https://digitalcms.lib.buffalo.edu/upimage/1928-buchwaldk-thesis.pdf

Media

Part of A Study of Ultra-Violet Absorption of Certain Organic Compounds

extracted text: 't .fr

/) /

A Thesis
presented to the Committee on Graduate Study and
Degrees in partial fulfillment of the requirements
for the degree of Master of Arts, University of
Buffalo;
by
Kenneth W. Buchwald//

iN/y6y9a6
Prepared under the direction of Dr. E.R.Reigel. May,192S»

IT

1 -

2.

.

rW.- •' •

I wish to express my appreciation to Dr. E.Raymond
Riegel for all his kind attention and assistance during
the prepeuration of this thesis. Also, at this time, I
wish to thank Mr. Melvin 0. Reinhard, Physicist at the
State Institute for the Study of Malignant Disease,
Buffalo, H.Y.,, through whose courtesy the use of the
sector photometer and quartz spectrograph made this
thesis possible*

!--••• A 'A'

A'.A,-./-,-A

3.

A Study of Ultra-Violet Absorption of Certain Organic Compounds

(l :

IHE LdCKWOOB MEMORIAL LIBRA*f

Table of Contents
Page
Introduction

6

II

Mathematical Relations

1^1-

III

Theories of Absorption in the Ultra-Yiolet

21

Ja) Dynamic Isomerism
[bj Isorropesis
,c) Electronic Theory
IV

Apparatus

^1

V

Procedure

57

VI

Experimental Data

70

(a) Source of Compounds
(b) Ultra-Violet Absorption Curves
1. Esters of p—aminobenzoic
acid and related compounds.
2. Benzene Homologues.
VII

Discussion

VIII Summary

^

1^3
179

-

. 3%..

"Les donnees niimeriques qui oaracterisent
1'aTDsorption in^gals dGS diversGs lujniGrGs conduiront
peut-Gtre prochainGmGnt a UHG mGthode d*analyse chimique
universGlle;"
BGrthelot - SciencG et philosonhie.

6.

•': • •

ry'"y:vv'y;f;y'.y7y;.

'•.:

?;

•:5tv'.::

.

•-

•;

4

' i.

•-V/'

?'••••.•-' ,-•••'•'la&ii*
SK. ^. 1-

-V ' . f

^^ -

' •

,M -

Z Jntroduction
r

\>

'Bio,

y

,

• •-

'

„»

.

A

• 4. ,-0

:

•

"l -•.

y-V- "•' -

"

''

'

y V ylOi-'O- • •.
>

^ •oo-'oV.-:

y ^
. v:;

'' n .
..._,' 'x,-y. ,

'
vyy ..O.yO

•
V'

y,

y/O 'Y- Y' • ••yy

Ultra-violet apectroscopy is one of the more recent
developments of science. The first paper on absorption
appeared in Proc.Roy.Soc.,23, pp»223(1379) by Hartley.
Previous to this date the only mention made of the subject
was by Miller (l) who states that :he could find no reason
to suspect any connection between the diactinic power of
matter and its chemical nature.
Since then several chemists have studied absorption,
namely, Baly, Desch, Stewart and Henri, but none as long as
Hartley whose investigations cover a period of thirty years.
Early investigators merely dijacribed where they fotxnd
a band as gallein in water according to Vogel (2) showed a
band between D and F lines. Sometimes the observations were
recorded graphically by lines drawn across speotr\im at the
positions of the center of the bands. But this gave no idea
of the breadth of the band; since this was noticed to be very
SAA /VVXJC/I/V?^-C

essential^ somey^reported results by black bands of the required
width across the spectrum. Iiater on it was noticed that on
varying the thickness or concentration of the absorbing solu
tion the width of the band correspondingly changed. As a result
some authors recorded the result graphically.
Some workers tried to show graphically whether the edges
of the band were sharp and distinct or if they gradually faded.
All attempts were unsuccessful. The best results for recording
this fact have recently been obtained in a slightly different
way. Light is passed thru the solution contained in a wedgedshaped cell, so that the light passing thru a thick layer of
(1)Phil.Trans.,152, pp.36l (1362)
(2)Practische Spectranalyse,Berlin,1339

a
the solution into the top part of the spectroscope had passed
thru a thick layer of the liquid, while that passing into the
bottom traversed a thin layer#

In the photographs from Mees Atlas

the absorption bands are black# (Fig#l) By this means an idea of
the complete band of a solution can be determined in one exposure,
a method well adapted to commercial laboratories#
In IS79, Hartley devised a scheme for representing the essen
tial points for the absorption of a solution by getting the position
of the absorption bands for different thickness of a solution, then
plotting a ciirve with the frequencies as abscissa and the thickness
of the solution as ordinate# This method of reporting absorption
curves is used even to the present day by all English and Grerman
workers with a slight modification introduced by Hartley# Instead
of using thickness of solution, the logarthim of the thickness is
used as ordinate#
At best the edges of many absorption bands are very indefinite#
The absorption is greatest in the center of the band and becomes
less and less as we proceed toward the edge#

Another factor is

the sensitiveness of the eye, for all peoples* eyes are not of the
same sensitivity# In part, the photographic plate overcomes this
difficulty but not altogether#

The point at which the first sign

of absorption can be detected in a photograph will depend on the
intensity of the source of the light, on the length of the expos-ure
and on the extent to which development the plate is carried#
Recently these difficulties have been overcome by using a
spectrophotometer by means of which relative absorption and not
actual points of absorption are determined. This is achieved by
dividing the light into two beams, one of which passes thru the

/

w V

Tsi"
iW'i/Z'.^C!,''-

Kr

7 f

' 4 '

//f /

w

>^fkli'<:i.i.:!.-\'^-^it,--^-r^'S^:r.'.-

k!

'.'ir ma: *T
^ 'r ii' f

1/5000 (6/i«e cwa ow/y)
P io. 50
Acridine Orange.

Mees' Atlas, Fig. 10.)

1/2000 soluhon
FIG. 51
Phenosafranine.
N

4v ,> A ,,

/\Y\/\

Nlli 1 ^^'NH

*«

xV

' '' fi

ip "'Wv T "U.f

/\

W!'

