peroxide.
,, Reference to the literature showed extensive application of
this method. The polarographic behavior of anesthesia ether due
to its aldehyde and peroxide content was studied (2)), as were
the p~oducts of radiation (52). The method was used to distin
guish between peroxide structures in oxidized fats (32, 54) •.
These studies showed,the use of mixed solvent systems with dif
ferent supporting electrolytes. The half-wave potentials of per
pxides were found to be independent of pH (31).
Infrared spectroscopy as a method of analysis for organic
peroxides has been only moderately successful, as it has been
impossible to assign a band representing the stretching vibra
tion of the 0-0 bond not influenced by the rest of the molecule
(42). Benzoyl peroxide and a series of aliphatic diacyl perox
ides in the range of 0.2 to 0.01 moles per liter were determined
in the .presence of styrene arid polystyrene (1). Hydroperoxides
and alcohols were deter~ined in the presence of peresters· and
dialkyl peroxides, using the absorption bands of the free hy-'.
droxyl groups (60).
Gas chromatography has been used to some extent, and further .. application is expected {7,25). Thin-layer chromatography of
organic peroxides was studied, and the peroxides arranged in a
eerie~ in decreasing order ac·cording to their Rf' values: dialkyl,
diacyl, peroxy esters, hydroperoxides, and hydrogen peroxide (8).
(10)
Infrared, dipole moment, and molecular weight studies have-,
been used in determining structures (59). W!th polarography, an
order of stability has been established which parallels reactiv
ities with the iodide ion. The polarographic half-wave potentials
of the various classes of peroxides serve as an indication of the
st~engths of the 0-0 bonds (5). These classes, arranged in de
creasing order according to their half-wave potentials, are as
follows: di-tert-butyl peroxide, dialkyl peroxides, tert-buty~
... peresters, hydroperoxides, diacyl peroxides, and peracids •
•
3. Colorimetric
Colorimetric methods for determining organic peroxides are
. mainly methods involving ferrous ion oxidation, iodometrio meth-
ode, or methods in which an aromatic organic compound, such as an
amine, can be oxidized to a dye form with multiple conjugation
and intense color.
The ferrous ion oxidation method has great sensitivity, as
was pointed out on page six, but poor specificity, and sometimes
poor precision and accuracy (38, 57). Kolthoff and Medalia (30)
compared this method to the iodometric method and found the lat-
ter to be more accurate. The reduction of peroxide by ferrous
ions and the colorimetric determination of ferric ions with thio-
cyanate, referred to as the method of Young (70), was recently
modified and used to determine peroxide content in radiat-ion-ox-
idized Polyvinyl chloride. Instead of determining ferric ions,
measurement has also been made of the excess ferrous ions, using
(11)
1,10-phenanthroline {38). •
A recent study was made of the iodometric method by which ' traces of peroxides in organic solvents could be determined.
This study by Banerjee and Budke (5) in 1964 modified the work
of Heaton and Uri in 1958 and the earlier work of Lea in 1931.
Dilution of the sample with an acetic acid-chloroform mixture
was followed by treatment with potassium iodide a~ter deaeration.
A one-hour reaction-time was allowed. The intens'i ty of the cdlor . of the iodine liberated was proportional to the concentration of
peroxide and was measured spectrophotometrically at 470 millimi
crons (or nanom.eters). Peroxide concentration was determined
and reported as active oxygen in the range of 5 to 80 parts per
million. The range was extended to cover 0 to 5 parts per mil
lion by using 1.5 centimeter cells and a wavelength of 410 milli
microns. It is believed that the absorption is due to the 13-
ion, which has a maximum at 362 mi~limicrons. In the method de~
scribed above, absorbance was read at higher wavelengths where
fewer co.npounds interfere. or the peroxiQ.es tested, only .di-tert
butyl and dicumyl peroxides, which have similar structures, failed
td react. Tetralkylammonium iodide has been used as the reagent ' I
instead of potassium iodide in the determination of traces of per- .
oxides in ~thers {24).
Hydroperoxidea, as well as dialkyl peroxides, were deter-·
mined in the presence of compounds which react easily with io-•• t
dine, using· triphenyl phosphine (16). The triphenyl ph~sphine
was oxidized to triphenyl phosphine oxide, and the excess was de-
{12)
termined, after treatment with formaldehyde and hydrochloric
acid to form lfh3PcH2oH] +Cl - , either gravime t;rically or photo
metrically. at 275·millimicrons.
Welcher (68} describes a qualitative test for the detection
of peroxides and persalts, using leuco methylene blue as reagent.
Leuco methylene blue was prepared by the action of sodium thio
sulfate on methylene blue in aqueous hydrochloric acid solution.
The method of analysis, using this reagent, was developed by Ueberreiter and Sorge (l7, 39) in 19.56 for hydroperoxides and dia-
cyl peroxides. The reagent, however, was difficult to prepare
and relatively unstable. This method was improved by reducing
the reagent in benzene with hydrogen in the presence of a plati
num catalyst immediately prior to use (15). Determination of
organic peroxides at the lo-6 molar concentration. level was re-
ported. A further improvement described a method for preparation
and purification of the reagent by reducing methylene blue with
phenylhydrazine, after which it was stable for several months (4).
The colorimetric determination described was carried out in a ··,'
mixed solvent of benzene and trichloroacetic acid. The time of
reaction was twelv~ to twenty-four hours. Beer' a Law was follow-··
ed for solutions containing 0 to lOmicrograms of peroxide per
millil.iter.
Eiss and Giesecke {17, 57) in 1959 substituted benzoyl leuco
methylene blue as reagent in· place of leuco methylene blue, as .. ,
it also reacts with peroxides and hydr~peroxides to form the
characteristioc;methylene blue color in a solution of benzene and
(13}
trichloroacetic acid.
+ (0) ---)
Benzoyl leuco methylene blue Methylene blue cation
Even this reagent is somewhat unstable, turning blue in ultra-.
violet light an~, ·to a lesser degree, in artificial light. or the naphthenates tried for· use as catalysts by Eiss and Giesecke,
zirconium naphthenate was found to best accelerate the peroxide '
decomposition and thereby increase the reaction rate. Benzoyl
and lauroyl peroxides, and p-menthane and cumene hydroperoxides
followed Beer's Law up to one part ·per million. Tert-butyl hy
droperoxide deviated. Di-te~t-butyl peroxide did not react. The
times· for complete color development (in the dark at 24 degrees
centigrade) were as follows: tert-butyl hydroperoxide, 30 min
utes; cumene hydroperoxide, 40 minutes; p-menthane hydroperoxide,
2 hours; lauroyl peroxide, 5 hours; and benzoyl peroxide, '30
hours.
A modification of this method (6) includes heating the reac- ·
tion mixture on a steam bath (in the dark) for thirty-five min
utes. The absorbance values for benzoyl peroxide by this modifi
cation were the same as those reported by Eiss and Giesecke (17)
after thirty hours.
An additional method described by Martin (40} was developed • by Tikkanen, using phenolphthalein as reagent. The absorbance,
however, was not linear and required the use of calibration
curves. This method was particularly useful: for the determina-
tion of hydrogen peroxide. Hydrogen peroxide may be the only pe,r~
oxide which .oxidizes this reagent, the other peroxides being
first hydrolysed to hydrogen peroxide.
Other reagents with limited use include chromic acid, phloro
glucinol, thiofluorescein, and p-diaminodiphenylamine. This
last reagent was used in a spot test to detect artificial bleach
ing substances in wheat flour (2). An intense blue color was . . .
formed by the reaction of organic peroxides with p,p'-diaminodi
phenylamine sulfate in acetic.acid (57).
Qualitative tests given by Feigl {20) include the use of po-, I I '
tass iwn iodide-starch paper,. p-phenylenediamine, ferrothiocya~-<'. ~
nate, and N,N 1 -diphenylbenzidine in concentrated sulfuric acid.
Organic peroxides could be detected, using 2,7-diaminofluorene
in ace~ic ~ciq, ~nly in the presence'· of peroxidases, which_ ra:ise
their oxidizipg_pow~r (21).
H2N-~.=J 0N~2 ............ 0/. [oJ '>
H2
Feigl {19, 22)' gives three tests for benzoyl peroxide using
amines as reagents.· :'In ~ne of these, benzoyl peroxide oxidizes . I
tetramethyl-p,p'-diaminodiphenylmethane after evaporation of the j.
solvent to give a blue stain.
(15)
•
In the other two tests, the products used in the determinations
are not amines. In the reaction with diethylaniline, acetalde
hyde is formed, and with hexamine, formaldehyde and nitrogen gas
are formed.
A method has been,developed to determine benzoyl peroxide and .
oumene hydroperoxide colorimetrically .after complexing with o-to-
luidine in the presence of styrene and dimethylaniline (29).
4. The spectrophotometric. method using N,N-dimethyl-p-
ph~nylenediamine sulfate
Dugan (12) in 1961 developed a method for the spectrophoto
metric determination of microgram amounts of lauroyl and benzoyl
peroxide, using N,N-dime~hyl-p-phenylenediamine sulfate. The ,
reagent solution was prepared by dissolving 0.3 grams of. the a;.;.·
mine salt in 10 milliliters of redistilled water and diluting to
100 milliliters with alsolute methanol. Standard solutions of
lauroyl and benzoyl peroxide were prepared in the range of 5 to
100 micrograms per milliliter of benzene. The colorimetric, de
terminations were carried out on either a Beckman Model DU or DKl
spectrophotometer, employing matched one-centimeter silica ab~
eorption cells.· Two milliliters of reagent solution were mixed
with two millili~ers of benzene containing peroxide. A reaction
time of thirty minutes· at'25,degrees centigrade was allowed.
(16)
Percent transmittance was then determined at 560 millimicrons, •
using a blank as reference. The precision of the method was cal-
culated to be 4.1 percent at the 95 percent confidence limit,
based upon ·eight determinations for each peroxide.
The spectrum of the reagent solution versus a solvent blank
was given. At 560 millimicrons the ·percent transmittance was
greater than 65 percent.
Absorption spectra were given for a constant peroxide con•
centration and varying amounts of reagent, 0.1, 0.3, and 0.5
percent. Transmittance was greater for 0.5 percent and approxi-
mately the same for 0.1 and O.J percent. Dugan believed that the
use of the higher concentration of reagent decreased the sensi-
tivity.
Spectra representing the standard curve for benzoyl peroxide
were given with concentrations of 5, 10, 20, 30, and 40 micro-. ,
grams per milliliter, as shown in Figure 1 in the Appendix. Ac
cording t~.Du&a~, ~~er's Law was followed between 5 and 30 micro
grams per milliliter with a deviation at 40 micrograms. The . .· > \ 11, 'l
spectrum for 40 micrograms per milliliter after 1.5 hours was ~ • , , t I , ,
given, and it sh9wed a d~o~ea~~ in.percent transmittance in the
400 to 525 millimicron range and an increase at 560 millimicrons.
Spectra representing the standard curve for lauroyl peroxide
were giveri with concentrations of 10, 20, 30, 40, 60, and 100
micrograms per milliliter, in which range Boer's Law was fol.i-,1:.;
lowed. In the spectra for both benzoyl and lauroyl peroxide,
there was a perc.ent transm"i ttance minimum (or an a~so:r,bance max-
' ·I, ,. I I I' '
(16)
Pere en t transmi tta.nce was then determined a.t 560 millimicrons, 1 .
• using a. bl~nk as reference. The precision of the method was cal-
culated to be 4.1 pe~cent at the 95 percent confidence limit,
based upon eight determinations for each peroxide.
The spectrum of the reagent solution versus a solvent blank
was given. At 560 millimicrons the percent transmittance was
greater than 65 percent.
Absorption spectra were given for a constant peroxide conJ
centration and varying amounts of reagent, 0.1, 0.3, and 0.5
percent. Transmittance was greater for 0.5 percent and approxi-
mately the:same for 0.1 and 0.3 percent. Dugan believed that the
use of the higher concentration of reagent decreased the sensi-
tivity.
Spectra representing the standard curve for benzoyl peroxide
were given with concentrations of 5, 10, 20, 30, and 40 micro
grams per milliliter, as shown in Figure 1 in the Appendix. Ac
cording to Dugan, Beer's Law was followed between 5 and 30 mi
grams per milliliter with a deviation at 40 micrograms. The
spectrum. for 40 micrograms per milliliter after 1.5 hours was
given, and :it showed a . decrease ·in percent transmittance in the
400 to 525 millimicron range and an increase at 560 millimicrons.
Spectra representing th~ standard curve for lauroyl peroxide
were given ·with concentrations of 10, 20, 30, 40, 60, and 100.
micrograms per milliliter, in which range Beer's Law was fol•·F;
lowed. In the spectra for both benzoyl and lauroyl peroxide,
there was a percent transmittance minimum (or an absorbanoe max-
(17)
I
imum) at 525 millimicrons approximately equal to the minimum at
560 millimicrons. •
· Other ratios of reagent and peroxide solutions were found to
be satisfactory, provided they were miscible. Greater color de
veloped with an increase in the amount of water. Dugan stated t b
that the reaction would occur in solvents for the peroxide other
than benzene, such as mineral oil.
The time allowed for color development was critical. The • . •'
temperatur~ was held constant at 25 degrees centigrade, and its
influence was not studied. According to Dugan, light affected
b"oth the peroxide solutions and the N,N-dimethyl-p-phenylenedia
mine sulfate reagent solution. Reagent solutions were prepared
fresh'daily, and the reactions were carried out in subdued light.
No color developed with dicumyl peroxide, even when iron, co• '
balt, or rare earth naphthenates were present as catalysts.
Dugan made the following observations:
Reagent in water + lauroyl peroxide in benzene + methanol ~
rapid color deve lopmenit ,_
Reagent in water + peroxide in benzene (no methanol) ~
immiscible, no color reaction ',,
Reagent· in water + benzene + methanol ~
very slow color reaction
Reagent in methanol + benzene~very slow color reaction
Reagent in water + methanol + laurio acid ---.::..
very slow color reaction
Reagent in water + methanol + laury1· alcohol '>.
(18)
very slow color reaction
Reagent in 90~ methanol + hydrogen peroxide ~
very slow color reaction
Color complex + 0.1 N H2so4 ~ no effect
Color complex + 0.1 N NaOH ~> colorless
In summary, Dugan stated that the reaction, greatly acceler
ated by the presence of lauroyl or benzoyl peroxide, appeared to
be: .. N,N-dimethyl-p-ptlenyl~nediamine sulfate +methanol~
blue colored complex
According to Dugan, although the reaction mechanism was not
known, it did not appear to be a simple oxidation, but rather a
reaction catalysed by a free radical mechanism, probably involv-
ing the splitting off of -Ng~3 groups by active OH. 3
The method of Dugan, developed to determine the presence of I
peroxides migrating from polymers formed using peroxide catalysts
(5), has been found to be suitable for detecting traces of per
oxide in diethyl ether, isopropyl ether, dioxane, and tetrahydro-·,,
furan (13). Because the reagent is an aromatic amine, it will
form Schiff bases with aldehydes if present. However, the alde
hydes tested did not interfere in concentrations less than 1000
micrograms per milliliter. They were.benzaldehyde, formaldehyde,
and glucose.
In 1963, Dugan (14) modified the method further to in~lude
other peroxides~ When added as O.l percent solutions in benzene,
the following rates of reaction were observed: for p-chloroben
zoyl peroxide and methylethyl ketone peroxide, two minutes; tor·· . '
{19)
t-butyl hydroperoxide and 2,4-dichlorobenzoyl peroxide, up to one
hour; and for myristoyl peroxide, cyclohexanome peroxide, hydr~x-. .
yheptyl peroxide, and di-t-butyl peroxide, two hours.
According to Dugan, the reaction with many peroxides would
proceed if the following solvents were substituted for benzene:
pyridine, N,N-dimethyl formamide, benzyl alcohol, ethanol, chlo-
roform, carbon tetrachloride, tetrachloroethane, and triacetin,
though all possible combinations of peroxide and solvent were not
studied. Di.ffere~t rates and occasionally different•:. end prod·
ucts in the various solven~were noted. No data for solvents
other than benzene was given. The only further reference to oth-
er solvents is that di-t-butyl peroxide reacted more rapidly in
carbon tetrachloride and chloroform than in the other solvents
listed, and a "color different from the spectrum reported was
observed in trichloroethane and benzyl alcohol".
Only in the reaction with benzoyl peroxide, which is rapid,
was oxygen removed by a nitrogen purge, with negligible results.
A spectrum scan was given showing the color formation between
fe·rric iron· and the reagent at pH 5 .5 with minimum percent
·transmittance at the same wavelengths as for peroxide. Addition
al spectra showed the effect of ferric ions on the reagent in
the presence of peroxide at a pH of 5.5. In addition to the 520
and 560 millimicron minima with ferric ions in the absence of
peroxide or with peroxide in the absence of ferric ions, a mini
mum occcn'ed at 720 millimicrona as well as at 520 and 560 milli-
microns when both were present. Transmittance through the solu
tion at 720 millimicrons became'' less with time. According to
{20)
Dugan, the intense red complex, which the ferric ions formed with \
the reagent could be differentiated from the peroxide reaction., •
product by observing the absorption at 720 millimicrons,·which
formed only in the presence of peroxid~. The following ions had
no effect on the reagent at pH 5.5: ca2+, co2 +, cu2 +, Fe2+, Mg2+,
Mn2+, Ni 2+, Ti 2+, zn2+, Al)+, a'nd,:·or3+.
When 0.25 milliliters of s.aturated ammonium carbonate solu-
tion were added to two milliliters of reagent prior to adding
two milliliters of pe~oxide in benzene, ·a green color formed and
the final pH was 8.7. Spectra were given for the reaction at pH
8.7 with the following peroxide concentrations: 10, 20, 40, 60,
and 100 micrograms per milliliter of benzanep A plot of the val
ues for percent transmittance at 675 millimicrons ind.icated that
Beer's Law was f'ollowed, The author stated that the previously
reported double band which formed in acid solution did not form
under alkaline conditions. Whereas the presence of benzaldehyde
had been shown to interfere in concentrations greater than O.l -.
percent at· pH 5.5, in the spectra of Figure 2, given for solu"' "L:.':)
tions at PH 8.7, little effect was shown on the 675 millimicron
peak for concentrations up to 1.0 percent. This is because alde
hydes do not form Schiff bases under alkaline conditions, Ac-• J .
cordingly, organic peroxides could b~ detected in the presence
of high concentrations of aldehydes by adding alkaline buffer to
the reagen~ to yield a final pH of 7.5 to 9.1.
The following summary of reactions was given. The "reagent" . .. is 0.3 per~ent N,N-dimethyl-p-phenylenediamine sulfate in 10 per-
(21)
cent water in methanol, described previously. The "peroxide" is l
\
100 microgi;oams per ·milliliter of either benzQyl or lauroyl perox-I
ide in ben~ene. "Aldehyde" refers to a one percent solution of
benzaldehyde in ethanol. "Tris-buffer 11 is two grams of 2-amino-
2-(hydroxymethyl )-1,J-propanediol in 100 milliliters or dis tilled
water.