CI C5H5
(Mees' Aflas, Fig. 70.)

fu^ , '

r w

w

1/10,000 solution
FIG. 52.
Methylene Blue
CI

'

N(CH,)/Y Y\|N(CH,)
(Mees' A tlaSj Fig. 120.)

• t-

n'i

5

,

*• >••

<;•

','i| J, !..ii,f*

IJ*

^ I. "f

i
if

... .^>,. .'.&,..)... 1.'? %. 1.

"1., .

X4C:

lO.
absorbing medium and tbe otber thru an apparatus by which its
intensity may be reduced by any desired fraction. By means of a
spectrophotometer a wavelength-absorption coefficient" cxirve can
be plotted. This system has been adhered to in this paper.
The first list of organic compound examined in the ultra
violet can be founded in 19OI Report of the British Association
for the Advancement of Science. Again in I916 this list was
brought up to date*
Before going further it might be well to briefly review
the several theories as to the nature of light.
According to Hewton, light consists of minute particles
thrown off at great velocities by light-giving bodies. This
corpuscular theory, however, no longer employed, as many
phenomena cannot be satisfactorily thereby. For instance, in
order to explain refraction, the speed of light in the optically
denser^ medium would have to be greater than in an optically less
dense substance which obviously is wrong.
Another theory, originated by luler, considers light to be
a wave motion, and early in the 19th century Yoimg employed it
to explain interference; while Fresnel, by assuming the transverse
nature of light waves, was able to explain the polarization of
light.
In 1373 Maxwell propounded the electro-magnetic theory, and
the conclusions forseen by him — that both electro—magnetic and
light phenomena are of the same nature — were experimentally con
firmed by Nichols and Hull in 1333. Subsequently, Hertz, Lebeden
Nichols and Hull proved experimentally that light exerts a
pressure which is equal to that calculated on the basis of
Maxwell*s theory.

lit

Assuming tlie theory of wave-motion as valid, there must he
a medium which is moving, and, as the movement is of extraordinary
rapidity, it follows that the medium must have an extremely high
elasticity, it must also have a very low density, so as to
penetrate all substances. To this hypothetical medium has been
given the name ^ether." It is essentially a carrier of energy
and hence, looked at from this standpoint, we may consider ether
to be matter.
Until the beginning of the 20th century the Maxwells-Hertzian
conception of light radiation had been foimd to be self-sufficient
but Planck showed that ordinary eleotro^dynamical methods of
heating with radiation did not lead to results in agreement with
experimental results on the relation between energy distribution
and wave-length as obtained from the measurements on spectra
exhibited by heated bodies. The revolutionary effect of Planok*s
work was supported by Nernst and Einstein, who foimd that an
absolutely continuous emission and absorption of radiant energy
was incompatible with the newer .discoveries. Thus originated the
atomic struot\ire of energy and theory of light c}ianta.
Einstein tells us that in the description which we make of
physical phenomena, there remains always an indefiniteness, a
q\iantity which we may dispose of as we please, and which relates
to the movement of matter in the ether. As a result a number
of physicists have come to the conclusion that it would be better
to drop the idea of the existence of the ether altogether firstly, because it is no material medium in the sense of the old
mechanics^ and secondly"^ because it contains that indefiniteness
which prevents us from stating definitely whether a body moves in
it or not. In reality, however, the imiversal character of tlB

12»
principle of relativity probably points more clearly than
anything else to the idea that the physical world does not
consist of separated independent atoms but there is in exist
ence a substance, which fills all space, of which noticeable
substances are only a special development. This world
substance is the ether#
On the basis of the electron theory, light may be explained
as follows: All atoms of so-called elements are complicated
structure of positively charged protons or nuclei aroimd which
are rotating in orbits, negatively charged electrons. The simple
atom is the hydrogen, which consists of one positive core charge
and one electron. Electrons have choice of many orbits. The
paths are labelled from inner to outer K, 1, M, etc., and any one
of these may be occupied. Nothing apparently connects these orbits#
If a substance is heated, the electrons may or may not jimp
from orbit to orbit, the radii of which are in a ratio: of the
squares of the natural numbers (1,%,9, etig.,) but it will not
taice up any intermediate position#
The greater the diameter of the orbit, the less the energy
connected with the electron and the more easily can it be
detached# The closer an electron lies to the nucleus the less
liable it is to be disturbed#

To get it out of this, energy

must be supplied# When a substance is being heated, energy is
supplied to the electrons but nothing happens until a definite
amount of energy has been supplied, when a sudden jump to a larger
orbit occurs. To cause a jump from an outer to an inner orbit
energy is emitted in the shape of radiant energy. As the
frequencies of rotation are, however, different for different

13.
orbits, since the rate of cutting out areas by the radii
vectors joining the nucleus with the electrons is constant for
all electrons, it means that different energies must be necess
ary to cause a jump from, say, the l6th orbit to the 15th, to
a jump from the 3rd to 2nd* But this energy is always a definite
multiple of the universal constant h (Planck^s constant) and is
equal to h f where f is the frequency of vibration* As this
frequency is the higher, the closer the orbit lies to the nucleus,
it followl that the spectrum which are emitted by a particle
disturbed from the innermost orbit represent a very rapid
vibration, high up in the ultra-violet or X-ray region of the
spectrum while the spectrum line to some outer orbit will be
far down in the spectrum below the red.
The reason energy is radiated when an electron drops from
an outer )'
to an inner orbit is due to the fact that the electron
gains a^-aurplus-~^i3f energy in the fall, tMa
being-double--the-balanci^is available and appears as light
radiation*

mimmp

111-,'

'.'^y

'r

'is.'"

S-i , ••i"; • 'fi^K
ja''

f

S Vi

,'

r«v ' '

ki --

H-

/?

T

itAi V-'-ii

V' ii.

)(' "

•> V ^I% Phi P

'1 V

•rvt'f.'^ -4

;vir
i

^ ^

I <

Att rij^

Ik,/.-'

I

'V.

IX Mathematical Relations*
rffs-^ •

-I'.UA

•If •'

,

i' f
''i >"•

'WM
k

•i'W
,.

111 »

^'tor^xsiisg

s\% > J
""<3!,-ir4,'

i&l

'

15^
In developing the mathematical relation, we must assume
that light is a vibratory motion of the hypothical ether of
space#

The vibrations are termed transverse because the to

and from motion or displacement of the particles or force
centers of the medium transmitting the disturbance is per
pendicular to the principal direction of the propagation of
the head of force or velocity-potential of the change.
Assuming that we are dealing with propagation of spherical
waves in a homogenous medixim, the oscillations being trans
verse to the direction of propagation the intensity ^
at a distance d from the origin or oC a where a is the
amplitude of the vibration.
When the absorption-coefficient K is defined as the
reciprocal of that thickness of the medium which reduces
the amplitude of a vibration to
that is, to a^e'

of its original value,

if a is the original amplitude.

Since the intensity is defined as a quantity equal to
the mean square of the amplitude, the intensity on reduction
becomes

> when d is the thickness transversed by the

vibration and k is the specific absorption coefficient for
that medium of vibration.
If we wish to measure in terms of critical units then
extinction coefficient must be in terms of critical lunits
viz., its wave-length when measured in vacuo. The amplitude
- Rv-x
is reduced to O-o^ ^ on traversing a thickness equivalent
to the wavelength A

, the wave-length in vacuo. Hence the

16<
intensity is reduced to

-j/xTX

^

for a thickness

equivalent to A or for any thickness d to

,

C

_ ¥-7/ X cL

7^

where Y\ is the reduced specific absorption constant or
extinction index*
If we put ^

, since both give eqiial

decrease in intensity we have

A ^ xT

The above relation holds only for normal or perpendicular
incidence. It is evident that the foregoing relations must
be obtained for monochromatic light. In this definition of
absorption absolute values aQ and i^ were used but absorption
also depends upon condition of incidence at the boundary of
heterogenous medium as well as upon actual damping within
one medium assiamed to be homogeneous.
When a beam of light, considered initially as unpolar-*
ized is reflected at a polished surface, it becomes polarized
(l) into two sets of tribrations polarized at right angles to
each other and for each of which the loss of intensity can
be calculated.
If I is the intensity of the unpolarized beam before
traversing a transparent medium, then ip and iq are the
intensities of the beam polarized in and right angles to
the incident plane then: I « ip - iq - 1
and
ip s
i« - *q
-i
z

(1) T.Preston. Theory of Light, pp.2^8.(2nd ed. 1^95-)

17^

Let /P be tbe angle of incidence,

tbe angle of re

fraction so that
sin ^

s /• sin ^

Where 7 is the refractive index of the second mediira compared
with the firsts If I, is the total intensity of the beam
after refraction at the surface while ip and ^ intensities
parallel and perpendicular to the siirface, then according to

•,

. •'

|*resnel*s law of reflection (l):-

^/p = s

1 - tan
tani?7^

r: .,"r

•

ill
1 = i
/q - q

at so
1.1 - i

tan

1-

e-4

tan {^-4- ^

tan

-h

sin
sin

4-4
/

When plane-parallel surfaces of absorption vessels are
used and the incident ray is perpendicular then angles ^
and ^ are equal to zero» Hence sines and tangents can be
replaced by their respective angles. The expression for the
intensity of transmission thru a surface becomes.
I - 1 - /V - 1
V +1

(l) Ann. de chim.et phys. (2) 17,pp.190,1^21#

When more than one surface is envolved, as is always the
o&se, the reduction of intensity by reflection becomes more
complex* Let

be the intensity of a beam penetrating the

first surface* At the second surface the quantity
I,
is reflected while I2 , is transmitted. The reflected beam
on return to the first surface is again reflected with intensity
2
(i-i,)
and reaches the second surface with intensity
(l—* The beam which has undergone fourfold reflection
has an intensity of (l-I^)^

, and so on we have the total

intensity of the beam immerging from the absorbing medium (l)j-

I, (i-i,

h = I, - I, (i-i,
- I ^ '"'""i ^ 1'
/ 1-(1-IJ^

^ J , (i-i, P
X
2-1,

^

If the qaantity (1-1,) is very small, then Ig is very near
I,

2

'

'

; otherwise the factor

1

o

The absorbing power A s 1^ - I
I.

cannot be neglected.
where

is the light

actxxally entering, I that transmitted. Lambert*s law may
be stated
f

«

lo

T being the constant called transparency, frequently
multiplied by 100 to give percentage.

^ (1) G.Kruss. Kolofimetfic und quantitative Spektralanalyse
pp*230.

19.
Whea a ray of light traverses an absorbing mediiim a
portion is absorbed which is independent of the original
intensity, i,e«, the aaiount absorbed is proportional to the
incident intensity (l)(Lambertlaw). It follows from
Lambert*8 law that if the thickness of the absorbing medium
increases in arithmetical progression, the light transmitted
should decrease in geometrical progression. Let I be the
intensity of light traversing a layer dl then: -

li! = kl
dl

Intergrating, if

is the original intensity and d total

thickness

-kd

I^

The constant K depends upon the nature of the substance and
the wavelength of light. It is called absorption coefficient (2).
Then
k g T

log ^

d

^ I

Bunsen and Roscoe (3) define extinction coefficient as
the reciprocal of that thickness of the medium reducing the
intensity to l/lO of its original value. Calling this ^
we have:/o

[l)j.H. Lambert. Photometria pp.1759
2J E.Hagan and H.Rubens. Drude's Ann. B, ^32 (19^2)
[3)0stwald*s Klassiker,
6.

•7

and E s

d

log

1<
T

Collecting the various qiiantitative relations we have:-

Transparency (1)

^

Symhol
Relation
T
T -T
~ I.
cL

Transmission Coefficient

a

I» I

Extinction Coefficient

E

I s I 10
E » 1 log ,

-ed

~

Molar Extinction Coefficient

M

^

T

M «t concentration
E
M

d

log

I

.T

Where
lo ss Intensity entering a medixim
I = Intensity transmitted
6 •• Concentration in gram — mols
d s Thickness in cms.
"^cL

(l),In the electromagnetic theory of light, for Isle
put K

2' ^ X
^

given mediiim.

where A is the wavelength of light in the
If the thickness d ^Awe have I » I^e

^

A

where x is Oauchy's extinction index or Drude^s ^hsorption
index.