Reagent + peroxide~ red-violet color ~ + 0.5 ml 6 N H2S04~
stable colo'.r
Reagent (pH 5.5) + ~.5 ml 6 N H2S04 + peroxide~ NR (No observable color reaction)
Reagent (pH 5 .5) + 0.5 ml 6 N H2S04 + aldehyde-) Schiff color
Reagent + 0.5 ml 1 CN NaOH + peroxide~ NR
Reagent + 0.5 ml l N·NaOH + aldehyde---1 NR ' . ~ + o.5 ml 6 N H2S04
--7 Schiff color ' Reagent + 0.25 ml satd. (NH4)2C03 + peroxide~ green color
Reagent + 0.25 ml satd. (NH4 )2C03 + aldehyde~ NR
Reagent + 0.25 ml 2% tris•buffer (pH 7 .4) + peroxide~
green color
Reagent + 0.25 ml 2% tris-buffer (pH 7.4) +aldehyde~ NR
Reagent + 1 drop of cone. NH40H (pH 9.1) +peroxide ----t green color
Reagent+ l .drop of cone. NH40H (pH 9.1) +aldehyde~ NR
p-Dimethylapiinobenzaldehyde + peroxide~ NR
p-Dimethylaminopropioni trile + peroxide~ NR
Dugan concluded that "the peroxide will not react if strong
acid . C~. N H2S04) is added "to the reagent. Undoubtedly the per-
(22)
. oxide is destroyed in the acid. Strong base (l N NaOH) also
destroys the ability of the peroxide to react." •
(23)
II. Oxidation of Amines
Benzoyl peroxide is a compound known to be an oxidant and a
source of free radicals. The reagent used in this research to
determine this peroxide, N,N-dimethyl-p-phenylenediamine, is ar
omatic and has two functional groups, one of a primary and one
of a tertiary amine. Therefore, it should be easily oxidized
in numerous ways depending upon the oxidizing agent (49).
reaction between peroxides such as benzoyl peroxide and amines
results in the production of free radicals (65). It is known
that N,N-dimethyl-p-phenylenediamine can be oxidized by such
reagents as bromine and ferric ions to a free radical, red-vio
le t in color, that is called Wurster's red (18, 67). In the
literature with regard to Wurster's red, higher oxidation prod
ucts are not given (45). When tertiary amines are oxidized by such oxidizing agents
as hydrogen peroxide and pe~acids, which can supply an oxygen
atom with six electrons, the amine oxide is formed (49).
'b• . . . . ~ The same reagent·s oxidize primary and secondary amines by the
following steps: ' \ ll l
RNH2 fQl) [
0 ] . OH R-~-H -4- RN-H RNO
( Rz-lf-H] ~ 0
RzNOH The primary' amine is usually oxidized all the way to the nitro
compound. The secondary amine is onl~ oxidized to the hydroxyl
amine. In the oxidation of aniline, .the products, which may be
N-phenylhydroxylamine, nitrosobenzene, or nitrobenzene,depend
(24)
upon the temperature, and t~e amount and kind of oxidizing a-. \
gent (50). Aniline is oxidized with sodium.dichromate in dilute
sulfuric acid to _1,4-benzoquinone. With oxidizing agents that
abstract a hydrogen atom or hydride ion, the roactions are more
complex, often· giving highly colored products.
A. Formation of Free:Radicals
When peroxides, such as benzoyl .peroxide, react with amines,
a complex series.of reactions occur. In some cases free radi~als
are formed (65). Thus benzoyl peroxide and dimethylaniline have
been used to induce polymerization of monomers, such as styrene
and methyl methacrylate. However, the primary process in perox
ide-amine reactions does not appear to be the free radical for
mation, but rather ·a polar reaction from which the unstable in-
termediate breaks down to form radicals.
An investigation.of the products of the reaction of benzoyl
peroxide with a series of primary, secondary, and tertiary a
mines was first made during the period 1925 to 1933 by Gambarjan
( 65}. A survey of the kinetics of the process was made .1?Y Bart
lett and Nozaki (65) in 1947• They found the reaction to be
very rapid 1n comparison to the ordinary thermal deoomposi ti on of
peroxide. Most of our present informa~ion results from detailed
studies by Horner (65) and associ~tes.
Radical formation was clearly shown in diacyl peroxide-ter
tiary amine systems, of which benzoyl peroxide and dimethylani
line is an example. In a dilute solution of chloroform, the
products of this react.ion were benzoio acid, in almost quanti ta-,
(25)
tive yield, plus monomethylaniline, formaidehyde, and small a
mounts of p-benzoyloxydimethylaniline and p,p'-di(dimethylamino) • •
diphenylmethane.
The reaction scheme for the decomposition proposed by Horner
is. the followit':g: ,,
0N(CH3~~2.' + (C6H5C0)202 ~
I
CH3 ¢000. ¢coo-I-> 0-Nt. + .. +
CH3 \... V"'
,,. II .
yH3 H20~
9H3 II~ 0~H . + 0COOH 0rj + CH20 + ¢COOH
CH20CO~ H
II~ ¢c90~ __ ,.N(CH))2 + ¢COOH
There is evidence to support only the first two steps. In . .'
support of step one, it was.found that the rate·or peroxide de-
composition was greatly accelerated by electron-supplying groups
on dimethylaniline and retarded ?Y elect~~n-withdrawing groups. j
When the concentrations '..Of peroxide and amine were o. 05 molar
in chloroform at 20 degrees centigrade, the half-life of the
perox~de was five minutes with p-methyldimethylaniline, thir
teen minutes with dimethylaniline, and six days with p-cyanodi
methylaniline. In addition, electron-withdrawing groups on the
peroxide accelerated the reaction. The compound, benzoylsulfo
nyl peroxide, r·reac ted almost instantly even with p-ni tro-dimeth
ylaniline. ·The initiation of polymerization by the system is" ·
(26)
.. evidence of radical formation along with the observation that
\ ' the system absorbed oxygen, keeping the perQxide concentration_
high. In addition, Boekelheide and Harrington {65) reported
the initiation of polymerization by acetic anhydride-dimethyl•
aniline oxide, which presumably forms a similar intermediate.
The rates found in kinetic studies of the reaction are consis-
tent with an initial bimolecular process.
Walling and Indicator {66) suggested that the unstable in~
termediate I deccimpos-ed by competing radical and non-radical
forming processes. Competing with the radical process would be
the following:
¢COOH
An inconclusive study was made by Roy and Swan (.53) of the re
action of benzoyl peroxide with tertiary amines. They attempt
ed, by trapping intermediates, to determine which products.re
sulted from radicals and which from ions.
Secondary amines also react re~dily with benzoyl peroxide,
methylaniline several times' more rapidly than.dimethylaniline,
although, generally, there is no evidence for radical formation,
such as initiating polymerization or. absorbing oxygen ( 9). Fur
ther ,studies by Denney and Denney ( 11), using benzoyl peroxide
labeled with oxygen-18 in the carbonyl position, tend to prove
that the ~echanism for the reaction with a secondary amine.in
volves nucleoph111c attac~ by the am~ne on the peroxide to give
(27)
a pair of ions, which then undergo proton transfer.
Primary amines and benzoyl peroxide giv~ a co11plex mixture' ·
of products, which from aniline include benzoic acid, benzani
lide, azobenzene, and a Arnall amoqnt of o-hydroxybenzanilide
(65).
However, very little is known of radical formation in the
reactions of other types of peroxides with amines. Initially,
only a few types of reactions and a limited number of types of
rad&cals were studied, avoiding the complexities of polar re
actions (62). Indeed, it·was not until 1937 that the role of f
free radicals as reactive intermediates in ordinary tempera
ture, liquid-phase reactions was recognized. During this year
the studies of Hey and Waters, of Kharasch, and of Flory were
published (62). Hey and Waters interpreted a number of reac~
tions, heretofore stu..~biing blocks in the development of the e-•
lectronic theory of•organic reactions, as being free radical
processes, Included was the "abnormal" addition of hydrogen
bromide to olefins, Independently, Kharasch proposed the pres-
ently accepted free radical chain mechanism for the same reac
tion~ In his papers, Flory treated vinyl polymerization as a
free radical chain reaction. I
Like pther types of compounds~ f.ree radicals have their own
distinctive physical properties:~, including molecular weight,
absol"ption spectrum, dipole moment, melting point and so forth.
Furtpermore, due to their unique structural feature,one or more
unpaired eleotrona, free radicals as a class exhibit a unique
,. I•
(28)
property, paramagnetism. Conjugated free radicals, particular
ly those in which the odd electron is conjugated with the aro~ •
matic ~uclei, show strong light absorption in the visible region
(63). Often in oxidation-reduction reactions the transient ap
pearance of color can be taken as evidence of the presence of
radical intermediates. Acceleration by light is a positive in
dication of a radical process (64).
Walling (64) gives some' general characteristics of radical .
reactions. They .wi11:, occur in polar, as well as inr" non~pol.ar,
solvents. They are generally insensitive to the ionizing power
of solvent,, since the intermediates are non-ionic and not high
ly polarized (with the exception of some oxidation-reduction
systems). In contrast to many polar reactions, they rarely show
catalysis by acids 'or bases (with th~ exception of certain oxi
dation-reduction systems).
B. Reactions of N,N-Dimethyl-p-phenylenediamine
'rhe free mnine::i:(51, 67) of the reagE:mt, N ,N-dimethyl-p-phen- . ·
ylenediamine _sulfate, used by Dugan can be obtained as a white
crystal from a benzene solution on the addition of ligroin. It
melts at 41 degrees centigrade and boils at 263 degrees centi
grade. It is soluble in cold water, alcohol, benzene, and chlo-
roform, less soluble in ether, and insoluble in ligroin. It is
easily oxidized and cannot be kept indefinitely in air (28).
Its salts, however, are more stable.
According to Welcher (67), this reagent has been used for
the determination of chlorine, hydr~gen sul~ide, manganese, and
(29)
vanadium. It has been used for the detection of bromine, chlo-
rine, copper, hydrogen cyanide, hydrogen sulfide, manganese, and •
vanadium. It reacts with hydrogen sulfide in the presence of
farri'o chloride in strongly acid sol.ution to form the dye, meth
ylene blue. It reacts with the oxidizing agents, chlorine, bro
mine, and vanadates, to form a color ref~~red to· as Wurster's
red. In contrast, lead salts show a weak turbidity,a,nd~bismuth
salts give a yellow-orange precipitate with the reagent.
Coppe~ can be detected by the reaction of cupric salts with
potassium iodide to form free iodine, followed by reaction with
tha,· amine reagent to form the red-violet color, Wurster's red.
Spot tests to determine N,N-dimethyl-p-phenylenediamine in
clude oxidation to Wurster's red (18), carried out best with
dilute ferric chloride solution. To a drop of alcoholic neutral
or slightly acid test solution was added a drop of 0.01 percent
ferric chlcride solutlon. The test was P?Sitive with the forma
tion of a red-violet color.
c. Formation of Wurster's Red
In his writings of 1879 and 1886, Wurster (69) proposed the
following e:npirical formulas ·for the oxidation products of two
p-phenylenediamines •.
The red dye from p-aminod~methyl~niline:
The blue dye from tetramethyl-p-phenylenediamine:
C10H15N2Br
These two oxidized forms, correct except for the numb.er of hy-
drogena, are referred to ~s Wurster'~ salts, Wurster's red and
Wurster's blue. These compounds are examples of compounds, in• •
(JO)
termediate with. respect to oxidation level between a diarnine ~nd
a diimine, which are similar to hydroquinone and quinone (43).'
By the 1930's an increasing number of papers were being pub
lished advocating the existence of free radicals (43) instead of
double molecules. In some cases, where a free radical exists,
such as with Gomberg's triphenylmethyl and Wieland's biphenyl
nitride, an equilibrium was assumed to exist between the free
radical and its polymeric saturated form. · In other cases, such
as in the oxidation of aromatic diarnines, the existence of only
the free radical was assumed, as shown, for example, by boiling
point determinations of Weitz and Fischer. A large contribution
in this area was made by Michaelis (43), who in 1931 used po.ten
tiometric analysis to study this type of oxidation, especially
oxidation by way of the two Wurster's salts mentioned above.
Bromine was used as the oxidant.
Michaelis recorded his observations. When the titration
was performed rapidly, at a certain point the color, red or
blue, which had developed disappeared again. If, after reach
ing this point, the solution was allowed to stand, the color
gradually returned, but not to its maximum intensity. The rate
of return depended upon concentration and pH.4 Spectroscopic
analysis showed the second colored sµbstance~to be the same as
the first, recognizable by a characteristic double band, which
differed for Wurster's red and Wurster's blue only by their
spectral location. According to Michaelis, other dyes might al
so develop· along with the. reappearance of the Wur4'.ter 1 s salts.
(31)
His interpretation of the above observations was that Wurs
ter' a red or blue differed from the parent substance by only
one oxidation equivalent. The disappearance of dolor indicated
·a higher oxidation level, very likely a diiminoquinone, which
would be very labile, undergoing irreversible changes into sub
stances inclined to still further oxidation.
Within a certain pH range, the most suitable pH being 4.6,
the first half of the titration could be carried out with con~
stant potentials; as ~hown in Figure 3. In the second half, no
constant potentials could be obtained under any conditions, the
potentials always drifting back to the negative side as though
the diiminoquinone spontaneously and irreversibly disappeared.
The amount of oxidant for each of the two steps was the same,
within the limits of error. The curve for the first step was
that of a regular oxidation-reduction system with the differ
ence between the reduced and oxidized forms being one electron.
Therefore, the dye, Wurster 1s red, and also Wurster's blue are
half-reduced quinones or semiquinones with an odd number of e
lectrons. :
A later report by Michaelis with Schubert and Granick C45) was concerned with the stability and color of Wurster's salts,
modified by substitutions at the amino groups and at the ben
zene ring. A study of the stability of these semiquinone radi
cals was difficult because they exist in equilibrium with the
diamines and the very labile diimines. Quinone diimines are
very unstable in all solvents not en.tirely water free. Somo ot
the free radicals a.re stable even in aqueous solution. Substi- ·
{32)
tution of methyl groups for hydrogen on the ring had no effect \
unless the methyl group was ortho to a methylated amino group,· •
in which case the stability was decreased. Substitution of
methyl groµps for hydrogen attached to nitrogen increased the
stability, the tetramethylamino compound being the most stable of
the series. Substitution on the ring by other groups such as
-OCH3 1 -Cl, and -S03H caused destabilization.
Radicals, such as Wurster's salts, are capable of existence
because of a part~cular symmetry of structure resulting in res'-._)
onance. According tp Michaelis (45), the resonance could occur
only if the aromatic ring, the two nitrogen ato~s, and the four.
atoms attached to the nitrogen were all located in one plane.
Michaelis showed that the radicals having little stability did
not have the planar structure necessary for resonance. It is
stated in a recent text by Hendrickson, Cram, and Ha~mond (26}
that these radicals are stabilized by extensive delocalization
of the electrons and that destabilization is due to steric ef-
fects or repulsion or like charges. The following structural
forms are included for Wurster's blue:
[o) -~. -e
These are not all or the possible forms. The first two were
given by Michaelis (45}.
In addition to structure, the stability of the radicals de
pends upon pH. In aqueous solution the necessary pH range was
(33)
found to be between 3.5 and.6. Michaelis gave the following· !
figures to represent the three possible ionization states of the •
radicals.
Only formula two can exhibit the resonance necessary for stabil-
ity.
In studying the absorption spectra, it was found that each
methyl group substituted for hydrogen in the amino groups had a
bathochro~ic effect, shifting the two distinct bands of the rad-
ical toward longer wavelengths. The two bands for Wurster's red,
the spectrum of which is given . in Figure 4, showed maximum ab••:::-:.·
sorbance at approximately 515 and 550 millimicrons. Attaching
methyl g:oups to the ring had no bathochromic effect, but
changed the pattern of the bands.
An increase in· color due to further oxidation by exposure
to the air was noted. The lifetime of these compounds was not
affected by diffuse daylight.
Accord~ng to Michaelis, in dilute solutions these radicals
did not combine with each other or with the original diamine,
but underwent condensation or other reactions with other mole-
cules in the solution, especially those on the oxidation level
of the diiminoquinones. In higher concentrations or at low
temperature, most Wurster's salts, with the exception of Wurs-
ter 's .blue, formed polymers, which d~ffered in color from the
free radicals, all .of the polymers being deep green-blue in the
{34)
crystailine state (~). In the case of Wurster's red, only the
dimer existed. For compounds, in which both ni~rogens were not •
completely methylated, a higher polymer might be possible.
As was stated earlier, benzoyl peroxide reacts with a terti
ary amine to form an intermediate complex, which dissociates in
to two ion radicals. Using the system, tetrrunethyl-p-phenylene
diamine (TMPD) and chloranil (C) in various mixtures of chloro
form, 1,2-dichloroethane, and ethanol, Isenberg and Baird (27)
attempted to show by ,electron spin resonance that the similar
complex .(TMPD~C) which formed could not dissociate into the two
ion radicals TMPDt and c.- in a non•polar solvent.
Steigman and Cronkright {$8) showed that the ion radicals
did form in non-polar solvents in the presence of excess acid.
Tetramethyl-p-phenylenediamine in reduced form is a diacid base
with the acidity constants, pKl equal to 2.20 for the dissocia-2+ + tion of TMPDH2 and pK2 equal to 6.35 for TXPDH • 'The fraction
present as TMPDH+ is at its maximum at pH 4.28, very close to
the pH found to be most suitable by Michaelis (45) for nadical
formation. Therefore, with the form of the radical capable of '. '
resonance as the product, the following equation best describes
the oxidation to Wurster's blue.
H H3c,~~CH3 H3c, t .,,CH:J
N
Q ~ 0 H+ ~ + + e
'N C ).i,CH H c""-'CH
3 3 H3 .3
(35)
Steigman and Cronkright studied t.he effects of different ac\
ids on Wurster•s blue, formed in benzene from tetramethyl-p- ' •
phenylene~iamine with chloranil as oxidant. They found that,
regardless of the number of acid molecules associated with
TMPDH+ prior to oxidation, one additional molecule of acid was
necessary for the formation of Wurster's blue. This additional
molecule was believed to stabilize the counteranion, which p~ior
to oxidation had been stabilized by hydrogen bonding with
TMPDH+. The additioQ of bases, proton acceptors, and salts ca-
pable of hydrogen bonding.caused the disappearance of blue
color.
The spectrum of Wurster's blue, in methanol containing·per
chloric acid, by Steigman and Cronkright, shown in Figure 5, was
almost identical to those obtained by Michaelis, Schubert and
Granick (45), and by Albrecht and Si~pson (58) for the perchlo~
rate in water. In benzene containing chloranil and trichloro
acidic acid, the 565 peak shifted to 570 millimicrons and be-
came more prominent than the second peak. A large excess of
tetramethyl-p-phenylenediamine in relation to chloranil was
used to diminish the diimine concentration.
(36)
EXPERIMENTAL
I. Reagents ,
The N,N-dimethyl-p-phenylenediamine sulfate, [NH2c6H4N(CH3)zj2·
H2so4, molecular weight 370.47, used was obtained from East-
man.
The benzoyl peroxide, (C6H5C00)2 , 99 percent pure, and the 2-
amino-2-(hydroxymethyl)-l,J-propanediol were obtained from
Matheson, Coleman and Bell.
All other chemicals used were of reagent or equivalent grade,
with the exception of purified annnonium carbonate, used only
in verifying the work done previously by Dugan.
All water used was redistilled from an alkaline permanganate
solution.
(37)
II. Apparatus
TM Scans of tho'visible spectrum were made with a Beckman Acta
III UV - Visible Spectrophotometer, employing matched one
centimeter silica absorption cells.
Absorbance measurements at a set wavelength were made with ei
ther the Beckman Acta™ III UV - Visible Spectrophotometer
or a Beckman Model B Spectrophotometer, employing matched
one-cef?timeter sil'ica absorption cells.
The pH me.asurements of solutions were made using a Sargent pH
Me·ter Model LS.