/

{!). cf. Drude, Lehrhuth, d. Optik. pp.33,1900.

.5 r" S «

-K

2X.

'&'ii
fH'i'M
• '* ?- --s-"'.

b'?-:ia

v^tiUr;

t*< ^K

W>J3

--r

W rt

r'stf'-,

^

}•,' ' h"

s, i 'fi

Ill Theories of Absorption in the Ultra-Violet
(a) Dynamic Isomerism
fb) Isorropesis
(c) Electronic Theory

%;/ •

•' ^ t if'

fimrVr#

;;

-

"i't'

" -"sv

v if'

w

\

>.

22.
Light going thru a medium is poorer than that incident
on it*

This decrease is noticeable on dispersing the light

into its spectrina. There are two types of absorption; general
and selective absorption. The former is a weitlcening effect
occuring thruout the whole region of the spectrum of the trans
mitted light. Selective absorption is the absorbing of a
definite section of the spectrum which is characteristic of any
one compound.
Selective absorption has thus fax been considered a con
stitution property rather than an additive property, except in
homologous series and here no quantitative relation has been
found to exist. The general effect of substitution especially
of groups possessing residual effinity is to develop color by
shifting the absorption to the visible part of the spectrum.
Groups in order of displacemtot of the band, least first:
OH3 On OOOH OH OKa m2 NOg
Reverse process is caused by salt formation of amino compounds
and carboxylic acids. According to the experiments of Dobie
and Lauder (l) it may be stated as a general rule that a given
substitution has a less effect on the absorption curves of
complex bodies than on those of simpler compounds. From the
occurrence of bands it has been found possible to infer the
presence of dynamic condition set up by enol-keto tantomerism(2)
by the dicaarbonyl group(3) or by the benzene system(^).
^ ^1) Bobbie and Luder. Trans.Ohem.Soc.,33,612 (1903)
^2) Baly and Desch. Trans.Ohem.Soc. ,35,1092 (1904-)
Stewart and Baly. Trans.Ohem.Soc.,39,502 (190b)
Baly, Edwards and Stewart. Trans.Ohem.Soc,,39,5^^(^906)

sfm

-•iSi

23.

Hartley says all compounds that exert selective absorption
are aromatic in character as benzene, pyridine, pyrazine and
derivati1»es. Those exerting strong selective absorption
possess cylic formation but are not true aromatics:- furftxrane,
thiophene, pyrrol, piperidine dihydrobenzene, cineol and many
other terpenes. On the other hand compotinds possessing weak
general absorption have an open chain;- fatty alcohols, acids,
esters, amines, oelefins and polyhydric alcohols^ The last
statement is not altogether true as some compounds containing
OHg - 00 — show selective absorption.(1),

;>•; •J.-,

•

'P: \

•'

'

'

SU t

^xX'imh ;a^n; tih^f ^ :p}^ipx%Ku;,1
fi-I'K'M? e'iftij.•.{.,»<%,

-V Cv • ^'

4||

^ 'i ;i HA

V>i' I '"I it

" 'A

(' '*[ !

•, •; • .

Is
er

htx4 w <j •

' .'y.' .)•

I*: .w,'

I'

\'%k

V •..'•.XT . •

>

/

i'

'

'

hHHi#Uc

(1) Baly and Desch. Trans.Ohem.Soc.,B5, 1009 (I90k)

•i-i'

•A'
v\

_

iiiii

Dynamic Isomerism
Baly and Desch from their studied of enol and keto
forms decided that absorption was due to dynamic Isomerism.
They studied ethyl acetoacetate, acdtyl acetone, benzoylacetone and several other similar compounds. In all there is
chemical evidence that they can exist in two forms, keto and
~ c — c—

:

^ —c —o—

,

H

To determine if the absorption was due to enol or keto
form oxygen ethyl derivatives of enol and keto forms were
examined. Since neither enol or keto form gave selective
absorption the only alternate would be the change of one form
to the other was the cause. This idea is supported by the
fact that increasing the alkalinity of acetoacetic ester
solution the persistance increased. This means that the
alkalinity was a means of controlling the speed of the tautomer
ic rearrangement. When different metals were used to replace
the hydrogen the

of the band does not vary appreciably.

Hencp the band must be caused by valency electrons. Consequent
ly the ultra-violet absorption bands would be due to the elec
tronic disturbances which results from tantomeric change. In
those substances which have the possibility of tantomerism and
yet show no absorption band they argued that it was beyond the
range of the quartz spectroscope.

V,

WiJ
m¥r'.
M

it

25.

it

tgfj- '•'•': •

The argiaments against this theory are:(1) Substances incapable of tmdergoing tantomeric changes
show absorption bands.
(2) Substances which are known to be mixtures of tantomers
do not exhibit absorption bands.

llfliil

li
.

.rvwt%
I

ic

'

J.

'

><

iV»

iv

S^t"

IA li V

, c>.f

^

'• .

\

^

>'

1^'

^i

't

i'Y ^

26.
Isorropesis*
irhen such substances as acetone ethyl pyruvate, diacetyl,
benzene and benzoquinone showed selective absorption and yet
the idea of tautomerism wa,s impossible, the idea or "iso
rropesis" ( i <r
and Baly»

equipoise) was proposed by Stewart

The difference between this theory and the pre

ceding one is the former has no labile hydrogen atom.
^^3

//

o

— e

(f

0

•

/

/

o —o

'wi
h,-

Isorropesis according to Stewart and Baly is the vibra
tion between two forms in wMch the valencies are arranged
differently. They observed that chemical reactivity and
absorption were directly related. Those ketones which showed
the greatest absorption react most readily with sodium bisulphite.
Baly and Stewart (l) attempted to explain the seven bands
by means of isorropesis:(l) Baly and Stewart. Trans.Chem.Soc.,67, 1335 (1995)

27"In applying this to "benzene we may therefore, differen
tiate "between the transition phases in which any pair of the
caJTbon atoms, or any four, or all of the six are concerned.
The various transition phases may, therefore, be represented
as follows

(7)
f

-'V

The staxs being attached to those carbon atoms which

A)

are concerned in the process.
"The seven forms represent all the possible conditions of
making and breaking the linkings which can occur and at the
same time they are so different in character as to justify
the view that each of them is the origin of a separate
absorption band."
The same scheme is developed further by Baly, Edwards
and Stewart (1).
"How in order to bring the seven phases into existence
it is necessary to assxame the displacement of the carbon
atoms of the ring, and we can do this in the simplest way
possible, that is to say, by the ordinary vibration as is
accepted by any alastic ring. Thus we may say that the
benzene ring is pulsating between the two displaced forms
a and b.

(l) Baly Kdwards and Stewart. Trans.Ohem.Soc.,S9, 52^,1906.

•

2g.
)»• 'V' lt!ii t'/n

C3

(a)

t

Cr

C 3

(to)

a' fe

*Each carbon has residual affinity, and consequently in
the condition represented in (a) when the atoms 2 and 6 and the
atoms 3 an<i 5 are brought close together, these residual
affinities will produce linkings as shown by the dotted lines.
"The atoms 1 and

however, are far removed from one

another and from the atoms and are, therefore, unsaturated.
On the other hand, when the ring has passed into the other
phase (b) then the three atoms 2,1 and 6 come very close to
the three atoms 3>^ and 5 respectively, and linking may be
considered to be formed between these pairs of atoms. The
linkings existing in phases (a) and (b) are shown for greater
convenience on the ordinary hexagons in & and b. As the
ring is pulsating between the forms (a) and (b) many of
the seven phases of linking change described above will be
obtained. For example, let us consider the ring to have
reached the form (b): as it starts opening, the first break
will occur between the atoms 1 and
breaking of the other linkings 2:3 and

followed by the
When the ring

passed through the half way stage, that is, the circular
>V;

•

29<
form, then we shall ha^ve the centric formula, with the result
that phase 7 is produced. We csui in this way aco&tmt for

,•)

phases 1,2,3,^,5*^ sin^i Ji numbers ^ and 5 can raadily be
understood if the motions described above are slightly interferred with by collisions between adjacent molecules.®
The main objection to this theory is its imcompleteness
and indefiniteness.

rWM V
*^1

W'lf % k ^

r

•'SI'"

$k

J,V f
:! .H

f

\\nf

.t'

'' k'^4

-J

TP41 ^

-p.

''

m

4?

;M% '

iitpmiS.
'

' .

'i •

•il®
• 'f'd !

t
'V

1,1||| V I

'it'

'',p !l '

fft,.. 'i,u,
i

'i' '

•
' ' ' ' ''

,

' v'

V'** «
\ ^

'

,

<• !.^
•"V' ^

j

,

!?,{'. M to
' - .' •

1

\

•'

, \

MiilB
''- w.''
if I

i, N <• '

;A> t'

' ".•'•Vi'
,

'.

I>

h'

,0kt

€'\ '

'"i."'}.!

'A'!;'/..;'•

•AfeiA

^

•V'' ' ^.'^'-V

'I

'"l

\

• M, i ,
.!, •'l ^
I

i>. ,•<' \

,'/•;, .; .tAS

, '' X '# i

„ v"'> i> -lA'.Hf'i

f •••Jk- P%«SE,. P' ,

.

11. ..-•tVA

1'';A,'" ''51,r"'

' IT'

' . >-,

> Al;

30<
Electronic Theory
Watson in discussing color and chemical constitution
says:- "The quest of the ultimate cause of color has revealed
the great complexity of the problem and has shown the need
for further work in this direction^** Harry Shipley Fry in
his monograph "Electronic Conception of Valence" develops
a relationship, in the form of a linear function between
systems of dynamic equilibria of the electromers of benzene
and the oscillation frequencies of the seven bands which a
solution of benzene in alcohol exhibit.

f'

jf

Before going into the systems of equilibrium which
cause the absorption of ultra-violet light, we must briefly
outline Fry*s conception of the benzene molecule. Stewart
points out, "It is becoming generally recognized teat the
benzene molecule is in a state of continual vibration and
that the only satisfactory space formula will be one which
represents all the other formula as phases of its own
motions, and which may even suggest the possibility of new
phases as yet unrecognized." Hot only does the electronic
formula explain the ultra-violet absorption of benzene, which
other formula at the very best explain only partially, but
it also gives a satisfactory explanation of substitution in
the benzene nucleus. So we see this benzene formula going
a step further and pointing out the causes for each of the
seven bands.

i*

\ 4 ^

.V I'' V''- ''•

^

1

-

I,

' i • ' 'Vl/,,-V'4*•'
'

31.

The electronic conception of positive and negative
valence, in the case of the "benzene molecule involves five
types of carbon atoms thus:
-t4-

0

-I-

-h

—

0

-f

^

II

—
.

0

-f~

- 4-

III

^ +

0

—

0

_

IV

V
r '

'Vjf

Since each benzene nucleus (Centric formulae) consists of
three pairs of the combined types I and V: II and IV: III and
III arranged symetrical, these six and only six eleotromers
(centric formulae) are possible. Before developing the com
plete outline of the dynamic equilibrixim of all the electromers
of benzene, let us look carefully at all the electromers in
equilibrium with the centric formula which is composed of
carbon atoms of type III (Fig 2 )•
It should be noted that the above formulae are projections
of space formulae. The above rearrangements are very similar
to those proposed by Collie (1) except that electrons are
taken into consideration. Since with the five types of carbon
atoms there can exist six centric electronic formula, there
must necessarily be, in complete equilibriiam, six such re
arrangements which are intereonvertable one with the other.

v (1) Collie. Trans.Ohem.Soc.,71 pp.1013 (1S97)

'4'

r ^

ills

32.

r 'v;

BEnZEHE ELECTROriERS OF TYPE H

^+H

,H

H,

="H

rf

FIRST KEMJLE
. PHASE

CEhTPlC

PHASE

f1^

5FC0HD KLKULE
PHASE

LAST PHASE

Hi ^ Na

ill*
mSm

Fig. 2,

J«

•-J,
M'HI#-! . A
• M.i

1

i;; fl.

.

fJ'lA ^

J '.-A •>• "L .

'

m
•,

_

' I
tig,

Fig. 3.

• fc.' .>''i|3'l|l
^

.... .

\«

.. v .

«

'•/•.. .s"i, '••!..