A scan of the infrared spectrum for the oxidation product ob
tained was made with a Perkin-Elmer 137 B Infracor~ Spec-
trophotometer, using a potassium bromide wafer for the sam-
ple cell.
Sample weighings were made with either a Mettler Type H Analyti
cal Balance or a Mettler Top-Loading Balance. '
Miscellaneous laboratory glassware and equipment were used, in
cluding volumetric flasks, pipets, erlenmeyer flasks, gradu~
ated cylinders, a distilling flask and condenser, a Bunsen
burner, separatory funnels, a Buchner pyrex fritted funnel~
and a filtering flask, and a centrifuge.
{38)
III. Preparation of Solutions and General Procedure
•
All reactions were carried out under fluorescent light and
at room temperature, which varied from 21 to 25 degrees centi
grade. All solutions were stored in the dark.
A 0.3 percent reagent solution was prepared according to the
method of Dugan, by dissolving 0.3 grams of N,N-dimethyl-p-phen
ylenediamine sulfate in 10 milliliters of redistilled water and '
diluting to 100 milliliters with methanol in a volumetric flask.
This solution will be referred to in the sections that follow as
the reagent solution. Solutions of O.l, 0.2, and 0.5~peree~t a-
mine sulfate were prepared in a like manner as were solutions of
·0.3 and O.l percent a~ine sulfate in methanol only and in water
only. Due to their rapid color development, each of these solu
tions was prepared as'.needed and only freshly prepared solutions
were used.
A stock solution of benzoyl peroxide was prepared by dissolv
ing 0.0500 grams in 100 milliliters of benzene {or pyridine) af
ter which l, 2, 3, 4, 5, 6, 7, and 8 milliliters of stock solu
tion were diluted to 50 milliliters with solvent to make standard
benzoyl peroxide solutions, containing, respectively, 10, 20, 30,
40, 50, 60, 70, and 80 micrograms of 'benzoyl peroxide per milli-
liter. Generally, scans were made using two milliliters of an .·.
appropriate solution containing the amine sulfate, mixed with two
milliliters of benzene or pyridine containing the peroxide.
In order to have a miscible solution with the addition of
(39)
acid to the reaction mixture, sulfuric acid solutions were pre~
pared by adding concentrated sulfuric acid tQ methanol. (Aqueous
acid solutions were used with the am.ine . .in:water only.)
To prevent the formation of two layers upon the addition of
tris-buffer, the buffer solution was prepared by dissolving two
grams of 2-amino-2-(hydroxymethyl)-l,3-propanediol in 10 millili
ters of redistilled water and diluting to 100 milliliters with
methanol. This solution will be referred to as tris-buffer. A . two percent aqueous solution of tris-buffer was used to study the
reaction with no methanol.·
For studying the reaction, rather than making a standard
curve or determining factors influencing the standard curve,
methanol was used instead of a reagent blank. In studying the
effect of the amine concentration, a separate reagent blank was
used for each concentration.
In cases where only the wavelength of the peak values was of
concern and no~ the solution concentration, no values for a~aor
banoe are given on the scans • . ...
(40)
IV. Data and Re·s ul ts
A. A Study of the Effect of Variables on 'Dugan's Method
A preliminary investigation was carried out according to the
original method of Dugan with N,N-dimethyl-p-phenylenediamine
sulfate and benzoyl peroxide. A study was then made of the ef-
feet of the variables, time and pH, on the system.
Scans of the ~isible spectrum were made at intervals other·
than thirty minutes in order to study the development of the ab-
sorbance peaks with time. When benzoyl peroxide in benzene was
mixed with a solution of N,N-dimethyl-p-phenylenediamine sulfate,
a scan of the spectrum between 400 and Boo nanometers shows ab
sorbance peaks at 515, 555, and.to a lesser degree at 670 nano
meters. This scan is given in Figure 6. The 515 and 555 nano-
meter peaks increased rapidly to a maximum in approximately five
minutes and then decreased. The 670 peak increased less rapid
ly. Scans made over a two hour period showed that the 670 peak
had become more intense by the end of that time than the 515 and 'I
555 peaks. Wit~in twenty-four hours, there were no 515 and 555
peaks, and the 670 peak had shifted to a sharp peak at 640 nano
meters, almost identical to .the peak which developed when the
amine salt in methanol autoxidized. (See Figure 18.)
The effect of changing the pH of the solutions before and I
after mixing the reagents was studied. Dugan (12, 14) had stat-
ed that the addition of O.l N sulfuric acid to the colored prod
uct had no effect and tha~ the addition of 0.5 milliliters of 6 N ,-'l
{41)
sulfuric acid stabilized the color. Addition of the stronger
acid solution before mixing the reagents prevented the reaction, • .
and Dugan concluded that the peroxide was destroyed in the acid1
First'the effect of the addition of acid was studied. The
concentration of acid was varied, and also the time of addition.
Adding acid to the reagent solution prior to adding the peroxide
prevented the formation of color as reported by Dugan. The
addition o~ acid at any time after the reactants were combined
stabilized the re~ction at that point. Figure 7 shows the max-,
imum absorbance, which occurped five minutes after mixing. It
shows also the effects of adding acid to the reagent solution
prior to adding peroxide and immediately after adding peroxide.
The addition of acid greatly inhibited the color formation. How-
ever, scan b shows that in the few seconds before acid was added,
a certain amount of color had a chance to form. For each of ':.,'i..::
these scans, 0.1 milliliters of 6 N sulfuric acid in methanol
were added to the reaction mixture. It was found that 1 N sul-
furic acid was as effective as 6 N for stabilizing the reaction,
but weaker solutions were not. This is shown in Figures 8, 9,
and 10. The pH_ of the reagent solution was approximately 5.5 in-
itially. The pH after addition of O.l milliliters of 1 N sul-. I
furic acid in methanol was approximately 1.8. Figure 11 shows
that, after the reaction was stabilized at· peak formation, Beer's
Law was followed at 555 nanometers for concen~rations of peroxide
from 10 to 60 micrograms per milliliter. Figure 12 shows the
variation of absorbance with time at 555 nanometers for 60 micro-, ''
/ , grams of benzoyl peroxide per milliliter of ben~ene with and
I" ' ' I ' . ... . ' ,. ' '
• I {. .,,...- . ~ , ', .', : • ! . ~ •. '· .1 .
<42)
without the addition of acid. . ~
In an attempt to stabilize the color formation by lowering, •
the pH slightly from 5.5 to 4.7, the reagent solution was made
».
up, substituting 1 N acetic acid for water. The color, which
formed in this solution after peroxide was added, showed the
same instability at 555 nanometers and slightly .less inten~ity ·
than before the substitution.
Dugan made the reaction mixture basic by the separate addi-.
tions of tris-buf,f;'er, concentrated ammonium hydroxide and satu'~·S···
rated am.~onium carbonate solution. In each case a green color
was observed, but spectra were given only for the solution to
which ammonium carbonate had been added. Dugan stated tbat the·
previously reported doubile 1-:band which occurned1 ·.ia.· acid·;solution
did not form under alkaline conditions.
Because they were not given, spectra were made of the reac~~
tion mixture to which tris-buffer was added. When 0.25 millili-
ters of tris-buffer were added to two milliliters of the rea-
gent solution (giving a pH of 7.4) ,and then two milliliters ·or
peroxide in benzene &ere added, the solution first turned a red~
violet or magenta color (as at pH 5.5) and then green in less
than five minutes, with the development 6f peaks at 465 and 670·
nanometers, which were fairly stable. Figure 13 shows the ab~
sorbance at 555, 465 and 670 nanometers with time. Figure 14
shows that· the peak values at 465 ~nd· 670 nanometers follow
Beer's Law'. (Figure 14 was made using the data from the scans
..
(43)
showed a n~gligible decrease in abaorbanoe as compared to add~
ing it before. ' ,···:
• A time 'study of the reaction, given in Figure 15, shows that
after two hours both peaks were increasing, the 465 peak more
rapidly than the 670 peak. A scan after three hours.shows· the·
465 peak increasing and the 670 peak decreasing. This was. con
tinuing after five and a half hours.
The same color formation occurred when the, tris-buffer·.was
omitted and pyridi:ne w.as used in place of benzene to achieve ap~
proximately the same solution pH. Figure 16 shows the peaks at·
465 and 670 nanometers, along with 'the diminishing peaks at 515
and 555 nanometers when the scan was begun immediately after ' .
mixing. Figure 17 is a scan between 600 and 400 nanometers only,
begun at zero mixing time, which shows more clearly the forma-·
tion of the 515 and 555 peaks.
B. N,N-Dimethyl-p-phenylenediamine Sulfate in Methanol
An attempt was made to better understand the Dugan method and
to improve it by studying the effects of the solvents used. Du~
gan (12) had stated that the colored reaction that occurred was ·
between the amine sulfate and methanol. However, he observed
greater color developmerot as the amount of water in the mixture
was increased. The reagent is pale pink in a freshly· prepared
water-methanol solution. Even without peroxide, noticeable col-.
or development occurs with time.
The first study involved a change to methanol as solvent for
the amine sulfate rather than the water-methanol mixture. Ben-·
(44)
zene remained the solvent for the peroxide. When the ·amine salt
was dissolved in methanol, a scan made after twenty-focir:hours~ •
given in Figure lB, shows the development of a peak at 640 nan6-·
meters, The solution at this time was dark blue as contrasted
to the pale pink color of the freshly prepared solution. A scan
after only two hours shows slight peaks at 515 and 555 n~nometers, .. . half as intense as those for the amine salt in water. (See Figure
25.) (For these scans, the concentration of the amine salt wa~
changed from 0.3 perc~nt to O.l percent due to its low solubility
in methanol.)
When two milliliters of the peroxide in benzene were com-
bined with two milliliters of the amine salt in methanol, the
same sharp peaks appeared at 515 and 555 nanometers, as shown in
Figure 19. A scan twenty minutes after mixing shows these peaks
decreasing and a 670 peak developing.
When the peroxide solution was added to a twenty-four-hour-
old solution of the amine salt in methanol, sharp peaks appeared
at 515 and 555 nanome tera in addition to the peak at 640 nano• .. -,\;. ·
meters. These can be seen in Figure 20. The 515 and 555 ~eaks ~.
were approximately the same height as from a fresh'.solution of
the amine salt in methanol, or water and methanol.
Figure 21 shows that when acid or. base (ammonium hydroxide)
was added to a twenty-four-hour-old solution of the amine salt,
in methanol, the 640 peak remained. With the addition of base,
an immediate scan showed a 465 peak forming.
When tris-buffer was added to a solutio·n of the amine· salt ., .
·,
in
(45)
methanol, a scan after twenty-four hours, given in Figure 22, '.-~
shows a peak at 465 nanometers and a slight rise near 640 nano-·-. •
meters {pH 7.7). A scan of the amine salt_ in methanol plus·one_
drop of concentrated ammonium hydroxide (giving a pH greater
than 8.3) after twenty-four hours shows only a peak at 465 nano-;
meters, more intense than for pH 7.7. Because the reaction oc-
curs very slowly without peroxide, the time interval of twenty
four hours was allowed for sufficient color development. .
A study was made Qf the effect of. the addition of acid and
base upon a solution· of the amine salt in methanol plus peroxide
in benzene after the 515 and 555 nanometer peaks had decreased.
below the intensity of the 670 peak. For these scans, given in
Figure 2J, two milliliters of the amine salt in methanol (O.l
percent) were mixed with two milliliters of peroxide in benzene
{50 micrograms per milliliter). After ten minutes, concentrate~·
a-mmonium hydroxide was added to completely remove the 515 and
555 nanometer peaks. Scan f in Figure 2J shows only a peak at
465·nanometers, the solution was tan, and the pH was greater than
8. The pH was then varied by the dropwise addition of sulfuric
acid in methanol and concentrated ammonium hydroxide. As the
solution was made more acidic, the color changed from tan to
yellow-green (pH 7.7) to green-blue (pH 4.0) with a decrease in
the 465 peak and an increase in the 670 peak. As the color
changed from green-blue to violet (pH 1.7), the 670 peak began to
decrease and slight peaks reappeared at 515 and 555 nanometers.
As the color changed from violet to pink (pH 0.5) to red {pH les.s
(46)
than 0.5), the 670 peak c:bntinued to decrease, a peak appeared, at
510 nanometers, and the peaks at 515 and 555. nanometers were ,.n~ :' ·
longer seen. With this solution, it was possible to change. 'froni ,;
acidic to basic and back again several. times without evidence of ·
decomposition as shown by the repetition of the color changes. .,.
(In, making the scans described above, after scan: f was made,· ·the
solution was made very acidic and scan b was made. Then base ,,;, ·
was added and scans d and e were made, followed by the addition
of acid to make scans ,c and a. The ammonium sulfate which formed
in the solution had to be removed by the use of a centrifuge.)
Figure 24 shows maximum formation of the 515 and 555 peaks
from the reaction of the amine salt in methanol and the peroxid·e
in benzenel After making this scan, 0.1 milliliters of 6 N sul
furic acid were added, which stabilized the reaction but at a
lower intensity. A continuation of the addition of acid greatly
decreased the two peaks already formed, with no appearance of
other peaks.
When acid was added to the amine salt in methanol, the solu~
tion became colorless and remained colorless after the addition
of peroxide in benzene. The addition of one drop of ammonium hy~
droxide produced a pink color, which immediately turned blue-
green.
c. N,N-Dimethyl-p-phenylenediamine Sulfate in Water
The color development of the amine salt in water only was· al-:; •·· >
. . so studied, as was the reaction between the reagent in w~ter and
benzoyl peroxide in benzene with varying pH. Soans were made of
:!
(47)
the separate layers of this two-layer system after mixing. The .
pH of these layers was changed before and af~er separation. ·'Du~ · ·
gan (12) had stated that the reagent in water and peroxide in'
benzene were immiscible and that no colored reaction occurred.
·· •.. i.
Figure 25 shows that the amine salt in water slowly formed o
peaks at 515 and 555 nanometers. After twenty-four hours, 'th~re
were sharp peaks at 515 and 555 nanometers. When tris-buffer or
a drop of concentrated ammonium hydro~ide was added to this
twenty-four-hour-old solution, a scan of this solution, give~ ih
Figure 26, shows a raised section between 515 and 555 nanometers,
but no distinct peaks and no other peaks.
When one or two drops of ammonium hydroxide were added to the
amine salt in water,•a scan after two hours, given in Figure 27,
shows a peak at 475 nanometers. In a solution containing no
methanol, the amine salt in water reacted with peroxide in pyri
dine, forming peaks at 675 and 485 nanometers as shown in Figure·
28.
When five milliliters of the amine salt in water were shaken
with five milliliters of peroxide in benzene, the intensity of
the pink color of the wat.er layer increased, and the benzene lay
er turned yellow. A scan of the water layer, given·in Figure 29,
shows peaks at 515 and 555 nanometers., and a scan of the benzene
layer in Figure JO shows a triple peak, centered at 445 nanome
ters. Wit~ the addition of tris-buffer or ammonium hydroxide to
an identical two-layer sys tern, the color was extracted into the'
benzene layer. Scans of these two layers are also given in Fig-
(48)
ures 29 and 30.
Because of the intensity of this yellow ~olor in the benzene.,.·
layer, an attempt was made to use it in a quantitative test for
peroxide at the concentrations used previously and at lower con
centrations. It was impossible, ijowever, to obtain duplicat~
results. :. Peroxide could be detected at a concentration or· two
micrograms per milliliter.
When acid was added to the amine salt in water before addipg
peroxide in benzene, ~cans of both the water and the benzene lay
ers, given in Figures 31 and )2, show little or no color forma-
tion when compared to the same solutions without aci~.
It was possible to separate and scan a similar yellow ben-
zene layer which formed in the presence of methanol. Two or
more drops of am.~onium hydroxide were added to two milliliters
of the reagent solution used originally, turning it from pink to
blue. With the careful addition to this basic solution of two
milliliter~ of peroxide in benzene, two layers or bands of color
formed. Am.~onium sulfate precipitated from the solution. Slight. I '
agitation caused the.bands to disappear, ~giviog a uniformly col
ored solution. A ~can or: the benzene layer, given in Figure 33,
is similar to Figure 30. A scan of the methanol layer in Figure
34 shows a peak at 465 nanometers.
In order to compare the yellow color described above with
that of a Schiff base, propionaldehyde was added to the amine
salt in water plus benzene with no peroxide. A very light co_lor
formed in the benzene layer, which was lost upon the addition of
(49)
tris-buffer. No. soans were ~ade of this soluticn ~ No further. ·:.:
tests with a~dehydes were made. •
D. N1N-Dimethyl~p-phenylenediamine Sulfate in Acetone
The behavior. of ,the amine sulfate in a solvent less polar ··~
than water or methanol was investigated. The amine sulfate was
·insoluble in ;·benzene. It was only slightly soluble in ace tone,. ,.
forming a•yellow solution with maximum absorbance at less than
400 nanomete~s, as·shown in Pigure 35. Combining this solutio,h ~ \' ', ; '
" ' with an equal amount of benzene containing peroxide caused no·
change ·in.the spectrum but showed only the effect of dilution.
No attempt·to change the pH of this solution was made.
,•:, .t
E. Separation of the Colored Reaction Product . '·
When an acid solution was added to the yello~ benzene layer ~ ' . ~
described in section C, the color was eACtracted almost complete-" ly out of this layer into the polar layer, which turned a bright
red. This occurred upon the addition of either sulfuric acid in '.; l.
water or in methanol, or an aqueous solution of hydrochlor:Irc :•.ci , ...
acid. This color was apparently due to a reaction product. Its
behavior is characteristic of an amine and its salt.
Figure 36 shows that a scan of the red aqueous layer gives a l, ·'
very intense peak at 510 nanometers, similar to Scan a in Figure
23. Addition of base to this solution caused precipitatio~:
Figur~· 37 show~ scans made of the red acidic methanol '1aye:f·, " '?}
with scan a having the same intense peak at 510 nanome tars ·~s in
Figure 36 and a slight peak near 640 nanometers. (Compare with
scans a and bin Figure 23.) Addition or one drop of ammonium
(50)
hydroxide caused a decrease in the 510 peak and an increase in
the 640 peak. /•ddition of a second drop of ~rnmoriium hydroxide I
ca~sed the .~~.O peak to decrease along with the formation of a
peak at 460 nanometers, similar to scans e and f in Figure 23 •
. When glacial acetic acid was added to the benzene layer, the
solution turned a yellow-green, with an intense peak at approx
imately 460 nanometers and a slight peak at 650 nanometers, as
shown in Figure 38, similar to the scan for the solution ex-.
tracted into acidic m~thanol and after the addition of two drops
of ammonium hydroxide, which was just described.
The red hydrochloric acid solution was evaporated to dryness
on a steam bath, but without the formation of good crystals.
When water was added, a greenish-yellow solution formed, which
turned red upon the addit~on of acid. Figure 39 gives a scan of
this solution.
The addition of methanol to the dry red product caused a
blue solution to form, the scan of which is given in Figure 40,
with peaks similar to those seen previously in Figure 37.
The addition of ethanol to the same product caused the for-
mation of a green solution. A scan of this solution in Figure
41 is similar to but slightly different from. Figure 40. When the red hydrochloric-acid solution after separation
' . from benzene was made basic with five percent sodium hydroxide,
a greenish-yellpw precipitate formed. This precipitate appeared
to be stable. Figure 42, a scan of the infrared spectrum of
this product shows only slight pe~ks, which occur at 6.2,· 7.3,
(51)
8.7, and 12.1 microns. Although no definite identification was
made of this product with the Sadtler Spcc-Finder,(79a), it ap• •
peared to be an azo dye. In Figure 43, Scan a is the greenish
yellow precipitate dissolved in methanol and shows the 670 peak.