3^*
In the two Kekule phases there are two distinct types of
double bonds. The first phase each of the bonds in the double
bond the valency is exerted in the same direction, because the
adjacent ends have the same polarity; while in the second
phase, the valency is exerted in the opposite direction, because
the adjacent ends have opposite polarity. The two distinct
types are called "diplex" and "contraplex" respectively. As
we shall see later the change from diplex to contraplex bonds
is the cause of ultra-violet absorption.
In the complete scheme (Fig, 3) the first and last phases
have been omitted for brevity. Kekule supposed that the
carbon atoms in the benzene nucleus oscillated in such a way
that A' represented the molecule at one period of oscillation
QMA A** the molecule at another period. This islaeither
isomerism nor tautomerism, however Brtthle (1) called it
phasotropisim in the sense that Hhe unaltered benzene nucleus
and analogous ring system are phasotropic**

The centric phase

may be said to be in a state of strain or dielectric polariza
tion because of the balance between three positive and three
negative charges within the ring. The rearrangement of these
charges so that the positions previously held by negative
charges is occupied by positive charges and visa versa, produces
not only a similar condition but another centric electromer.
There are threeof these rearrangements in the complete scheme:-

(1) Brtthle. J. pr.ohem.,(2) 50, 218,

•V'-'s,

M

\I

55.
. B
r U
J

T W
, 'U"l

The electromer B can be transformed into 0 only by going
thru the intermediate step of B' or B'* first. The same is
true of D and E.
Thus it will be seen that there are two types of dynamic
equilibrium, primary and secondary systems of phasotropio
equilibrium. A primary system involves three phases: one
centric electromer and any two of its directly related phaso
tropio electromers.
'

A

//

ryik
V

/r *
A

' JB^=?B±==;:B
4-,

0

^ 0':=====^0

There are twenty possible primary transitions in the complete
scheme. The secondary systems involves four phases two centric
electromers which are interconverta.ble by centric rearrange
ment and one phasotropic electromer of each of the interoonvertable centric electromers.
A.

?• A

rB

rB

,f

\ t •'
' V'."

There are twenty-eight transitions of the secondary type. .
table of adl the possible jbrimary and secondary systems of
phasotropic equilibrium follows.

36.
Primary systems of
Phase tropic equi lifer iiim.

Secondary systems of
Phasotropic equiliferium.
f

1.

A-

2.

A

B-

B-

B

i}-.

B-

B-

B-

Ii y 1

•B

0

0

7-

B-

0

•0

B.

B-

0

^0 ^

9.

B-

0

10 •

c-

0 "//•-J

C

0'

D

l^i-.

15. B
16. E

//

•D
B-

B*
A--A-A--B-—B >

'

w

tf

/

7. B--0--D-—B /^ M
4-

// <

«.

//

ill

B--0--B —B^

f^U

//J

/

9. B--G--D-—B ff

•,f

10. B—
-0--D-— D
/
11. B—-G--D--E'
/

[/

D»'
/-

1.',

12. B //—-

c—-D-—E /
B —-c—-D-—E

E;c
•E

-c—-B-— B ^
15. 0 —
/

ft

i i

* ,4'A

/

ff

l6. 0—-0 —-B-— B 7 ir
//
/
-0 —-B-—D
17. 0—
//

1
E

ff

12. 0—-0 —-D-— B ^
/

!?• E—-E—— E
19^ E— 1
/

/

f/

20. 0—•0—--B-—E
//

—D

if

22. G —-0 —-B-

—F

-r

-r

i

-E — F--ri
23. D—
tf
//
VT
21)-. D—-E — F-—jr
/

25. E —-E— F-— P/ff
/

- >.

•

•'•V"

26. E —•E-4- F-_yA

27. E— E— F/f

^ {,

f,

21. 0—-0 —-B-—E/

//

!•

I. 'i

.

o
CVJ

F— F

fJ

19. 0—-0 —-B-—E

IB. E —~E——D

!

ff

13.
//
//
li^. B—-0 —-B-— E

D —Ex

13.

X

f

/>£-

12.

f

5. A--A--B-—0^>
X
6. A--A--B- 0 7

0

D

ff

3. A--A--B

.'4

t L-''

5- B
6. B-

11.

A--A --B —B^
/
A--A-~B —B^
ff

y

B-

1.
2.

//

ff

C\J

E — E — F-_pA

vt

w?'

37.

Those systems which are asterisked are the ones in which
contraplex-diplex transitions occur. These **contraplex-dipleB
transitions in any types of dynamic equilibriiM constitutes the
structiiral and electronic e^splanation of absorption bands that
is, of color (l)*. If there are seven bands in benzene then
there must be seven contraplex-diplex transitions if they are
the seat of an absorption band. The electromers which contain
a oontraplex double bond are B, B, 0, B, 1 and E; while those
with a diplex double bond are A, A, 0, B, F and F. Consequently
only the forementioned electromers can be responsible for the
absorption bands. In the complete system of oynamic equilibrium
of the electromers there are six centric electromers, therefore,
there are six classes of primary transitions each involving one
centric electromer# However, only six of the possible twenty
primary transitions contain contraplex-diplex rearrangements
namely those number B to 13• These can be subdivided into the
following four groups! 2 transitions numbered B and 9

Group
"

1 transition

*

10

tt

1

«

«

11

2

«

•

12 and 13.

*

^

The twenty-eight secondary transitions are divided into
three groups 1-6; 7-22 and 23-2S, because the complete scheme
involves three centric rearrangements:-

(1) Fry. Electronic Conception of Valence, pp.193*

..

'.trA'fej..

3S.
A'

=rB

0-

=?D

EEighteen of these transitions are contraplex-diplex and
are divided into seven groups as follows
Group I
Xii.''

- Sin
'^

2

n

H

III

2

n

H

7 and 5

if

2

»

It

15 and 15

7

2

* H

n

21 and 22

II

"t
'

X

VI
VII

f:

jsr

-

5 and 6

if -2

If

'

' 1?

II

23

k

If

'' Xi"

If

25 - 25

CVJ

•.•t
" .. .'''