Scan b, made after the addition of acid, shows the 510 peak.
F. Reaction of the Amine Sulfate with Bromine and Ferric Ions
According to the literature (18, 67), N,N-dimethyl-p-phenyl-
enediamine reacts with bromine or ferric ions to form a free ...
radical called Wurster's red. Consequently, a comparison was
made of the reddish~violet color formed by these reactions with
the color of the reaction being studied. The addition of one
drop of bromine water to a solution of the amine salt in water
caused the immediate formation of intense peaks at 515 and 555
nanometers, shown in Figure 44. The solution tur~ed from pink
to a deep magenta· color. Bromine water was added to equal
parts of the reagent solution and pyridine (no peroxide). A
similar test was made using ferric sulfate in methanol. Both
solutions turned red•violet and then green. Figures 45 and 46 ..
show these reactions with intense peaks at 465 or 475 nanometers
and at 670 nanometers.
G. Development of a Method for the D.etermination of Peroxides
Substituting Pyridine for Benz~ne
Because the peaks which occur in basic solution appeared to
be more stable than those in acid solution, because pyridine
could be used as both a solvent for the peroxide and a buffer at·
{52)
the proper pH, and because, in addition, Walling and Indicator '
{66) showed that the reaction between an aromatic amine and ben-
zoyl peroxide occurred rapidly in this solvent, the development
of a method with pyridine seemed practical. Dugan indicated l
that pyridine could be substituted for benzene when using N,N-
dimethyl-p-phenylenedia~ine sulfate as reagent.
To be sure that this system was better than the previously
tried tris-buffered solution of water, methanol and benzene, a.
comparison was made o~ these two systems. Figure 47 shows scans
made, fifteen minutes after benzoyl peroxide in benzene, with
concentrations ranging from 10 to 80 micrograms per milliliter,
was mixed with the 0.3 percent amine reagent solution to which
0,25 milliliters of tris-buffer had been added, Figure 48 shows
similar scans fQr which pyridine was substituted for benzene and
tris-buffer w~s omitted. Figure 49, corresponding to Figure 14
(the Beer's Law curve for the tris-buffered solution), shows
that the reaction in pyridine also follows Beer's Law.
The concentration of the peroxide was held constant and the
concentration of the amine was varied. Figure 50 shows that
changing the concentration:·of the amine salt which was combined
with the peroxide in benzene changed the intensity of the ab-
sorbance peaks much more than changing the concentration of the
amine salt which was combined with peroxide in pyridine. This is
shown in Figure 51. Table I gives :the absorbance at 670 nano
meters, obtained, using the Beckman. Model B spectrophotometer, ' for 60 micrograms per milliliter of benzoyl peroxide in pyridine
(53)
TABLE I
The Absorbance for a Constant Concentration of Benzoyl Peroxide
with Different Concentrations of N,N-Dimethyl-p-phenylenediamine Sulfate
Concentrationa Absorbanceb Average Average Absorbance Deviation
0.1% 0.580 0.575 0.585 0.570 o.565 0.575 0.006
0.2% 0.570 0 .. 575 0.575 o.565 0.580 0.573 0.004
0.3% 0.550 0.545 0.555 0.560 0.555 0.553 0.004
0.5% 0.525 0.520 0.525 0.530 0.525 0.002
Percent Average Deviation
1.0
0.7
0.7
0.4
a The amine concentrations are in grams per 100 milliliters of solution, 10 milliliters of which is water and the remainder methanol. The peroxide concentration is 60 micrograms per milliliter of pyridine.
b The absorbance was measured at 670 nm, using a Beckman Model B Spectrophotometer, with a reagent blank as reference.
with 0.1, 0.2, O.J, and 0.5 percent N,N-dimethyl-p-phenylenedia-
mine sulfate in a ten percent water-methanol solution. . . A time.study was made of the reaction, using one concentra-
tion of peroxide in pyridine. This solution was mixed with the
regular 0.3 percent reagent solution. The scans in Figure 52
show a slow decrease ,in the 670 absorbance peak in the time in
terval from fifteen minutes to one and a half hours. These
scans were made versus a reagent blank. These scans were par~~
tially repeated in Fi~ure 53, after al~owing the reagent solution
to age three hours, with no apparent change in absorbance. These
scans were repeated in Figure 54, using methanol as reference in
stead of a reagent blank., in which case the peaK at 650 nanome
ters increased with time. For Figure 55, scans were made two to
eighteen minutes after mixing and show the development of the
670 peak. Fo~ the scans in Figure 56, the amine reagent was dis-, • I
solved in water, omitting the methanol. Unlike Figure 52, these
scans show that the 670 peak continued to increase after fifteen
minutes.
In the solutions described above, for example, those used
for the scans in Figure 48, the green color appeared more rapid
ly in the more concentrated solutions. However, Figure 57 shows· t'
that the absorbance became relativel~ stable after fifteen min
utes for 10 micrograms per milliliter, as it did for 60 micro
grams per milliliter in Figures 52 and 55. Figure 58 shows the
absorbance versus time for the reagent solution with 10, JO, 50,
and 70 micrograms per milliliter of benzoyl peroxide in pyridine.
(55)
These curves are ne.arly hori.zontal; be tween ten and thirty minut~s,
during which time absorbance measurements oowld be made.
Table II gives the absorbance after fifteen minutes for the
reagent solution with 10. 20, 30, 40, 50, 60, 701.and 80 micro
grams per milliliter of peroxide in pyridine, based upon four
sa~ples for .. ~ach concentration. The ~verage of the percent av
erage deviation obtained from these values is 1.6 percent. Fig
ure 59, using the average absorbance values from Table II shows . that Beer's Law is' fol,lowed. ( The values for Figure 58 and Ta
ble II were obtained, using the Beckman Model B spectrophotome
ter.)
A slight coloration of the standard peroxide solutions in py-
ridine was observed several days after preparation, This was not
apparent with the benzene solutions. For a period of three days,
a fourteen percent loss in strength for 60 micrograms per milli~
liter of peroxide in pyridine was calculated from the decrease in
absorbanoe.
(56)
TABLE II
The Absorbance for Different Concentrations of Benzoyl Peroxide •
with a 0.3 Percent Reagent Solution
Concentration Absorba.ncea Average Average Percent ~g/ml) (670 nm) Absorbance Deviation Average
Deviation
10 0.113 0.113 0.102 0.108 0.109 0.0040 3.7
20 0.256 0.258 . 0.247' 0.256 0.254 0.0038 1.5
30 . 0.397 0.406 0.391 0.405 0.395 0.0068 1.7
40 0.535 0.547 0.528 0.543 0.538 0.0068 1.3
50 0.682 0.692 0.672 o.693 o.685 0.0078 1.1
60 0.824 0.833 0.814 0.840 0.828 0.0088 1.1
70 0.950 0.960 0.943 0.980 0.958 0.013 1.4
ao· 1.098 1.113 1.078 1.096 1.096 0.0093 o.85 The Average of the Percent Average 1.6 Deviation
a Absorbance measurements were made with a Beckman Model B Spectrophotometer, using a reagent blank as reference.
{57)
V. Discussion
A. Identification of Wurster's Red
Comparison of the spectra, given in Figures 6 through 10 and
also in Figure l by Dugan with those given in Figure 4 by Mi
chaelis and in Figure 44, indicates that, when a solution of N, I
N-dimethyl-p-phenylenediamine sulfate is mixed with a solution
of benzoyl peroxi~e, the first product of the reaction is W4r$
ter's red, and the reaction is an oxidation reaction as with the
a~ine sulfate and bromine or ferric ions.
The pH of the reagent solution, 5.5, falls within the range,
3.5 to 6, which, according to Michaelis (45), is necessary for
free radical formation. According to Steigman and Cronkright
(58), the amine salt, N,N-dimethyl-p-phenylenediamine sulfate,
used in this study is 1~ the proper ionization state for the re
action. It would have the following structural formula,
[(cH3 J2~~-!H2] 2 [ S04:), with the extra proton on the ni
trogen of t~e tertiary ~mine group, since the unpaired electrons
of this nitrogen are more available for sharing than those of
the nitrogen of the primary group (75a). The following equation,
similar to that of Steigman and Cronkright for Wurster's blue,
best describes the oxidation to Wurster 1 s red.
[oJ ~
+ -e
(58}
This form of Wurster's red is the ionization state which, ac
cording to Michaelis (45), can exhibit the resonance for stabil-
ity. Other resonance forms are possible, similar to those given
for Wurster's blue on page 32.
·If Wurster's red is formed by the reaction mechanism pro
posed by Horner (65), .a. proton is lost and the amine reao:ts "Wi.:t~h
benzoyl peroxide according to the followin~ equations.
Q-c,!'o +.~ ,.,.8 ~~o
+
+
+
.o ~-~ '~ 'o-
The electrons of the free radical can easily shift to the quino-
no id s true ture. · .·,
The appearance of color, denoting the formation of the free
radical by autoxidation, in the reagent solution with time is in
accord with the observations of Michaelis (45). It occurs when
the reagent is dissolved in methanol, as seen in Figure 18, but
it occurs twice as rapidly in water, as s~en in Figure 25, form
ing more rapidly in the more polar solvent, which can more easily
accept a proton. No color formation characteristic of Wurster's
red is observed in acetone, as Figure 35 shows. The reaction
with or without peroxide is therefore not between the amine sul-
fate and methanol aa was 'suggested by Dugan (12).
. (59)
B. Identification ''of p,p•-Bis(diinethylamino)azobenzene
According to Micha.ells.·· (43), after the fQrmation .of Wurster '-s
' · -red, further oxidation occurs~ It was found that, in the reagent
·.· s~lutton (ptt·5.5) ~as· the peaks ·for the free radical a·t ·515 and
.. 555 nanomet'ers. decreased.;· ·a peak formed at 670 nanometers; which .·,. ., . . . ·upon standing· became sharp· and shifted to 640 nanometers. These
peaks can' 'be seen in. the scans. of Fi.gur~ · 6.
In basic s~lutlorr the~ 515 arid 555 peaks formed and then ra.p-' .. ·. . '
idl~ decreas~d(as'peaki at'670 and 465 na~omete~s ·formed, as
. shown in Figures .. 1),' 16 and' 17. Fig~re 15 shows·. that. upon stand
i~g the 67o'peak reached a·ma.Ximum and then decreased.while the
·465 pe,~k continued to increase, This fact is not apparent from
. Figure'i3, 'which covers a short time period. As the pH of the
· solution ·~h,ang~·d, g·r~ate·z. basici ty favored the 465 nanometer
peak;' a peak at .510 'nan'ometers a·ppeared fn· strongly acid solu-.•
tion'~ with the 670 l'l'anometer peak a't' intermediate pH values, as
Figure 23 .. sh,ows. The tnree warvelengths ·at 465, 670 and 510 nano-' r,
meters appear to be pharac'teristio of the higher oxidation prod-
. uct. The stability of this' product can be seen by comparing the '-'·.,_
-_ spectrS: immediately after formation in Figures 23 and 48 with
the spectra of the salt extracted from benzene in Figure 37 and . '
the spectra of the dissolved salt i.n. Figt.lre 43. , J '~
As: the pH of the solution was changed, causing changes in the
:·intensities of these peaks, virtually the entire spectrum of col-'.:
Ors Was observed, tan ',to yellow-green··. to· green-blue to Violet to . \: . . " ; ·'.\.,.·\ "·.. , ·.-~.. .. .
pink .to red. This' c~~ be. _achieved with Just two wavelengths
: (60).
:(7ia):_if:one ~s in the yel~ow to purple rangei (5800 to 7200 -'···: ··.·. : ... \
anstroms) and th~ other is centered on a wavelength shorter by~ . ~' .
1500 ans trams •.
The products of the-reaction between benzoyl peroxide and
~dimethyianiline, a tertiary ~mi~e similar to the ·one being stud~ ' '
ied, ar·~ benzoic acid,. monomethyianiline, formaldehyde, and'
small amounts of p-benzoyloxydimethylariiline andp,p'-di(dimeth~
yl~mino)diphenylme~hane 0 (65). 'The·proddcts ·of.the ~eaction be
tween be.nzoyl peroxid~ and -aniline·,· a primary amine similar to
the one being studied,· are.b~nz6icjacid,~benzanilide, azobenzene,
and a small amount or·o-hydroxybenzanilide (65). Of these prod-. . ~._, " ~ -
' ucts, the azo dye should have the greatest color.
Although no definit~'identitication was made~with the Sadtler
Spec-Finder of the ~oli~ product 1 i~olatea in this:researc~, three
compounds are: listed· ( 79a) with·· the same prominent peaks as the
product.''in question:·; Although comparison of their structures ' '
with that of the amineusedin'the reaction eliminated them as
possible products;. all three oi' these compounds are azo dyes.
" ' ... ,·: .''•' '· ,_
·N-o. 360_.
·-._ ··No •. 6991. - - -·
CH3 ' J l I [ CH" ~-N=N~~-N~ ) . .· ' 'CH)
(61)
Roberts and Caserio ( 78a) refer to the ,spectrum o,r ,P-dimeth-·-· .. '
ylamin.6azoben~ene •. Thi·s compound in aqueous solution, is. bright ' •, . , '·1 . ' ' , • ' '<. - '
yellow (...\.max 4200 A), but it turns intense red (A. max 5300 A) I. . - . ,' ·,•: '->.'" . LI " • ·,
~upon t~e ~ddition,of.di~ute ~~id~ :With the. addition of strong_~·
ac~'d, the red changes to' a yellow color (A. max 4300 A) different·.
· from the .. s ta~ting s<?lution. ·. The shifting to longe~ and . .then , ..
. shorter wavelengths .by this compound with ·Changing pH is indeed.··. ' .; '· '
~· • I
.similar to that observed for the second reaction product of N,N-;. . . . . ~ "
dimet~yl-p-phenylened\amine sulfate and benzoyl peroxide.
The azo dye, p,p 1 -bis(dimethylamino)-azobenzene, .. \ '
CH3 . CH3 \ ,-, ,-\ I' N-1 \-N-N-4" '\\-N
CH3" '. \::::-./ - \=.I 'cH3
a specific stain for. unbleached coniferous sulfite fibers (72a),
has been prepa?"ed by .the au toxida ti on , of N ,N-.. dimethyl-p-phenyl~ , .· •'' ' :. .,; ~, ' ' :;. ·: ·' ·'
enediamine in the presence of alkali alcoholates, particularly ",., ~
'potassium. tert-butoxi.de (73a).
In using Wurster's red, formed by.the oxidation of N,N-di-'·, ., . • ~ l,
methyl-p-phenylenedi.amine by potassium thiosulfa te, to determine , ' ' ' ' / ' . ' '
the reactivity sequence of compounds of. the gene,ral formula, ~ \ I·/ ·" . 0
XCH2Y, when attacked by free radi.~,als, Hiinig and Pie ~stocker
(74a) noted that Wurster's. red also dipierized, and. the hydrazo ' f • : ,t .. ' . ' ' . '
compound which formed was oxidized::to p,p~-bis(d~methylamino) . . . I . ' , ' '•·
azobenzene. The ease with which a.hydrazine can be oxid~zed to ' 'I' A , l
'• .·'
the corres~onding azo compound was pointed out by Roberts and·: . . ' :; , ,~ ; ' ' .
caserio (76~). · ·- "~~ .
{:: .' ~ .
: ···Figu.re. 60 is the spectra giyen by Gerson and Heilbronner t, •..•.
(62)
(71~) 'io~;· p,p'-bis(dimethylamino)-azobenzene, '.which show peaks·. - - -- • . , - l , '
at ·~·ppr:~xirp.~tely' 670, 510, 465 a~d 440 nanom~te.r.s, corresponding .
. clo'sely 'with. those, observed iri' this lab~ratory. The forms of ·~ • -<
th~"-dye''corr~espondi.ng.to these wavelengths were given as the ' .,.., ....
following: .....
. . •
.' . _, ~ ' -~ ' 'i '' ~ '·"'· ' ·'; •
T~e scans of Figure 60 sh~w the' tw~ forms giving peaks at 446 ·
and 670 nanometers' to -~e iri sol,ution in different ratios depe~d-•( ., .. ' i'ng upon the pH.
(' .. ' ·. '·
From the information given above, it was concluded that the ' ~- -~ _,,.. ' ~-·. '' ; '"'\· \ , •· ..;
second oxidation product in the reaction between N,N-dimethyl-p-
~henylen~di.aml~~, ~ul·f~ te 'is ::..p, p.' -bis ( di~~thyla~ino )-azobenz~ne ~ ~hich for~s by ·wa; ;6r .Wurs.ter 1 s red.:. This formation is sh.own in
F{g~res 1"3, '16,''·~~d 17. ·Frorn Wurst·e~'~ red the.hydrazine forms • ' '·, "J.. r \ '1 , ~ ~ • ~-. •
with 'the los's" 'or protons from tri'e nitr'ogeri anci. is further ox1.:..:
di zed. ··In acid solut1on,' t·~e oxiclati'.on of th~ hydrazine occurs .,
with the·'r~rmatio~ of the··~zo dye with structure correspondini'
to that given ro~ tne p·aak ·at. 670 nano~~ t~~~, as shown irl Figure :·.· f-:·.
6. It ·appears r~~~ the spect~a. of Figure's\ lj and ·15 'that this· _. ·, . ' .
. ·structure,:fo~s_ simultane~usiy in basic solution.with a structure
(63)
corresponding to the peak at 465 nanoneters. Considering the
structure of the.hydrazine, it would be likely for the structure
giving a peak at 670 nanometers to form firs·t and rearrange to
the latter structure.
CH3 + H 2 .·· · 'N-:/=\-N:
" '==./' .• CH3 ··. . H
+ - 2 H)
Although care must be taken in making identifications using
visible spectra, for the free radical, Wurster's red, and the azo . . . dye, p,p'-bis(dimethylamino)azobenzene, the slight deviations of
the wavelength peaks _obs·e!'ved appear ~o be due to solvent effects,
similar to those· observed by others,,such as Steigman and Cronk
right,··as is shown in Figure' 5. (See.also Figures 40 and 41.) ,,
Of the different structures of the azo dye corresponding to
the different wavelengths, the one given for 670 nanometers seems
to fit the observed data because of the way in which the azo dye
forms, because of its existence in slightly acid solution,_ and '
because the location of the proton favors resonance •
. The structure given for the 510 nanometer peak also fits the
observ~d data, with two protons attached to the molecule and
with charges separated in such a way as to favor resonance. The
shift to the lower wavelength occurs when the proton becomes at
tached to the unshared pair of electrons on the nitrogen of the I ", , '. I• l,;
ter~iary group, and they are no longer free to move.
{64)
The structure given for the 465 nanometer peak is in line. • • ,, : - • !_ ~
with the observed data for b~sic solutions· in which· the· color ' •
-.that for.ms also gives maximum absorbance at approximately 46.5
nanometers. depending upon the solvent. These :·a tructurea: are in ·.· .' ' ' .
:agreement with Roberts and Casario (78a), that the shifts in'the •• ·-' ...... _ •• c•
.spectrtim of p-dimethylaminoazobenzene are due to the. addition of
··one and then the second proton to the uncharged molecule.
The reaction whereby the azo dye is formed, as well as the
. f.orma.tion of .the~:LnteX'!.mediate, Wurster's red, are not specific ' ~ .
for peroxides but will occur with other mild oxidizing agents,
~s Figures 45 and 46 show.
·c. Further Analysis of the ·spectra ... ,;,
. -In light of.the above conclusions, further analysis of the
spectra ·given will be made.·· In titrating th~ amine with bromine
pa~ t the point for complete oxidation to the semiquinone, Michael· . "\ . . ;
is (43) observed the reappearance with time of the color charac-. ·.
teristic of the free radical, al~hough this color was not as in-
tense as when it was fira.t formed • He concluded that this second
. color was due to self-oxidation of the diamine by the diimine. ) - ;
.. In_· the pr:esent work, the reappearance ·or the peaks characteristic .
. of thejfree radical was observed within a narrow pH range when the:_
pH was changed and the scans for Figure 23 .. were made. The return·
of th~ magenta color was also observed when the reaction mixture ·"
;--,_ <!"':
containing pyridine was made' acidic•.:
In' the 'ten percent water.;.methanol solution at a pH or 5.5, ·'""
the amine sulfate can lose a proton and: be -oxidiz~~.to Wurster1s
(65)
red. ·This/pH also favors th~ toss of. a proton 1
t'rom Wurster•s~ ' \
:red ~nd further oxidation. Addi ti on ·or acid to the reagent , · • ' '
: solution 'prior to mixing with. the peroxide solution does not ,.1 ·
.·- ~· . ·- ,· :
des~~oy the peroxide as was reported by Dugan (14)but prevents
·the loss of the proton from·the amine salt, and in this way pre~ ' ~ : .
:vents ~adical formation. 'rhe subsequent addition of base per-..
mits the ~~r~ation of the radical, as shown by.the a~~earince of
the red-violet color, which turns blue-green, the colo~. of 'the"'.. .. .~ "" ..
azo·dye. ' ''. ·'
The addition' of acid to the reaction mixtu~e st0.bilizes' the'
reactfon at the time of additlon, as Figures 7 through 12 srfow,'.·:··>
·by preve~ting the loss of a proton froill the. Wur~t~r'~ re·d wh'.lch·
h~s formed. . With the addition or excess acid;· the 1
·~oi~ti~n 'pH
is too''low· for the stability of the rree radical,: a~d mJch 'too '
low ror the· azo dye to form •.•. Judging from' the . scans .of' Figure ;t"
. 24, with ex'c:ess acid the free· radical. is· lost and 'the resulting
p'roducta a~e not .:Colored· .... No,"atten1pt was m~de··t'o ·analyse this
·sol~tiori~
Figure· 20 shows simply that there was aurri.1
0 ier.it arriine '. su1-·.
' ' fat~, in ·~ddition to that already autoxidized~ for oxidation by
· benzoyl". per-oxi~e to occur •
,~·-, '
. The: color of the two layer water-benzene syst"e'm was .extracted· i.. ( .'">,· ' 'i ,1'
·into' the benzene layer with the addition of tris-buffer, as seen
in Fig~re .JO. · Thie tends to 'prove that this peak for the ben
zene layer ·-is due to the uncharged form or the azo dye/ as 'is the -· - '·
, .. ·:· !
465 .. pe_~:k. b't a basic solution,. with the shift in waveletfgth. ob-~
(66)
- . . .served' due to solvents effects.
\,'
D. The Modification of Dugan's Method ··~ - .
By Dugan's method the absorbance was measured thirty minutes . - .
after mixing, at which time the color had decreased considerably
below the maximum and was decreasing rapidly. Therefore, advan-
tage was not taken of maximum color development. Taking advan-.. "
tage of the maximum color development by stabilizing the reac-
tion with ~cid was considered. Although this worked quite wel~ t . '
for standard solutions of benzoyl peroxid~ as Figure 11 shows, .-
the time of addition of acid.was critical as can be seen from
Figure 12. The fact that sample solutions might contain impuri
ties which:would alter the rate of reaction slightly so that the~ .. , .:
would not compare well with standard solutions led to considera- ·
tion of carrying out the determination in basic solution.
When tris-buffer was added, the absorbance varied greatly
with the reagent concentration, as Figure 50 shows. Tris-buffer
could not be made up in aqueous solution because tf the ratio of ,I,<
water to methanol was' increased, two layers formed. By the use
of pyridine, this variation was greatly lesse.ned. The small
variations -which did occur with pyridine did not seem sufficient
to change the preparation of. the reagent solution • . . In the pyridine modification which has been worked out, no
": ,• .·· ,' - -'i:~.. . :· • . . - ..
change was made:in the water-methanol ratio. This amount of
water was n~9essary to dissolve the reagent; a larger amount ; . ' ~·- ''
. <?aused the \too rat: \d · oolo:c-ation of the solution by autoxidation. ~· . • '!.
·--.-,,.;.'Autoxfdation of the reagent solution along with loss· of
(67}
strength of the peroxide in pyridine necessitated the use of
fresh solutions. Altnough a nitrogen purge might have prevent• •
ed the autoxidation which occurred, the use of fresh solutions
and a reagent blank instead greatly simplified the method.
Whereas Dugan reported a deviation from Beer's Law for 40
micrograms per milliliter, Figure 59 shows that with pyridine
Beer's Law was followed up to 80 mi~rograms per milliliter.
The procedure that has been worked out using pyridine is as
follows: The reagent ... solution is. prepared by dissOl·ving O. 3
grams of N,N-dimethyl-p-phenylenediamine sulfate in 10 millili
ters of redistilled water and diluting to 100 milliliters with
methanol.
Standard solutions of peroxide are prepared in the range
from 10 to 80 micrograms per' milliliter of pyridine from a J;OO
milliliter stock solution cbntaining 0.0500 grams of benzoyl
peroxide. Sa~ples can be dissolved in pyridine to give peroxide
concentrations in the. required range.
Two milliliters of reagent solution are mixed with two milli
liters ot pyridine containing peroxide. A reagent blank is pre
pared at the time of mixing. Absorbance is read at 670 nanome
ters ten to thirty minutes after mixing.
To use this method as modified10~ Dugan's method requires a
knowledge of the reaction time for the particular peroxide to be
determined. ·
(68)
.SUMMARY
.'. _,..
The colored reaction which occurs'with N,N-dimethyl-p-phenyl
~ enediamine sulf~te in a water-metha~ol solution and benzoyl.per-
·:.oxide ··in benzene, or some other appropriate solvent, is the ox-
idation of the amine sulfate by benzoyl peroxide, first to the . CH3 + _ ,,,, H
type, 'N:<::'):N• CH3,,... '-H
free radical of the semiquinone , ·call~d
Wurster's red, with the loss of one electron, and then by further
p,p'-bis(dimethylamino)azobenzene,
, with the loss of a second electron
(or two electrons·from the dimer which forms).
The Dugan method was modified by substituting pyridine for
, benzene as the solvent for the peroxide, and the absorbance was
read at 670 nanometers, the peak which occurs from the oxidation
· of the . amine to the azo dye.
Although different peroxides react at different rates, the
· .. ·oxidation of benzoyl peroxide with these modifications was rap-· ·'
, id, the color which formed was fairly stable, and absorbs.nee
readings could be made ten·to thirty minutes after mixing. Py
.·ridine served as the needed buffer for the system, and Beer's
·Law·· was followed for a wider. conoe,ntration range than previous-, : ....
'•,
FIGURE 1. STANDARD CUH.VE FOR BENZOYL PEBOXIDE
Uugan, Pa trick li.: Hap id Spectrophotometr1 c Determination of Nicrogrrun Am:>unts of Lauroyl and Benzoyl Peroxide, Anal. Chem., .2J., 697 (1961).
I ••
Corte. benzoyl peroxide - 50rg/rnl solvent Cone~ benzaldehyde - (1) none, (2) 0.1%, (3) 0.25%, (4) 0.5%, (5) 1 .. ()%.
F·IGURE 2. REACTION SPECTHA FOR BENZOYL PEIDXIDE AND N,N-Dil1ETHYL-P-PHENYIENEDIAMINE AT PH 8. 7 IN 'llIE PRESENCE OF BENZAIDEHYDE
, Dugan, Patrick R. and ttichard D. 0 1 Nei1l: Modified Spect.rophotornetric · reaction for Detecting Or~anic Peroxide, Anal. Chem.; .J.2, 415 (1963).
-·--- - -·--·-. -
ZA ! +600 -A 2
A +550
== A t ~ 1 :.+;
+soo-
0 0.5 1.0 1.5 2.0 Cc. of bromine.
DimethyJ-p-phenylened1amjne hydrochl~ride in acetate buffer (pH - 4.62). Arrows signify drift of potential. (A) is the tota] theoretical amount of bromine for compJete oxldation to the semiquinone level.
FIGURE J. POTENTIOMETRIC TITHA TIO!\ CURVE FOR N ,N-DIME THYL-P-PHENYlENEDIANINE HYDhOCHLOHIDE WITH BftONINE
.
I . l 1
I 2
I I
50001
i : I
2500 ~ !
H2N 0 N(CH3)2
Cli.3
Ii2N 0 N(CH3) 2
460 540 mµ.
620
I
I !
FIGURE 4. SPECT.HA FOR T1fllRSTER 1S RED, SHOWING THE E1''1''1'~CT OF HING SUBSTITUTION
Michae11s, I., ~·j. P. Schubert, and S. granick: 'l'he Free hadicals of the Type; of Wurster's Salts, J. Amer. Ctem. Soc., g, 1987 (1939).
.. -1--1--1--T=1.:.++.+= : ,_:+_,__,._,_ -++ 1- + ~-- -~ :_ ---1-m---f~m-0::1, -ri~ -~~---- . 1~+-- - - --i-++ 1--H-+- --H--1-+---1-1--t-+-- -I- - - i-\\- -- - -H- -p l hi. L ,)Im~ ttJe "ffi~)( ir, o-1-- -1-1--1-•-'
- - -~ -t--t--- -1/t ;-t- - ;- - ; - - • - - .. -- - - ~ --rt-+--1- -H--+-
· -i-+--+--i-+-++- - -•- 1- -1\ + - ·· ra \- - - --1--1- -ltJLr.·:.JL-t.; -~, ·lchbi L!: · Jni:.i--iJ-J.alrt-:,;.;__r +- -"--J·-'---'-'
1-1-i-- -1-- !-t--1-- - -lf- - -i-- -- - f--- -~i- -1--1-- + -- -+ _ -_, dn-j~-fy-/Cl'-~he-t+ ,.. __ ,I ~--1-H-
2.1 't= ~t=~ -!~ -l=+=fj==-~1\+=-jJ :=~~I : 1~-t2= -~=f1d~~\~~~~Jl~~~1~~2~~-j'> -.-:Yi1~=:-i ~-=-H -t _] ++- -1-l\iJ- - -N-~ -1+-1-1-+-i--1-j~) J>~-hl-o,.,L-l-~--H-+-1 H--+-
H -1-f-H-f: -rl-'H -l~b-l - -J · - - ; -- -r'-'~f"['--l--J- - --t- -_.__,>-+-_,_1--+-H-- --1-1-+-f'i-'----f-1- I·-~ H--1- -1-1-- g-)--~ !rAj n.Lr-H-1-+-I-- - - -1-- -+--l-+-f--t-i-+-1--t-H--- --!-' - -1--,-H-i - + --t-H--t-1- --rf.i..:.. -b-,-~,:;l~ 1-v1iilllri!--l-+-l-H-l- - - -H--+-
1--1-t- - H~J:+-~J~=t:I - 1--t-I I H- --+-+-1- -- _Jf1).· -p1.+~ .... ,..f-1-+ - -i-- -H--H-H +-H-t-l---j •--+-+-+--+-1'-+-+-+---1-!(1-1 +-- f +-HI -1----,..t --i-t-1-'-l•P__j!_H---+ --- -\ ~-+-+-+-<>--+--~--+-·•1t- -l--1--[t-r -I -!- - - '_ --t-+-Hf-i-H-11--1-+--l-~-l--I-+· H-f-1-1- H- -LH-t-J
1. 8 ~-+-+-t-+-1++-1--1--11- -L-1 -l- -1\i.::,; - -1--}&1- -1-+-+--1-t---1-11- --1--t-t- -1-t-H- - -+-+-1 --1-H-+- - -!=j
+-t-- ~- --l---i--l-+-~L-1 ~t-- 1 - +---1---1--1-+-1-1-- -H--+-- - -t-t- -t-. -H-- -•- -- -1-+- -l-<
1-!---+-+-+-H -+-+1r - :y- - i +-- - - II+- -+ i -- - +-+- - -~ =t-=-- - H- :.++ -- -~ fl ti +JS t- -+--I/ - -- I 1- -!-+- -- 1-t- _U
l-+--+--+--+--+--4---•-l~I- --, •. - - -L 1-+-- -j- - - -+-1- -1-f- -1 t--H-f/1- l--11·,-+-- :;i_ -t-jJ -~ -t----1- -H-+- !- -
l-+--+-"-1--1-+-1- 1-17'-- -----j\-+V-f~fi !--\-- I--+-+-·- !-1-f;\~ -- +.I- -l-l--+--l-+-~1-+--l-+--+--1-1-+ 1-t---t--1--+--1-+---1.J - -17 - IH- -1--t-\ ~ -u f-j\- t-+++ -1-+-l-- - -- +-t-1 -I~ T 1-+--1-+-'-'-'--+-+-1--'1-1--+-'--+-1 1.5 I I] II- -/---l---J-t--k-j/'-{ +·111 1-f--f---f-j-.;{.-_J -t-t-J-t_!-+--+- 1--1--+- -f-+--H-
'T -~t)1--k_--[t-i-J -+-t-~ ~-- -- -H-l- ~q.gl--~ \-- - -1-+-->-+--+---l'-LJ.' l-l---1---'"f·JJI - ![_ 1--ii--j \ ---, I/ J-1-+-t- t-- _ _ _ -+-+---_l I I t h i- +-!-- --1-+-+-~-.--t--H-1--1-+--+--l--t i-+--+--+~+--~-+-+--jf - ' - - - - ~---1 f-1+-+- - H-1-- - . IL' i..\ 1-t-+--+--i--t-+-1-~- -'--'-'---'-'--• l-+-+-1--+--l·--l--11-+I ,-'.-H-c -1-+-r-t.Hz , ~h -1--t- - - -- +-- __ ,__,__._.__._ ·'--l--l-+-!--1---1~1-+--
CV If ~-- 1...-1 11 . - H--J - - - H-t-- -+ h-+-I 11'=1-r- _ ~J I-' H--!~f- -+ J Ii- - _ -t~+--+--+-+·+, -t-t-+--ll-1!--t-Hf-1--1-1---l--1-<
0 1-t-t--t-+--~-f-+-i7 - Pf I- -H tHH- - 1---1--+- +-+ t-+-t-1-+-1-+---'-'--'-+-+-t-11-+-+-+-+--t
~ 1.2 I ,-t+-+111/1--t--,- - -~I-- - -H- Ml- -!-- -1-1--+-j-l-!---I-' -H - -!--~~ i! +i=d ),-t-1/:v J...1 - I' _L -H -l--j-1-1- - -l--1- - - ~\++-1-1-H i-+--1-1
g -~1-4+-~1 f--+--1--l-- '+-+-+-+- :,±--:::::-~,_ -~-t-t't~~-1--1--1-r-t-+---~-:-+-l--14-!l--!-~ ~ ~r-t-- - 1/-1-/ :I-++- 1--t--+- .i..-n\I i"b, - -»-->-+-<>-
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500 700 750 Wavelength nm .
Benzoyi peroxioe j n benzene (80~/rnl) and .N,N-dimethyl-p-phenylenediamine a~lfate in water-methanol (0.3%) vs. methanol •
.r FIGURE 6 •. COLOR DEVELOPMENT WITH TIME IN ACID SOLUTION
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Benzoyl peroxide in benzene Wavelength run
(6~g/ml) and reagent solution (0.3%) vs. methanol
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" _FIOU}tE 8. THE EFFECT OF THE CONCE?iTRATION OF ACID
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WaveJenp:th run Benzoyl peroxide in benz~ne (u0/'4-r,/ml) and r~a~~nt solution (0.3~) wi~ O.l Jill or O.lN H2S04 in methanol added after 5 min. Ve• methanol
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650 100 ,. · ' Wavelengt.h run
Benzoyl peroxide in benzene (LOl"-g/mJ) and reagent solution (O.J%) with 0.1 ml of O.OlN H?S04 in metha?ol added after 5 min• vs. methanol.
FIGURE 10. 'JJIE EFFECT OF THE CONCENTRATION OF ACID
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0 10 . .20 ' · 30 uO SO 60 70 80 "·· .- · Concentration of benzoyl peroxide
· 1
· ( rg/ml) · . 2 ml. of bf'nzoyl peroxide in benzene and 2 ml. of reagent solution (0~3%) with O.l ml of lN H2$04 added 5 min. after ·mixing vs. reagent' blank.
FIGURE 11. BEER'S LAW CURVE - REACTION STABILIZED WITH ACID AT 555 NANOMETERS
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Benzoyl peroxide in benzene (601"' g/ml) and reagent solution (0.3%) vs. methanol.
35 I,
FIGURE 12. ABSOhBi•NCE VERSUS TINE WJTH AND WITHOUT ACID
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Time after mixing (minutes) 2 ml~· of benzoyl peroxide in benzene (BO;n g/ml) a~d 2 ml. of reagent solution (0.)%) plus 0.25 mJ. of tris-buff er. Scan vs ... methanol.
FIGUI<E 13. ABSORBAN:E VEBSUS Tii"iE. AT 555, 465, 4ND 670 NANOMETEWi
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FIGURE 14. BEER'S LAW CUfiVE FOR A TRIS-BUFFERED SOLUTION
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. 2 .4
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o.o -- L--- - _ ___.____..~-' 400 450 500 --- - 550 600 650 100 __ LJ
Wavelength nm ) Benzoyl peroxide in benzene (Borg/ml) and reag~nt solution (o.J% ,with 0.25 ml or tris-buffer solution added 5 min. after mixing vs. methanol.
FIGURE 15 • COLO.Ii DEVMOP.MENT WITH TIME IN A SLIGHTLY BASIC SOLUTION
7So
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11 •-4---+-<--+- -+--+--+·-+--·l-+--+--+--t--l-t-t--+-'---'-~lt--+--t--l-+-+-f·-t-1--t--t- --t-- --~t--t- t-t-t- t-t-t- -- -t--t--t-t- --t-t--t--t-- -t-t-t-- - - -+-I- --~ 1. 2 1---l-- -t-+ --1-t---t-t--1--+-++- --t-+--+-- H--+-t--t--t--t- r-1-·+--t- -+-t---t-- t--r--r---t--t---·- t- --r-+-t- t--r- --r---r+l--'ll :i ... :> n :i (
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o.o l--++-l-t-+-t-i-t-t--t--1h-t--t-t--t--t---t-t
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400 450 soo sso 600 650 7<XJ 750 ; Wavelength nm
Benzoyl peroxide in pyridine (60r-g/ml) and reagent solution (0.3%) vs. methanol
. FIGU.HE · 16. EARLY COLOR DEVELOPMENT WITrt TIME IN A SLIGHTLY BASIC SOLUTIOlJ
t--t-t-1-++-1,-+- -t-- -t-- - - -t-t-++-t-l-i-·i-1--t-1- t--t- -H-t-t- t-+-- -1--t- -t-t-t--t-10-t-+-+-t-- -+-1H--r-T--r-t-l- t-, - - f-H- - -t-t-H - -· t-t-t-t- ! -t-t-t-· - '
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} . 5 1-t-+-1---+-l-+-I- - -H--t-, t--t--t--t- -- t- -H-i- t-t- t--1-·
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o.6 .........,_.._ ......... _. -
O.J
o.o uOO - -450 500
Wavelength run 550 600
Benzoy1 peroxide in pyri.dine (60 l"'g/ml)- and reagent solution (O.J%) vs. methanol
FIGURE 17. EARLY COlOR DEVEIOPNENT WITH TIME IN A SLIGHTLY BASIC SOI.UTION
1;6,....,...,...........,~ I ' ·-r "
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o.o - -:-450 · .-, --=. . 500 • 550 WO 650
: · .Wavelength nm N,N-Dil!'et~yl-p-phenylenediRmine sulfate in methanol
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{0.1%,) vs. methanol
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FIGURE 16• COLOR-· DEVElOPMENT OF THE AMINE IN METHANOL
..