^ Transitions numbered 1-^1-

"The existence of seven distinct groups of secondary

contraplex-diplex systems of equilibria constitutes the basis
of the correlation of the seven absorption bands of benzene (l)»
The following seven b:ands are reported by Baly and Collie(2)
for the absorption of benzene in alcohol solution.

Band
' ki'.

Oscillation

Frequency

one

3725

two
foxir

3765
3&30
3915

five

iwas

six

4110

seven

4200

three

(1) Fry. Electronic Conception of Valence, p.95(2) Baly and Collie. Trans.Chem.Soc.

m

'.M

„-„jp

5'

39.

Two assumptions are necessary to complete the hypothesis
namely, that the smallest number of secondary transitions in
a single group are responsible for the band of lowest frequency
and that all the transitions both primary and secondary produce
the band of highest frequency. In other words, the vibrations of
the two secondary contraplex-diplez vibrations are synchronous
with light waves of frequency 3725; while the vibration of 2^
contraplex-diplex transitions are synchronous with l|'ght waves
of frequency ^200. However, the foregoing assumption can be
justified if a linear function exists between the oscillation
frequency and the integral nximber of contraplex-diplex transi
tions. If assuming the above two points (3725, 2) and (4-200, 24-)
the equation for a line passing thru these is:y - 21.59IX 3621.gig
y =s oscillation frequency
y — no.contraplex-diplex transitions#
' iMejjKs

§&'.»•

'WP
-1'

„

r .<U' •
r

'k;

•

't;

'i'f

ko
A further step is taken "by relation each of the seven
hands to its proper so^lrce. The circles in the graph represent
the number of transitions which are producing the corresponding
hand of that oscillation frequency. The following table shows
the assignments made by Fry:Ho•Transitions

Origin

Band

2

IV.

one
two

k-

(III.or 7.)

7

three

IV.+IIIj*

or/)

four

IV.<- Ill.t V. + (fl or 0 +(II.or

five

IV.^ III.. V.

six

IV.H-III..V. Y<^IVVI..a.4d.+(I^or VII^)

20

seven

IV.. III..

2^1-

All.^
+ /.

or d)

d.
vy a.+ d^f I^-^VII^.

11
l6

The subscripts indicate the nimber of transitions occuring in
that particular group.
Fry goes on to show by a similar means why chlorobenzene
and bromobenzene have seven bands similar to benzene, while
iodobenzene shows no selective absorption. Also the three
bands of napthelene are assigned to their respective contraplexdiplex transitions#

M V
...
V.

, t ^

'V J'

' <

n-

'.•• : •'. •; • •', • •
','0 f ,•

' '*^-1

>»

•7-. .-;• •

^ i

i ,«

')!

•" ^ /:

^Si

It

* r.iii^'.
1

rv <

w.

ItAf '

.

.; 'iti fefei

^

j'V

^f. V , >

1. 'TS i'l'H
/ ')!

»^

^

• H'.SVA

•r

•t'f

.t.f

'

'«

W

A

i.1

Ijfclkt.,

il

»|tf}|'

;.i, •;••;,

-'yksus-,

si

'. ' .1* V'- i«

k' .'^y

.#X fs.* ' «7tl=l3

V f

4

Mm
'V.-'

yV'v
'"i' %f;' ik '-i A ^•..Jf n.

yi\y i|k^ y ^ ".

"ir'}

iJy

1, V

•4-

V

»^VA 1('^•

«? 1,1

,

f

/ n, \ <. ...
. yy,\,

^

.

t

t .V '\>'
;; i

^

\) S

X -. >•'

t \

yi .
•f/k t\,
ft. f

<
'

kAfe' "'1.

JstU AV>{wJ.

' -ftk-

1

sr.-

V

*,

^ ^

:'•

'.Vi

•', '^,1

«.«;?

;

'it

>1, ,v

M

,

XV Apparatus

f

»vi'

J

liV}

•' '-"A, '

ft

itv*'

,.'5^ •witfi •!:

: A' ^ f?> •' \i f4''^ V 'I'

••''f

MI# n..
by

J?:*' • . ^'4 ••

•''A->''

'V ' .

i.di'M

, ' ,•;' '•

Q t i -M,

^

^2.
Apparatus
The apparatus consists of an iinder-water spark sector
photometer (Fig.^) and a quartz spectroscope (Fig.5). The
purpose of the first is to emit ultra-violet light, the
second to cut out a definite percentage of the light which it
divides into two beams and the third resolve the two beams into
their respective spectra.
The under-water spark is made of a glass jar ^x^l-xlO in
which a hole has been drilled in the bottom to admit one elec
trode and another hole in the side over which a piece of quartz
is sealed. A hard fiber washer is sealed in the bottom with
De Kotinsky^s cement which is tapped out and the electrode
holder screwed in. The top of the jar is made of fiber with
a hole also tapped out to hold the top electrode holder. In
one corner the inlet of distilled water is made while in

; h .'il

another the siphon for removing the water. Water is circulated
by gravity and siphoning at the rate of about 1^ liters per
hotir. The electrodes are made of tungsen. Aluminum, brass and
molybdenum have also been used by some workers but altminum
and brass wear away much faster than tungsen and molybdenum.
The electrical hook—up (1) for exciting the under—water
Bpaek is shown in Figure 6. Either 220 volts 25
220 volts 6o

or

, preferably the former, is used as a service

line. The resistance cuts the voltage across the step up
transformer down to 30 volts. From the secondary of the

(1) Howe. Phys.Rev., (2) S,pp«67^, I916.

,• • - •

-

"fll-

i,y

Fig. H 16

Sector Photometer
Fig. il-.

"3:)

fl- ^ .

IBHIIM

Quartz Spectrograph
Fig. 5.

Wmmi
• J--;

mm

A/v/VW
istc. ".gsiii

VOLTS
60 ~

. 002 -mfa

STEP-UP
TRANSFORMRK

AIR
SPARH GAP

TELSA
COIL

UNDER WATER
SPARK

ELECTRICAL COiiriECTIOnS
Fig. 6.