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500 • 550 600 650 700 750 Wavelcn~th nm ·
Benzoyl peroxide in benzene (60./f\-g/ml) and N,N-dimethyl-p-phenylenediamine sulfate in methanol (0.1%) vs. methanol.
FIGURE 19. COLOR DEVELOPMENT IN A SOLUTION WiTHOUT WATER
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45-0 500 550 600 650 700 750
Benzoyl peroxide in benzene dia111ine sulfate in methanol
Wav-elength nm (60~g/ml) and 24-hr-old N,N-dimethyl-p-phenylene-(O.}.%) vs. methanol. · ·
FIGURE 20. THt: EFFEI; T OF PEROXIDE ON THE AIR-OXIDIZED AMINE IN METHANOL
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FIGUftE 21. 'lHE EFi:<'ECT OF AC ID At\D BAS~ ON 'I'!i.E r.:.1-0XIDIZED MllNE IN. N.I!;THl>!'lOL
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500 550 6oO 650 700 750 Wavelength nm
Benzoyl peroxide in benzene (501"-g/ml) and N,~-dimethyl-p-phenylenediamine · sulfate (0.1%) in methanol vs. methanol.
FIGURE 24. THE EFFF.CT OF EXCESS ACID
•
CV u c
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Wavelength run N,N~Pimethyl-p-phenylenediamine sulfate in water (0.1%) vs. methanol.
FIGURE 25. COLOR DEVELOP,\IENT WI TH TIME OF THE AHINE IN WATER
:750
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Wave~ength run 24-Hr-old solution or N,N .. dimethyl-p-phenylenediamine sulfate in water1 (0.1$)
ve. methanol.
· FIGURE 26. THE !,1FECT OF BASE ON THE AIR-OXIDIZED AMINE lN WATER -,
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0 • 5 H--l-t--f-t-1-1--- -1-t- -1--f-+-l--t-4-+- t- - -+-~l-l--l-l--t-'-1--1--t--t-l-l--+--<1--1--1---l-t-t--1--1--l--+--l-l--+--11--t---l-l-+-t--l--+--l-t-l--l--l-t-t-t-+--+--1--1-l--l-t-l-l~l---1--I-~ J-++-l-+-1---1--f- - I-- - -1-+-l---t--t-+--+-+-. t-+-+-._..-+-+-+-+-+-t--+--1-+-t-r-+-+-t--+- ,__.___,__._.. _ _,_ _ _._.__,___,_,-+-I-- -- -l-+-t-'---·-+--1--1- - -1--1-1-i--+-l--l-H '
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l-+-t--t-t--t-+--l-+-+--l'-i-·-t-l-+-t-t-+-t--t--~-t---<-+-+--l-+-+--l1-1--1-1-+-+-+-t--+-+-+~H--l-~-t--l-+-f-l-ll-+-l---l-l--+---l-+--l-l-l-+-+---1'-l----l--l--+I-+---! 0 0 2 l-+-+-+-+-+-+-+-!-+-1-!-+-!i-++-i-+-+-;-+-+-+-+-+-+-+-+-+-+-+-+-!-++-!i-+-t-1 ""-. I
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0 • 11-1-+-+--l-f-+--lf--l----l--l-t--l-l-f--+---l--l--l--l--l--l-+-t-l-+--l---t-+ r-1-t-l---l--l'-l-+---H
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0 • 0 _._.._._.._._..._,__.......__.__._._,_._~~_._.__._.___._,~.__._._._..L-'--'-'--'-'---'-'-' ·-400 450 500 550 600
Wavelength run N,N-Dimethyl-p-phenylenediamine sulfate in water plus
2 hrs. after addition of Scan vs. methnnol ..
650 700
l drop cone. NH4oH. Scan made base.
FIGURE 27. 'IHE EF.F'ECT OF BASE ON TIIE COIOR DEVELOP1'1ENT OF THE Ju'1INE rn· WATER
t-
750
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0.2
o.o 450 500 550 600 650 700 750
Benzoyl peroxide Wnvel"ngth nm
in pyridine (60,.,..._g/ml) with th~ reagent in water · trs. methanol •
.. FIGURE 28. COLOR DEVELOPMENT IN A BASIC SOIUTION. CONTAINING NO METHANOL
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Wavelength nm Benzoyl peroxide in benz~ne (50/>'g/ml) and N,N-dirnethyl-p-phenylenediandne
sulfate in water (O.)%). Water layer vs. methanol.
COLOR DEVELOPJvJ.ENT IN A T~lO-LAYER SYSTEM THE EFFECT OF BASE ON THE PINK WATER IAYER
FIGURE JO. COLOR DEVEIOPHENT IN A T.'10-1.AYER SYSTEM
THE EFFECT OF TRIS-BUFFER ON THE YELLOW BENZENE LAYER
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400 h50 500 550 600 650 700 Wavelength nm.
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t-+-+-+-+-1-+-+-+-+- -1-1-+-1---•--+-+-<--+- l-t-H-+ - H-+-t-H-H-+-1 1-1 - -H-+-H -t-t--t--t-!-+-+--+-<--.J t-+-+-t-+-t-+-+-+-+- l-+--11-t- -l-+-1- - I- - t--1-1 - - I -t-++-1 - - --+-t--t- jl-t--1--1-+-t-+-t-+-+-IJ
t-+-t-+-+-+-+-+-+-+-H- -1-t-t-t·-+-+--+-f-t-+ --1-t•-+--+-1r- -f-t-t- -1-1-1-1-t-+- l-t--f-1--1-t-H-' - -1-t--t--1--1 t-t--+-·+-<-+--+--l-+--+-1-1--1-+-+-I--+-+->-+- -t-t-t- -1-;-h H -1-t- -f- -1-t-: -1-1-· -j-l-t--+--+-+-
'--'-1-t--t-rt-+--t-t-t- -f-t-++-· -!-!-I-· - -1--t--i-j-· -t-t-1-- -1-f-t- · 1-t-J-t- --t-+-t-t--'-->-+--+-+--l·-+-+--+->-+-+--+-+-<-+-+--+-,_f--+--+-t-1- -1-1-- - - -1-11-H- -+-t-+-l- - -t-t- -t-t-t--1
t-i-1 ·-t-+-t-t--t-t--t-+-r-j- -1-1--1-; - -t-+·-1-1-1·-1--1-+-l-l -/-+-t-+ 11-t--t-+-t- -t-t-l-+-l--t-·H--1-t-+-+-+--+-t--t-+-< --t-t-1-1-1--t-l-l--.---t-t-+-t-l-t--t-l-t--1-t-t-t-j-t--t--lt-t--l
l-+-+-t-+--t-H--+-11-1-+-1-l-H---t-+- -- -- t-t-+--+-ll-l--1--1-+-l-t--+-I t-- ·-+-<~t--+-1·-+--+--+- 1-1 -+--•--+-t- -t-+--+-<--.1
>-+--+-+--'·-+-H-t-1- -1-1-+--+-•--t-t-- t- -l-t-1- ·l-+-H-11- -1-1-H--•-+--+-+--+- -+-·•-t-+-t-+-+-+-+-j
'-+-+-t-+--t-+-+-t-+-1-1-1-+--t-11-+-t--11-t- -t-+-t--1-t-t·-+-1-1-1 -1-t-++ H-1-+ -1--1-H- H-H-1- - -1-t-H--+-+--+--+--<J
[.-+--+--<-+--+-<-+--<-I- - 1-1-H-t--<--t--+-+-+---+·- -1--1-1 -t--t--t- -H-1 - - -1-t-l-!-t-< H--!-t--t-t-t--t-11- ---'--1-+-t-t--t--t-1-+-1 -H-l- -1-H+I r -H-t-H 1-t-t-i-t- - -t- - -1- -t-t- ·-1-+-t--'-'
HHt--t-Ht----H--1-1-Ht-- - t-t--t--1-1-t--t-- t-t--J-t-t-l-t--t-1-- --Ht-H-1-H
Ht-i- --t-t--+- 1--t-I ·t-- - -- -t--1-t-- -t--+--1- - -1-- -!-·!-! -t---H- -!- · - -Ht-H r-r--1-l-+-H-hl- - - I- - -1-t-t-+- --!- -t-- -H- -- - - -t- -t- --t- -t- -1-+-·-H-H -H- -1-+-+....-. f-t--1- t-- - - -1-- -1-t~- --t-1 -H-t-1- ·-!-H- --!-+-·- -1-11-H - -- --·!-+-,-- -H-- - -t--t--- -!- -t-1-· --1 - -t-H t-- -1-t-t-H- 1-t-- - ·-t--H-1- --H- -+ -t- -1+1- -t--t-H-l-t-1- -t- -t-t-+ - ·t-++ - - -H - -H-· - - -1-hH-
t-+-+-1-+-1-t-t-1--1-1-t-1-H- --1-t-·-t-H -H -H--+H-· --· - -t-- - · H-+--1-1- -t-t- - -H-+-t-l-t-t-H-H-1-1-t--1 1-+---+--1--+-.-+-+-t-+-1-;-...-+-+--•-+-<--<--1- -- · 1-1- -H · H -1-+·-+-+--+-1--+--+-+--+-< '--'--+-t-+-+-+-+-+-·t-l-t-t-+-+-lt-t--1-l-+- -+-+-1--+-t-t--+-·t-+- -t- -t-+- - I - ++-+- -1-t-H - 1-t-t-t-- -+-+-t--'-'
§0.8 1--+-+-+--+-+--+-+-t---+--+-+--+--+-+--+-<-+--I·-+- -t--1- -t-- ·+-+-!- -Ht- I H -H
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o.6
1--+-+-•~--+-~-+--+--+-+--+--+-+--+--tf--+- -t-1--+-+-+--+--+--·t-+-t-+-+-+--l-l-t--+-<>-t-1-1--t-+-1--+--t-i-+--t-•--+--+-<-t-t-t-+-1 ~-+-t-+-+-+-+-+-+-t-t-+-1--+-+-+-+-+-+-+-l--l--l--il-+-t-1-+-l--+-<-+--+-•-+-•-1--+-1-+-~-+-+-t--l--t-t--/-lt-H-++-it-+--t-~-.
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0.2 N
..-.-+--t--t--Hf-+--t-l-t-+-t-t-t-t-t-t-t-t-t-t--t-t-t--Ht-t--1Ht-f-+-t-t-+-t-+-t-t-+-t-t-+-t-t-t-t-t-t-t-1--+~~-.... ~T'-t---t-t--+-~, 1-+-+-+-+-t--+-+-ll-+-l-+-+--+--+-1--+-+-+--+-•-+-+-+---<--I-+--+--+--+- -1-;-1-+--J-ll-+-+-l-l-t-+-+-+-+-+-+--1'--f-·--+-t-+-t-~•r-~t .... --t-. 1-+-t-+-1--t-+-1--t--t-1-4-ll-+-+-ll--+--+-t--1--l-·l--+--l-lt-l--1-l-t-·I- ~--+--+-t-+---+-1-+-+-1-l--H-t--t-1-+-t--+-l~-t-+-l-f--f-f--t=~
t-+--t-+-1--+-+-+-t-·t- -1-t-+--+--11-/--t-t-- - - --H-f- --1-1·-t-I--+- ·-l---t-l-/--l-l-l--l-l-1-+-t--+--+-- -l--+-·+--H--t-l-+-1--1 t-+-+-t-+--t--t-t-t--t-l-4-l-t--t-11-1--1--11--1--1-t--t-H- -- -l-+-+-+-·i-+-+-t--1- -1--H-t--Hl-+-t-I- -11-t--+-11-t--+-1-+--t-1
1--t--t-1--t--+-11-t-l-t--t-+-+-l-+-l-l-+-1-ll-+-+-+-+-t-+-+-t-~--+-+-+-t--H--t--+-l~~-+-t-+-+-t-+-+-+-+-l-+-l-+-l--t--+-l-1 o.o 400 450 500 550
Wave1enp,th nm 600 650
(0.3%) plus
'700
Benzoyl peroxide in benzene (60ft.'- ~/ml) and reagent solution excess NH4~H. Methanol layer vs methanol.
·FIGURE 34. THE METHANOL iAYEH AFTER ADDITION OF EXCESS BASE TO. THE ilEACTION MIXTURE
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Wavelength nm :N,N-Dimethyl-p-phenylenediamine sulfate 1n <11cetone vs. methanol
FIGURE J.5. COIOR DEVELOPMENT OF THE AMINE IN ACETONE
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± 400 450 500 550 600 650 100
Wavelenvth run Benzoyl peroxide in benzene and rearent in water. 6N H2so4 added to benzen~ layer to give red suJ fate. Scan vs. metta nol.
FIGURE 36. THE RED .SALT EXTRACTED FROM BENZENE INTO WATER
750
(49)
tris-buffer. No.scans were made of this solution. No further··
tests with a~dehydes were made. •
D. N,N-Dimethyl-p-phenylenediamine ·Sulfate in Acetone
The behavior of the amine sulfate in a solvent less polar ··
than water or methanol was investigated. The amine sulfate was
insoluble in benzene. It was only slightly soluble in acetone,
forming a yellow solution with maximum absorbance at less than
400 nanometers, as shown in Figure 35. Combining this solutiqn
with an equal amount of benzene containing peroxide caused no
change in the spectrum but showed only the effect of dilution.
No attempt to change the pH of this solution was made.
E. Separation of the Colored Reaction Product
When an acid solution was added to the yellow benzene layer
described in section C, the color was e~tracted almost complete
ly out of this layer into the polar layer, which turned a bright
red. This occurred upon the addition of either sulfuric acid in
water or in methanol, or an aqueous solution of hydrochlor~c ~ct
acid. This color was apparently due to a reaction product. Its
behavior is characteristic of an Sl)line and its salt.
Figure 36 shows that a scan of the red aqueous layer gives a
very inteqse peak at 510 nanometers, similar to Scan a in Figure
23. Addition of base to this solution caused precipitation.
Figure 37 shows scans made of the red acidic methanol layer,
with Scan a having the same intense peak at 510 nanometers as in
Figure 36 and a slight peak near 640 nanometers. (Compare with
Soans a and bin Figure 23.) Addition of one drop of ammonium
1.6
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Benzoyl peroxide benzene layer to
soo sso 600 650 700 Wavelenp,th run
in benzene and reap,ent in water. 6N H2S04 in methanol added to giv~ red sulfate. Scans vs. methanol ..
FIGURE 37. THE RED SALT EXTRACTED FROM BENZENE INTO HETHANOL THE EFFECT OF BASE
' 750'
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400 450 500 sso 600 650 700 Wavelenp:th run
Benzoyl peroxide in-b~nzene plus tris-buffered rear,ent in water. Benzene layer plus'g1acial acetic acid. Scan vs. metranol.
FIGURE 38. 'rt-IE F.lf'FECT OF ACETIC ACID ON THE YELLOW BENZENE LAYER
i'-..
750
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400 450 500 550 Wavelenp:th run
a) rted anti ne hydrochloride (reaction product) yeJlow-?reen solution.
b) So1uti.on from (a') plus acid. Both scans vs. methanol.
~
600 650 700
dissolved in water, giving a
FIGUhE _39. THE RED SALT DISSOLVED IN WATER
LOO LSo
Red amine sulfate
5CXJ 550 600 Wavelength nm
(reaction product) dissolved in methanol, scanned vs. methanol.
650 700
~I
. ......o 750
giving a blue solutio~,
FIGURE l!O. THE RED SALT DISSOLVED LN &'!ETHANOL
Q.J 0 c
"' ..0 H 0 en
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coo h50 500 550 650 700 750 Wavelength nm Red amine sulfate (reaction product) dissolved in ethanol, giving a green solution. _Two concentrations scanned vs. methanol.
FIGURE 41. THE RED SALT DISSOLVED IN ETHANOL
4~00 3000 2000 1500 r1 ~..L...L.l...l. .L ..l. ..l. ..l. ..L.l..L.l ..L J ..l. .l .J.. l ..l. .l .l. l.
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FIGURE 42 •. INFRARED SPECTRUM OF THE SECONp_REACTION PRODUCT
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t-+-+--t-•-+-+-+--+-l-1-1-t-+-l--t-1-H-t-1-+-++--1-11-1-+- -1-+-+--1r-t--t-t-+-1-~-.-+-t-+-t--+-t-+-t-t--+-++-l-t-+-+-t-t-l--t-+-l-+-+--H-t-H --.-..-+-<-•-t-t--t-1-1-+--+-•-+-·r-t- ;-1--1-1-+-+ +-+-1-1-+-t-+- t -+-1- -t- -1-t-+-+-~t-t-+-t--++-+-+-+- --t-1--1--1--1--1-t-+-+-t--+-1-1-1-0-+-+-+--1--1
t-+-+-l-+-t-l-++-f-1-f.-t-t- - -+-+- -1-1-1-._,__,_,_,__1-1-+-+-1- - f- --·1-+-H-+t-f-+-t-t-i-· -1--t--+-+-l-t-l--+-i-+-·+-+--+-l~1-t-+-1-+--l-+-i-l'-h
t-t-+-+-+-l-+-+-+-t-1-t-t-i-t- . H-1- -1-+-1--1-1-f-l-+-1-1-t-+-+--t-·1-t-+-+-+-t-t--+-t-+-+-l-·4--l-t-+-t-·-t-1-+-+- -i--+-+-+-t-+-+-1-t--t-+-+-ir-+l-+--+--+-+-0--1-+-+-+-ll-t-+-t- - - _._,t--·t-l-1--'-'-l-l-l~l-!-t-1-l-+-H-1-+-++-1H-+-+-l-l-t-1-1--+-+-i-l-t--l-f-1-+--t-+-+-1-l-+-+-+-l-l--l-t-+-+
l-+-~--+-~--'-+·~l-~-+-+-t-+-~-+--+-+-~
1-t--+-l-+-t-+-+-11-+-t-+--t-r--t- -l-+-+·4-11 -+-t-t- -1-+-+-+-+-,_,~t--t-·t-t-1- 1-1-t- -+-+-+- -t--1-t--+-~-1-11--1-·i-t-l-+-l-+-l-t-·+-4-+-+-
-+-+-+-+-1-.-._,,_..-1-J-+-t-- -r- t-1-t-- -l-+-+-+-+-t--1-+--l-lt-t-+-+-t-1-t--+-t-l '-+-+-+-+-l-+-+-+-+-1-1-+--l-+-i-l-t-+- - -t-H-+-1 l-l--+--.-~~t---l-lf--J-l-+-·+-+-l-+-+-+-+-1-t-+--t-+-t-+-+-1--+-~-+_,_.._,_
-t-+-++-t-+-+-+-t--1·-t-+-t--+- - +-1-1- -4-+-+-·+-+---t-1-+-+-t---1-1-+--1-1-1-1-t-+-1--<-•-1-+- -t-H-1-l--l-+-H-t--++-HH-+-+-t-H--+-t-t-t--t-++-1-1~-t-+-+-+-t-+--t-f--+-~- L-~-"--'--1-\-f--~+~-H-+-~-l-l-+-+-t-l--!-+-H-J-+-+~~- l-t-l-t---+-~-+-t-+-+-+--+-+-+-1-1-+-++-t-+-+-+-+-t-
1-t---1-t-+-+-+--+-+-+-t-t-t-+--l-i-+-+-l-l-++-HH-+-+~-f-l--+-t-l-+-t-+-1-l-t-J.+-1H-+-t-+-t-++-t-t-+-+-l-lt-t-+-+-+-+-t-t-i -i--t-+-t- -.__,_-~--+-+-+-f--l-J~l--l-+-+-l-~-l-+-t-.L...L...L.-J-.+-++-+-~f-l--+-t-+-H-++-t-t-t--t-l-t-t-t--t-i-t-t-T-t-1
H--1--t--1-t-J-t-t-+-+-+-+--t--1-t-r~+++--1-1-+-1--+-1~
t-+--+--+-1-+-~·-+--+->-•-1-.v~-t-r-r-t-t-i-+-1-1-+-+-+-1-1-~•--+--t--+-~-t-t-t-V ~ l-l---t-1-t-+-+--1-11--t- 1-+-t-i- -1-1-1--h-.--ri-+..jf-+-l-+-+-H-+-t-+-H-++-+-H---H-t-H-·+-+--l-l-l
l-+--1-t-1-4t--t-+-+--+- .,'J."+-t--+-j~t!\ t-t-+- ·-1- -1-+-+--+-<<-+-+-+-•-·t--t-+-+-t-t-+--+-t--l-t--l-l-+-+-+-J-+-+- l-+--+-+-+-+-+--1-1-+--l-+--1-t--1-+-+-1-t-+-+--<-+-~t--1-t--t-OFl-+-l---l-li-+L~- +-+- - l·-~-l---t-1-t--t-+-i-lf-l-+-+-+-t-t---1-t-+-+-~+-i-+--t-l - - -1-t-t-+--r-t-+-.,.-t-+-+-+-t-t--+--t-t-+-+--t-i-t-t
-I ll
sso 600 6.50 100 75 Wavelength nm
Benzoyl ti~roxide in benzene and reagent solution (0.3%) to which 0.25 ml or triebuffer had been added. Scans made 15 min. after mixing vs. reagent blank.
FIGURE 47. SPY.CTR.A REPRESENTING STANDAHD CUHVE lt"OR BENZOYL FEROXIDE IN A TRIS-BU1''FE.RED SOLUTION
1.6 -· ~-+-+-+-4-+-l-f-l--+-+-l--t--l-t-1-t--+-4-1-1-+--+-+-+-IH-+-t- l-t--t-t-t-1--1-+-+-t- t-·t--+-1-!H-+-t--;-t- --;---;--+---;-1--+-t-t--.-..-rlH--+-t--t-t-t-t-,_,__,__._,_ .......... _._,_.._.._._ 1-t_ -+-+--+-t-+--1--+-+-t--+--l--+-+--•-+-·t-t--t--1--t-~--l-t--+--t-· -1-t-t-1-........ ·1--t--t-t-t-+--i-+-,.._,1-t-.,.......,...-1-t--+-<1-+-+--+4->-+-.....
1-+--+-1-+-~-+-!--+-l-+--+-+-+-f-+-+-+-+-l-+--t-+-l-+-+-+-1-1-- -++++ . -t-t--t- - l-t--t-t-1
1-1-+-+·-+-l-+-+-1-+-t-1--+-1--t--1-+-+-1-t-1-+--t-t-+-+- H--t-t- 1-1- - -'r-'-f-+-+.-1-1--1-1-+-+-+--1-1-+-~_,__.-+-.._....._,__._.._1-+--1--+-+-+-+--+-<-+-•-+--1--+-+-,_~-1--+-+-•-+--+-+-+-•-t-t--t-t- r-t-t--t-t-H-f-~-!·--+-''-'--'--+-+-1-1--t-t--;--t-
l. 4 1-1--+-+-+-1-+-+-H-+-+-t--+-+--t-+-1-H-1-1-+--+-+-t-t-t-H +++++- -H-1-1-H-~ ·t-t-t-H-t-t-t--t- - -t-
t--H - -•.....,1-+-+-•-l-t-t- - -1-H- - -+-t-+-+-1-t-f-+ H-1-t-+-+-+-+-t-1-1-- t-t- - -t-- - t-+-H- 1--t-t--r-r-+-+·-+-11-1---1-+--1-1- 1-t- - -t--t-t- -H-H- -+-t-t--,-,-,.-1-t--t-t-+--t-t--t-
l-+-+-f-+-11-1--+-+- -t-+--+-+--t-t-+·++-t--l-+++-t--lrl-1-t-t-t-+--t--1-+- ·t--t--t-t--t-t-+- -t-t-+---t-+-+-·l--t--+-t--t--1-·t-t-+-t-f-t--t-+-+-t-t-+-t-t-
l-+--1-1-+-·+-+--l-1-+-t-+-l-j'-t-+-+--l-lf-+- -l--l--t--1--1--1-!l-t--!- t-+-~-l--IH-+-t--1-+ -l-t--+-1--+-t-+--lH-t- - j-j- f-H-J- -•-+-->--+--+-<l-+-........... 4-ll-l-t-J-I-• -t-+·-t-t- \·--j-•--+-~--+-;-
L-l...+-l-f-1-1--1-1-1-l-+-t-+-+-· - I- - f-t-+- - -+--H--'--'---'-l-+-t-1---1-t-+-t-J. 2 -- -t-1-·-•-t-1----t-l-f-t--,-t-i-t--r-- -t-t--t---1-- -t---t-1··--t-+-- -· r-- ·1---t- H-t-1-+-t-- +-
:~'~ ~:= :r;~~-- ~-:1=~-- :-_- ~ ~~~- --~-~: -~-~~~:~ __ ';_;~ >~:~~~~~~~' ---1- :t:~~-=,:~i~=-~~;~ - --· -H- --1-1--- - I-+ - -t- --1- -I-- - -1-1- -H H - - - ·-t-- ·-t--H-·t- -- -- --t--- - - - - - t-- ~ · - -- -t- - - -trl--t- -t-++- -·
1-+-t-- t-+-+-· -t--t-+-- -1-t-·f-f- -1-t--t-t-t-t-+- -+-- -t-1 -H ·t--t- t-t- r" 1"1- -'-'--i I- -H- +- 1-1-1- ·!--- t--r-t-1 '-, 1--f-H--,-t-t- -1-- - · v -r--i- -t°"~
1.0 t-1--t-1-1--+---+-.--t--t-1- - t--+-i 1-t-- t--t--t-1 1--t-t--t- - -1__,-V-l1~trt.l::c.E::Lmlih:I t-1-t-- - 1-t-- - ... ·t--t- - ! y ± ---- · 1-t-t-!I..
r-rl-1- - -I-+--+- ... +--- - ·-t- '"' -+-t-t--l .. J..._,..~-t-t-t--+-t-+-t-- -t-t-"-t-t-lf- - - - -t-+- - - r-+-- t-r·t-i-r-1;,1-t-- -~ -M +-+-I\~'1 1-+-+-1-+-+-+--1---1-+J
-+-1-+-+-1--lJ-+-I- - --1-t--1- -1-t-1---1--t-t--i- - -r---1-t- -t-- +- Y-t~!:iiD. _, ,1rn--~,~~h!l-t---1--11\•-+-+-+--+-'1--+-+--;--+--1
0.2
j_ .._,_...._,__ ..... _ -0 • 0 L-J....J'-L..-1~-1....1-........_......_ ........... __.__, _ _ I
400 450 500 550 600 650 700
Benzoyl peroxide in pyridine and Wavelength nm
reagent solution (O.J%). mixing vs. reagent blank
Scans made 1$ min. after
" FIGURE 48. ('
SPEC TH.A REPRESENTING STANDARD. CURVE FOR BENZOYL PEROXIDE IN A PYRIDINE-WA'Th.R-&THANOL SOLUTION
750
; 1 ••
10
Benzoyl peroxide
·FIGURE u9. BEJ:t:R' S 11'.W CURVE FOR A PYRIDI.NE-METHANOL-WATER SOLUTION
o.a r-r- - . ,-,- - r.- -,---,-- - - r-;
..... I-++- t-H->-+--+--t---1- -t-t-t-·t-+-t--+-+-+-l--t--t-+-1-r-r---r-r-r---·1-r-t-t-t- -t-t-t- --1--1 ·+-+--t-l--t--+-+-t-
t-++-~--+-1-1-4-+-+---l--HHf"t-1'.~~=]~j)~_:: ~11~11,~l=;:::;:=;=:~H-+++-+-t-+-+-+-t--tl-+-+-f--t-l·-+-+-+-+-1--t-r-~-1-r-t-t--t-i-+-t~- ~t-+--t-+--1-l-f-l-t-j llt-t--H-+- -t-t-t--t-t--t--t-t-tr-1-t-t-t-t-·t-t---t-t-t-11-t-+-t---t-t-t-t-t--t-- l-t-t-t - -- - - i---r--t-1 -t-f-1-- _,_._,___,_..__.
t-~ ;} -\~ + -t-t--+-++--t-++- --l-t---f-t--t--t·-t--+-+-t--1-t-+-+-t- -r-l-t-t-V't-t-h~- I~ -r-t'\ I :\i- --t-+- --1-1'-'-'-' -t--lr-H--jj-+- H- -t---t---t-t- ]J'I ~ '~t--1-'l\.-~-H-
/J -I- .. ~~-..-.,t-t-t-+--+--+-t- •-r-t-•-t--•-<-t--t--t-t--t--<~t--t- --fit--rf-1 l-t-t-t-t'-1-1\l--+-f/_ ll II~ +- -lf-rlj_ t-t-t--1-H-1+ [l+-' --+--~~ j \\ t- -I- -f-1-t- - t-t-1/i-/t- - -·H-t- - -~:\:-+- I
j,JZ - i-\\ 1--t- -t--t-j-/-Jll--t- -1-t-j- -r- t- -1-1- -r\H-l+l---+!-+-1--<-Ht-1
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o.6
t--t--l-+-t--+-+--t-t-+-+-+--t~ --f-H-1 ~ -t--1-+-+-t--1-tl.--I' ·Jt--+--t---t-t-t-t--t-+·+11--ff1-++-+-t--t1--t-1--+-t-t-t-1-t- -1-+--+- f\-1- -1-il-H -1ll llll I/ +-+-~ 1--1-+-+--+-1-+-+-+---i-l-+-+-+--t-l--+-I-!-\ ~ 1-.r-- t-t-t-i t-+-- i-\ -H +-H
o.5 ,_ H-+-1-1- i 1~1-t---1-t-t-t-ll- '1 '--U 1J 11 , l-+-+-+-+-1--f-f-t-+--f--t-i--Hf-f-f-t- __ j\ I j --r--t-r-·t-t·--t--<'-t-·t- ,__,_,__,J,..,..._._,_r--t--~- .,_..,..._,__,_--t--<-i--t-T-·f->-·.._,_-,1- >-->-->--+---<
lLl-+-t-t-+t-1-1-4-+-Hlll'l-l-++-l-t-H--H-t-l-+rl---H-+-r~-t-!-t-t-l-1----Hl-lf--t--t-t-t- ~ JI- IL t-t-t- - _._,_,__,_,.1r t--+-+-
L'l L t-+-H ~ ~-~-~~--t-f-t-+--t-t-t-t-t-+-t-1'-t--i-t--t--t-+-t---t--t-r-t-IM
t-+-t--t-t-l-+--f-+-t-l-+-+-+-+-+--+-1-+-+-l[H~~+-t-t-+IS:'ol--f-l+-f-t-+-+-t-tH ~ - ~l-t--+-t-+-t--t-t-t-t--f-+-+-11-t-+-+--t--t-t---l-f-Hl_\\l-J--4-!-t-l-f"'t--++-l---t-JH-t-1--f-f--+_y:l-t-+-t---t--l:-tr-t-t-+-1- - -tr--+-t-+--+-"1\-\ HH
rt i---rt--tr ~- --~- -H+-+--t-- - l-lc--+-t-t-+-t-il..1--,,-~--+-t--+-+--+-+-+-+-1~-1-r-~ r]'i ~
ll Ll.L I'\ 1 ~-t-~\+-i-+--+-+-+-1-t--f-t--t--1-+--i-+--+-~-~t-t---1-1--+--•~~~~-1-+--+-<-+-i-;-t-t--i--Lv"~-+--..-.--+-+-•~~~,._,_-T-t-t-•~-t-t-t-t- ~ ~~ 1--t-+-+--+-t-t-+-+--1-1-Ht-+-i-+-+-+-t--t-t-~ff+-1--rt-tr-t-t-1-+-t--t--Hl~-t-1--t-t-t-~-~rr++-H--t-1~--t-t~-t-t--r--t~r-1r-r~~+--i-t- u
~ J\. Li ~ Y- ~ &
\ ll
0.3
0.2
-- t-+-t-+-HH-+-+-+---l-+--1-++-+--HH-++-+-l-+--l-+++-+--l--t-l-+-t-t-l-+-+-+--Hf-+-4-+-HH-4-+-+---l-t--1-+-++--+-l-++-f--H-+-t-++-t-t-f-
0.1 rt-t-t--t-l-t-t-+-t--+-+-il-l-+++-t-t-'-'--"--t-t-H--H-+-t-t-+-t--t-t--t-t-+-++·+-1H--t-+-t-i-t-~t-+-+-t-HH-++-t--l-t-t-t--t-t-t-t-t-+1
H-+-f--t-i-t-t-t--t-t-t-H--t-t--HH-+++-t-t-t-t--t-t-l-H---t-+-t-1H-++-t-i-t-t-t--t-t-t-H-i
-+-1-+-++++--l-IU-t--+-1-+-t-+--1-+-+-l-+-+-+-Hl-l-t-+-t-f-t-t-t--H--t-H-+-f--H-l--H-+-t-t-t+-t-t--t-H-++-t-1-~+-+-t-t-t-t-t-+-t-!,
o.o 1H--t-+-t-l-t-t-+-+4--h--'~~-I-~~
. l!OO 450
Bonzoyl peroxide in benzene buffer has been added. Each
500 550 600 650 700 Wavelength run
(601'-g/ml) and reap,en~ eolution to which 0.25 ml or aolut.ion scanned againet its own reagent blank~
FIGURE 50. THE EFFEDT OF CHANGJNG THE REAGENT CONCENTHATION IN A TRIS-BUFFERED SOLUTION
75C
tris-
o.a - .. ,,-1-+++-+-t~l-l-+-1-j-t-t-t- ! t-t-t-. -- -t--t--t--'- 1--1- -1-+- 1--1-1-' t-t- ·t-t-+-+-+-lf-+-+-+-+-l
- t--H-l-+-t-t-t-:·-+-t-1- - - l-t-t--·- -+-1-+-~~~-1-H -0-1--<-+-<-11-t-1-+·++-+-lH-+-1--t-t--t-t-t--t-+-+-+-1 t-+-t--t--t--f--11-+-t--1-.-r--r-+-•-t--t--1-H-l--t--1-1 -M--t--- t-++~t-t--+-+-+t-+-+-t-t--1-~-t-t-t-!-t-t-t--+·++4--+-1~ 1-+-+-+-+-•--+-.._.-+-1-+-1-+-1- 1--i---t-r-i--11-1-1-++-1-t-t-1--i- 1-+-1-1-t-··•--+-+-+--+->-_,-1-t-+-1-t-+-+-t--t-+-+-+-1--1-!-+--1-+-1-t-t-1--t-·t-+--+--t-+-1
t-1-+-t-+-+H-1--t-t-t-l-t--~-t-t-r+-t-f-+-t-t-t-+-1-t--l-t--t--·t-+-+-+-~~-+-+-+-+- t-J-+-t-t-t-+-+-+-1-t-t-+-l-I -t-t- t-- - 1-+-t-+- - - +-+-+-- - t-' ,.,
•-+-~+- t--+-+-+-1-1-' -t--H-t-1-t-- --1-1 H - -!-!..· - ~} -H-r--t-1-+-+-+-+-11-1-+-+-+-l Q • 7 - t- - - - 1-t- - - - -t-H - - - - t-t-+-1--t--H H- t-t-' -t--~t-t ~\- -t--1rl-t-i--t-+-+-t--1
l-t-+-+-t:>-+--+-+-+-1--t-+-+-t- 1--+--1--1--1-1-1-1--1--t- .. t-+-H- I- - /7Y': ~,.. _:-\..,b.i\H~~t--t-t-+--t-+--+--+-t--H Hl--t-H - - 1-1-+-+--t- 1--+--!--f-T--.- ,.---~ -H- -rr-· N-r~:t{"-•-+-t-•-+...,t-+-+-+-+-+-+--+~ 1-+-+-H t-t-+-+-+ ,_,_,_+-+-~-1·-r-+--1--1-;-·-+-~--t-+-~-+-•-H-+-1-! lp,J, -r-t-H~~ l-+-+-+......-CH-+--!-+-l-+-l'--t-+-l-+-+-+-t--l-H-+-+·+-1-1-1--t--t-t---t-+-t-< t-·~ - -t-+-+i!ZJ- lf-+-t- -P.t-· '.IJ '1\_)\t--l-Hi-+-+--+-t-1-1--+-I
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t-t-+-+--t'-+--t-t--1-t--1-1-+-+-+-t-t--11c--f-t-1-t-1-t-+·-t--t-1--t-+-H-J-J-t-l-+-t- t--V-i/-t--t--H r'\.~\ -t-t-f-t-t-1-+-t-+-+-f--+--t-+-H-+~~1~~+1--- rnl~.-+--+-+-i-+-t--+-+-t
l-t-+-t-t-11-t--i-++-t +-+-t--f-1-1-1-+-I- -l-f-f-+-+·~1-t--+- l--H-l-+-++-t--1-~-H-if]l_ t-t- II\~'+-t-+-+-t-1-t--1H H---11-1 - t- _l J ".\'
l ,I..
Wavelength nm Benzoyl peroxide in pyridine (60 .Ag/ml) and reagent sol_ution. Each solution ..
scanned against its own reagent blank.
FIGURE 51. Th.E t.FFJ!:C T OF CHA?\GING 'ffiE REAGENT CONCE.N TBA TlON LN A PYRIDINE-WATER-METHANOL SOLUTI~
t-+--t-+-+-1-t-t-1--+-1-+-1--+-+-+-t-+-t-,_,._-L-t--1-1-1-+-1---+-1-r-r-+-+-i--11--i--rr-r-1-t-t-t--i--+--r-t-t-t-·t-t-+-+-t-t-Hr-t--.i-t-Hl-t--t--l-<--~'--'
t-+-+-+-+-l-+-+-+-t--1-+-4-+--+--t-+-+-+.-.-,-,r-+-·l-l-+-+-1-+-t-t-t-1-t-t--t---t-T--t- -t-t-l-+-+-1--+-t-+- --..--.---.-,.-.-.-.-.-.- -+-+-1-1-f-·1-+-f-+-1
1-+-+-+-1-1-t--1-+--1-1-+-1-1-+-t--1-1-1-.r--1--1-+-+-1-t-+-+-1-1-1-+-+--+-t-+-1-1-+-t-1-t-t-t-·-1-r-.-,_,- ··t-r-i--r-r-i-r--r--i-- -+-1-1-+-+-t-1-t-t--J
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+-+-+-+·-+-+-+-t--t-1-1-+-r-l-+~+-H-+-+-l---1f-t-+.++.~--l--W--1---l---HH-+-l·-H--t-t-t-t-i--t-H
o.o L-1-'-'
' 400 450 500 ._.__.___.__._._,_.._.__.__._._._._.._...~._._.._.__,__~_.LJ_L.LLL.L_LJLJ,_LL.LJ__t__LI-.J.-J.--'-''-'-~--;-:
550 600 . 650 700 750 Wavelength nm
Benzoyl peroxide in pyridine (60r g/ml/ and vs. reagent bl.an.le. .
reagent solution (O.J%)
·yrGUhE $2. .. -. COIOR DEVELOPMENT WITH TIME IN A PYRIDINE-WATER-METHANOL
$01.UTION
l.·6 r.
t-t-t-t-rt-+-+-+-+-+-+-+-+-+-t-HH-t-t--+++-+-H-H-1-1-+-+-++-+·-+-~-+-tH-1-+-.+-1-1--1-·1-1-t-t-rr-+-+-+-•1-1-1-+-++-+-~-+-+~~ t-t-<r-.-t-•->-+-+-+-·•--+--+->-+-+ .... - H-t- -t-+-+-t-l-l-t-t-+-l -+-t-l-t-+--+-+-+-1--'-'--l-l-+-t-+---1-1-+- l--+-+-l--l- J
1. 4 1-+-+-+-t-l--1-+-+-+-l--+-+--+-t--........ -<-t--I- I -t-1-1-1 -1-+-J l-l-+-t--+-++-+--1-1--1-+-+- t-+-+-+-t- --t-+-t-l'-+--•--+-r-/j
l-+-'l-l-l-l--+-t-+-11-1-1- f-J-1-l-t--t-+-l-f-l-+-l-+-l-+-lf-t-l-t-l-l-t-t-+-f-l-+-t-+-t--l-t-l-t-+--f-1-1-+-+-+->-1-+-<-+-+--•-+-+-+-+-<>-+-<-+-·<-t
0.2
50 600 -· 100 •I,,
Wavelenp,th nm Benzoyl·peroxide in pyridine (60Jl-"g/ml) and reagen:t solution (0.3%) ·(3 hrs. after
preparation) vs. reagent blank.
.,. FIGURE 53. COIOR DEVELOPMENT WITH TIME AFTER AIR-OXIDATION OF THE REAGENT SOLUTION
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1.6
1.4
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>-+-+--+-+->-_,__,__+-~-•->--+---+--<- t-+-+- -t--!l-+-+---l-+--l-+-+-+-i-t-+-+--+-i-t-+--1--t--lt--t---1-+-t-1--H-H- -1-,----r-.--.-1- -r--r--- -+--t-t-T--+--t-1--1-+-1-1-+->-+- -+-+·-+-t---t--+--1-H - - r I-+++-- · -rt-t----1-r-t--t-t-1--it-t---t-t- 1-,-1--+--1-+--l--l-f-t-l-1-1-+-+--+-t-+-+- --f-- H--t- f--j-1-1-t--;1""1--t-+-t-"I "'1-"'1-"'1·""1-t-r-j-t-t-
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; 1-t--1-1--1-1-- +--1-+-t-1-t---J-l--1-1---t--1--1·-J,-tl-t-H-- -· -H - H -1-t-t- - -i--t--t---r-;- 1-t-t- -t-t--t-1·--t-t-1- -t-r--t-t-t-1- t-t-- -+--1-t-+.-1---t--1--1-1--1 •--+--+-4_,_l-.__._.____._.__.__,_,_+-•-+--+->-+--f- - j---t-t- --f--1-f-- -r-t-t-r-- "-t-1-f-t- -+--t-t-+-t--t-1-+---t--1 I- - i-+- - -f-+-+-' · <-f--+-1~ r--·t- - 1--r--r--1--t--t---t-r---,-1-1--t-'-~'-t---t-t- 1--+- - t--t-t-'-1--+--+-+--+--+-+--+r-t--+-t--+-+-t-+-+--t-t-++ -+~ -1- -- -+--t- t--t-t- t-r-1-- 1.:1" ~ M ~ ~ -~j n1~ 11 f-"'tj_r- mt~~ ngl-+-+--+->--+--< 1--i-+--l- --t--+-+-+-1~-f-t--l-1-1-l-t-· +- t-t-t- t-1-1- - --1--r--t-: - - '' --t-+-l- -l-+-+---1--l-< l-+---l-l--1--1--1---+---1--1-1-f--+-t- -- - -- t-t-t-#~-t--t-t- ·t-f-t-- -+---lf-+-+--+--+-+--1-t-< t--+-+-+-l--1 ·+-+_,,_.-•H-t-t- -+-"-1-H- -r-+++- t--t-~¥'t°" -~-+-->-+-+-+·-+ 1--1--+--t-t-t--11-+-1-+-H-+- -t--+--+-t-+---1-- --t-t-+-+-t--1-+---t--+- - - JL y~"" --t-t--1--t-1·-t-·t-f--t-1--t--t-t--+--1
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Be-nzoyl peroxide in pyridine (60ft g/ml) and reagent solution (0.3%) vs. methanol.
750
FIGURE 54. COLOR DE'lEl.OPl•lliNT WITH TIME USING METHANOL AS REFERENCE
() • 8 ..-.--,-,- -r-r-r-- - -,-,.-,-.,-r...,-r-.-..-r~.-.-...,-,, --H-t- --H--1-- -1--- --l-+-++-l-+-~j--l- t-+-+--l--l--11-- -t-+--t--l-t-H-1--1-1-+-- - i*ll 1
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400 - 450 500 550 700
Wavelength nm Benzoyl peroxide in pyridine (60 fig/ml) and reagent solution
. hla~.
(0.3%) vs. reagent
·FIGURE 55. EAHLY COIOR DEVELOPi-IBNT WITH TIME IN A PYRIDINE-WATER-.ME'IHANOL I.. SOI.UTIOJW
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Benzoyl peroxide in pyridine
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in water (O.J!b)
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-t-+-+-t-·1---1---1--1-+-~ --H--+--t- --t-+--+-f-l---+-1-1--1---f--+--+-Hf----I--+-+---+--+- --1-1- - - -1- --!-+--1 >-l-+---+--+-•--t--H-1--- -+- -++-1---t---+-f-I-- f-t-t- - +- -+-<-<-__._,
f-H- t-+-+-+-+-f--+--t--1-1----1--J--!---f-1-1---l----i-l-f- --+-<f-+--+- l--+-t-+---f-l-+-4-+-4--- -- f--t-H--C-1--+-'--1-L I-+-'--~--' "-'--+-+-~-~--+-+-1-->---•---1-__,__._.._, t-H- --\--+++- - -i--+-+-1-- +- -H--++-
1-l-l- - -1--1-+-W--+--+-1-- -- -1- - - 1-t-+- -!-+--+- -- -I-- -- ~-t-t-+--+-+_._, - -+---1--t-+- , __ _,__.__,_._, __ +-++- - --+-+-+-i----i-+-+_,f-+- -f-1-+--+-·l--t-t-
_,_ -1-t-l-
t-+l -+-t-+--l-~---l---1-1---+-i--1--L t-+--l---+--+--t-+-t-t---t--l-t-+-t--l--+-t--H---Hl-4---1-i-t-11--<--'-'-'---•-+--+-+---+- -+--+-+-+-+--+-1---1--~ I 1-+-1-I --+-•---<--'- t-4-4--1-'- t-+--+-+--+- ,__,_..__,____,_,-+-<~I-+- -f-+--1-+-l-+-+-t--~- -1'-+-+--1-l-+-t--+-+-I--1- - - -+-+-+--+--<
+ I --H---Jl-+--+-~+H---H+.J-+-J-1---1---J--j~l---W-l--LJ_ __j_ -f-f-1---J-jl-l--+-1-4-- -H- _,_,_,_ _ __,__, J: +--+--+--+--1- t-+-4-+-1---1---t-I- -+- -+-+-+--1---t-+--1--+-1-1-1-t-t-t-t--+--t-+-t-l--H--l--l-+-t--L--l-..j-1-+-t- -- t- -+-t--+--+--1
-l--+-i-+---'--+-+--->->--l--J-+--+--l- \ -- f-l- -- \---I-\-+--
r--r-+-f---+--l-f-l--~H--1-++-+-t-l-l-++-l-1--+-+-l-4- -t-t--+-t-t---+-+-t-----1----+-l--l--l--l-l-+--l-.l----I- -H-+-· ---1--+-+-+-t-1
+--+--+--+
t-r-t-t-+~-f-\----l--l-l---+--1--l---1-41---t-t--t---' --1--+-+- -1----1---f-4--l--l--1--i!-t--+-1-l--+-l-+-+-l·--+---+-+---+-l---+-l---+-l-- -t--+--+--+-1-- +-+--+-1--1
-t-t--t---t-H·--t-t-+--Hl-+----H-+--+-t-+--+-+-1----1-+-1-1-+--+-l-l---l-·l-+--+-,1-J-t---1--+- +- - -1-t-~-t-t-
-r---r-t-rt-t--+-+-t-t--t--+-t-f-++-1-+--+-1-+---+-l--+-•__,___,__,__,_t-1---+-•-+--•~---l-+---l---l---4-J rr-t-H---t-H---l--1-+--H-l--l---l---+----1--1-+---W-+--W_J___W_j___Ll-LLlJ- -t-++--1- ---<-<-~-+---1-t-+-' -1---1-+---+-+--+-l-4-+-+-t-t--t-t-++-f-l----l--l---1-+-1---+-i-1--t-r-t-t-t--H--+--+-t--+--+-+--+-~-+--+-+-+-l---J-+--t--+--1--1-1---t-1-t-+--1-+-+-t -1---f-t--+-t--t ~ 11-r-t-t---t-H--f--ll-+-H+-H-+--H-+ l-t+-W-!--W-l--1--1--1--W--l--H t--++-: -H --1----l--\ -+-1-+--+-l
I -·--1-H---l---lf---4-1---f- --l--+---+-L-1-1 _.__._.__,__,_t-+-f-t-t-+--+---,,_._ -f-+-1--t-I- H--t- -I-- - -I- - --1---+-l----t- ---+-1---1--4---l t-T-f-~-l---l-l---L-l-1-1--+--+-4-t-1-+---i-+-._-+-->----~-1-~-f-!- l--+-+-4-+-+-4-l--l----I-- -- -t-- -+- - -f-l- - -->-'--'----+--'
-l--+--+-+-~-++-l-+---t-1--+++ -l-l-+--t-11-1--+-t--l- -+-+--+---+--+-+---1---1>--+- -!--+-+- -1- -!---+-1--1--+-- -f-L-1---f- -t-+-~-1---l---l----1----L-1----l----l-4-1--1----1-1---l-H---t--11-1----l---l'-l----l--1-l----1-4--l--l---f-4-4-1-11- --~-+- --t--H-1--1--+--t--l-+-+--+-t-4
H+-H---l--l----\----1--jW---H-l -t-1-·+--+-1-1---1----1---t-+---+--+-t-+-t-+-+-+--+--l--+--+--l---l---1-1----1---~---1--1-t-I---' - -1-+-+---1---11-+-+-+--t r.--t-r-+--+-f-l----l--il-~--l---l--l---l-l---l---l-+-+--1-+-+-1-+---+--1---1----1---11--1---1---1---1--+-1---1---l--l--+-1-._._--+--1-~-r+--Ht--~-+-1-+-+-t-+---l--+---r-.
'-'----t--;t--~-+-ll-f---H-~.J-t++-f+l-++J--+---1--W-l-W--1--i-l-l---l---l---1---l---l---l-1--1--1--1----1----1--;_+-1--+---+-1-+--+--+--+-t---+--+-+-'-~ 0.2 i---t~1-t--t--l-~-t-l-+-+-+-+-l-t-+-+-+--+--~-\--t-l--\-l----l----!--ll-J--1-+--1----l----l--t--+-l-l--+--+-+-1>-~--i-4---+---~-,___._,_+---f-I-
0.1
~ I
i-t-H-t-t-H--1--1-1---+-~~'l"'-k++-H.-rf:-J7++-PK11---1-++-++--1--1-u+-.1j.-:1.,2t-lfJ~:r~_.. - i ~ rJT. in: r.ar. m !l •. ,_._.__,__,__,_, ,__._t-t-+t--H----1--J-jVWVi4--+--+--~~~~~~--1--l--l---~-l---l----l----W--W---l---l--l---l--l--.W-:l!-]-~~i;i-.~~t-+--+-+-t-1-+-+--~•--t-+----t--4---'--'
-l----1-4-4--1----+-+------4--+-~-1-I--~~ -~
I-+- J. ~ i- I - -
- -~
J:
::r o.o ,___,_
450 500 550 600 650 7:00 Wave)ength nm
Benzoyl peroxide· in pyridine (10rg/m1) and reagent solution (0.3%_} vs. reagent blank.
7SO
FIGURE_ 57 • COLOR DEVELOfi·lENT WITH TINE WITH A WW CONCENTRATION OF PEROXIDE
2 4. 6 8 10 20 30 Time after mixing (minutes)
Benzoyl peroxide iri pyridine and reagent solution (0.3%) vs. reagf>nt blank.
FIGURE 58. ABSOHBANCE VERSUS TINE FOR A PY.i:UDINE-HETllA~OL-WAT~tt SOJ.UTION
o.o 0 10 20 30
-: ~--; _i •. i -t ~
i_jj_ ±il i' ~ - ;. f 1 -t-t-l ; ~ - ; 1
:-.lLL 40 50
Concentration of benzoyl peroxide Benzoyl peroxide in pyridine and reapent solution (0.3%)
60 70 80 (re/m1) vs. reagent blank.
FIGURE 59. BEER'S UW CURVE FOR A PYRIDJ NE-i"lETHAl\OL-WA TER SOLUTION AT 67D NAN01•iETEhS
•
·<'----700 500 ~co· 300
i -1¢ i ! l i
1
~ wircH,1, I ~ .,
--~---- c, 1":~.v --+-----j------ sxi .\.
I /\/0 11 I : •
. 17V I I l C !i~ICH,J,! I £
I I 'J J ·- ' I '
-;::~ I ---1. \ --&- 6H,i, --11· .---n .. 10
v I ' . \/ ......... ~ ... J,~, N~liH - r -! --r l - ·... (') ].]Q'
'0' ! !H \y I y \" j ; f \ \ NICH,i, •
NICHJ, \ I I I : I l: . HNICHJ,
I , C . ! i ! ¢H.'llCH,J1 ¢ '.TO' ""'"' - I - : . A -- . : - " T- ' ~ "' /11
\ ! t }:"'-..._~"'\~: ~ I -~11 I I \ I i I\ y-:. "·.II I ~ ¢ I \ :t\A ,v:. y' 1" I \ f I I '\\ I: - ~
II ~I- I ,.:/ \ I \ NICH;i, ~L.:.ICH;l1 I i . \ ·. //
1.10'
, . I .. ./.. .., · ... /I \[ ··-.( .. " ! ·, / .
l---l~-L~..i--..:.._.:._-1...~~~~-"~---~~-----:~ 0 20 25 30 3SXi1 .. 10 15
--------'>-i> in cm-t
Fig. 1. A bforpt.ionsspcklmm des p, p' -Eis-dimelhylarnino-a.zobenzols (Charaktcristischc Datcn in Tabc!le S. 0000)
FIGURE 60.
Llisungs111ittel: ---·-···-· ~: Fcinsprit . --- ,-Fcinsprit/0,3:--: Salzsaurc (Vo!.-Vcrh. 9:1)
Feiasprit/konz. Salzsaurc (Vol.-Vcrh. 9:1) Feinsprit/Eiscssi0 (Vol.-Verh. 1: 9)
Ti::·: c:::.i:m~ Ii\ ABSOE3.C..l\CE WITH I-H i.''03. P, P ' - 21.s (:.:iL:1T::. YL.:-..::•"n;o )-AZOB!:..l•:ZEhE
Gerson£'. and~. EeiJ.oronrlcr: Fl~ysik2lisch-chcmjsc~it:· iigenshaft.rn unr. r:lcktr·on'=nstruktu:~ dn· ""zo-".!eroir~curir:cn, Teil XI): Be;;-:.:::rkunp: zur :3-~.::--c.:-::tc::· d .. S ·~zon-iU'".:_Y..,+-ionc- ·c.,.. 1 ->=<~.,..- 1 ~ c •• 1·i»-i -~ o'oQ 7 ' - ' '-·''' ci...~~· '· '· • - ... n"'-v- •• .., C .;J p,-;J ..;J..;; G-:ll<>TOY~o•T.~::10 ~z '-n ... o_,::;, •·'-'-'-'• ·--····~ .;~eta, hS, 54 (1962).
( 132)
:. \
•
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Addenda
Gerson, F. and E. Heilbronner: Physikalisch-chemische Eigenschaften und Elektronenstruktur der Azo-Verbindungen, XI: Bemerkung zur Struktur des Azonium-Kations des p,p'-Bisdimethyla'llino-azobenzols, Helv. Chim. Acta, !t2 ( 7-8), 51-9 { 1962).
Green, H~ V. and F. H. Yorston: Identification of Unbleached Sulfite Pulps in Mixtures, Pulp Paper Mag. Can., 2.1 (6),
.133-4 (1952); C. A., ~, 6832 (1957).
Horner, Leopold and Juergen Dehnert: Azoaryls and Phenazines from Primary Arylarnine Anions by Autoxidation, Ber., 96, 786-97 (1963); C. A., 2§_, 13948 (1963). ~
HUnig, Siegfried and Gunter Pielstocker: Substituent Effects, III. Reactivity Sequence of Compounds Containing Active Methylene Groups When Attacked b·1 Radicals, Ann., 2.2Q., 105-22 (1956); C. A., .iQ, 14599 (1959}.
Morrison, Robert Thorton and Robert Neilson Boyd: "Organic Chemistry," p. 745. Allyn and Bacon, Inc., Bos ton, 1966. 2 ed.
Roberts, John D. and Marjorie· c. Casario: "Basic Principles of Organic Chemistry," p. 692. W. A. Benjamin, Inc., New York, 1964.
ibid, p. 1032.
ibid, p. 1042.
1•1969 Sadtler Spec-Finder for Standard Spectra, u p. 304. Sadtler Research Laboratories, Inc., Philadelphia, Pa., 1969.
(138)
AUTOBIOGRAPHY
I, Bertha Brauer Cosby King, was born on May 9, 1931 in
Richmond, Virginia. I attended Richmond and Henrico County pub
lic schools, graduating in 1948 from Thomas Jefferson High
School. I then enter~d Westhampton College where I was elected
a member of Phi Beta Kappa, Gamma Sigma Epsilon, and Pi Mu Epsi
lon. In June 1952, I was graduated with the degree of Bachelor
of Science and received the Garnett Ryland Award in Chemistry.
In July 1952, I was employed as an analytical chemist by E.
I. duPont deNemours and Company, Incorporated at' Richmond, Vir
ginia. From June 1953 until November 1954, I resided at Johnson
Air Force Base, Japan, where my husband wqs stationed as a pilot.
While there I taught mathematics at. the Information and Education
Center. In the spring of 1955, I worked in the admissions of-·
fice at Virginia Polytechnic Institute and State University in
Blacksburg, Virginia. After my husband's graduation in June of
1958, we moved to Georgetown, South Carolina, and to Franklin,
Virginia in February of 1959. From September 1966 until January
1968, I taught science and mathematics at Franklin High School at
which time we moved to Richmond, Virginia. I entered the gradu
ate school of the University of Richmond in September 1968, and
plan to become a candidate for the aegree of Master of Science
in chemistry in June 1972. I am married to Henry Hobson King.