-

r. A/"

•iv

*•••> .A
;

1W

4N,

-f,.*
tF,. A
^ - V''

V

:V\

'

)'\ "^
f'

» '£
<(• \
•\ I"
E K'-l'''
K^
•-C, t : , T; ^

^

AvA.
'

*'^*'»^ 'A I"
rAts'-

^ V, ,

IC'C, ,'r . 1,'.A i* T'ikv

trajisformer an oscillating current is set up in the primary
of the Tesla hy means of the open air gap and the two con
densers of capacity #002 mfd each.

The open air gap consists

of two hollow zinc tubes which are adjustable and between which
a jet of air is blown continually. This gap is adjustable so
as to vary the intensity of the under-water spark more easily.
The voltage across the secondary of the step-up transformer is
35>000 volts. The secondary of the Telsa coil is connected
directly to the electrodes of the under-water spark. The
voltage across the under-water spark is 65,000 volts, the
current teo milliamperes, while the cycles are up in the
hundred thousand per second. When the system is in operation
the current thru the primary of the step up transformer is
5-6 amperes.
A condensed spark between carbon electrodes impregnated
with uranium nitrate and ammonium molybdate are often used
as a source of ultra-violet because its spectriam is very righ
in lines. This particular type of electrodes are referred to
as "Jones electrodes." A condensed spark has also been used
as a source of ultra-violet light.
However, the underwater spark has the advantage that it
emits a continuous spectrxim of even intensity thruout without
any bright lines. This insures greater acciiracy in the
plotting of curves.
The sector photometer is an Adam Hilger instrument (l)
Fig. 7, consisting essentially of two qxiartz wedge lenses,
(1) Adam Hilger, Ltd.,catalogue. Sector photometers|<Jan.l9l6.

VARIABLE

APERTURE

PkquARTZ LEHS AHD
WEDGE COMBinED

FIXED APERTURE

MOTOR FOR SECTORS

RLAK VltW

SCALE
eons

HLCLR SLCTQR PHOTOMFTFR

Fig. 7.

i

'Pvfvt

ikl % ^ ? 'X^

m viLW

on one side of which are the two rotating sectors and on the
other side the absorption cells. The upper apertxire is variable
with an opening ranging from 0^ to ISO®* The lower aperture is
fixed. Both sectors rotated at the speed of about 100 r.p.m.
The graduations on the variable sector are loguthmatic as shown
in Fig. S. Since both beams of light come from the same point in
the under water spark and variations in the spark effect both
beams equally so the error is negligible. The sector photometer
must set 2^ cm. from the under water spark and ^6 cm. from the
slit of the spectroscope in order to have the spectrum in focus
at the plate.
Radiant energy from the iinderwater spark may reach the slit
of the spectroscope by two alternative paths. An upper beam
passes thru a qmrtz lens and wedge, is refracted downward thru
a rotating sector of variable aperatxire, and is deviated by the
lower half of the quartz biprism to pass axially along the colli
mator of the spectrograph. A lower beam traverses a similar
path thru the lower wedge lens and rotating sector of fixid
aperture and is deviated by the upper half of the quartz biprism
to pass axially along the collimator like the first.
We thus have the spectrograph(Fig. 9)

two beams fxm

the same source. These are dispersed by the quartz prisms and a
spectrum image of the slit formed on the photographic plate.
This spectrum is divided into two halves by a fine line extending
along its entire length, which is the spectrum image of the re
fracting edge of the biprism. One half of this spectrum results
from the upper beam, the other half from the lower beam.

I

50,

t, J"

111

J

QUARTZ PRISM

QUARTZ BIPRISn

u

LRUS ADJUSTtlRITT
QUARTZ LRMS

ULTRA-VIOLLT
PLATR HOLDRR

HILGER SPECTROGRAPH

1

I- ;

•

,v

51.

If both sectors are open (ISO^) and if the spark is in
correct alignment, the densities of the two halves will be
equal thruout their entire length, thus indicating equal in
tensity of the two beans. It has been found that the densities
of the two spectra at any wavelength are eqtial if, within wide
limits, independentcf the exposure, of the intensity of illumina
tion and of the speed of rotation of the sectors. Furthermore,
the photographs are taken simultaneously and there are, there
fore, no errors arising from fluctuations in the light source.
Let the fractions of whole revolutions during which the
fixed (lower beam) and variable (upper beam) aperture sectors
allow light to pass be respectively % and t^, and let the
intensity of light of wavelength A. reaching the slit by the
'jjpp0]c gtnd lower beams be respectively IQ and X.
Then if at wavelength A the density is exactly the same
in both spectra, we have.

32 - f
I

According to Schwarzchild (l) the relation for Uninterrup
ted exposures is of the form

^
\«

J.*'* ""
/v.-v ^

^

(1) Schwarzchild, Astrophys. J.,11, pp.S9 (1900)

kttix.

'<V

' '

\f .

rif f

M9Lk<4iJUs'>

.

52.

where B is a constant depending on the kind of photographic
plate employed. Other workers, as we shall discuss later
have found that within the limits of experimental error the
index n may be taken as \mity. Thus we may write
'/

St

JX

"•i/ ir 1)!# ,

:Li;:

''{>• 1."

Then the equation for molar extinction coefficient
(pp.20) becomes,
d

log y<o

X 1

The variable sector is divided to read log10

(see Fig.S).

Undoubtedly , however, for the sector photometer the
value of n appears to be unity, within the experimental errors
of photometric measurements, as was first clearly stated by
Howe (1): «The photographic plate, the use of which in photo
metric measurements is usually considered questionable, inte
grates intermittent exposures in such a way that the compari
son of two intensities can be made directly in terms of sector
openings provided that the time from the beginning to the end
of the exposures is the same and that the two exposiires produce
equal blackenings on the plate. "Why this is true may be
seen from a consideration of the conclusions reached by
various observers. If a plate is exposed to a constant radiant

(l)Howe. Phys.Rev.(2).g, p.67it- (I916)

ilr

1]

53
power for time t (continuous) §nd then exposed for the same
effective time t, made intermittent by means of a rotating
sector, the blackening produced in the second case is less than
that produced in the first. This is some|imes called the Abney
relation(1). Weber (2) and Schwarzchild (3) find the difference
in blackening to increase as the ratioiiof "exposure interval"
to "darkness interval" gets less.
Assuming the Schwarzchild relation for continuous exposures
as valid, then, if one considers two radiant powers of intensity
I and I, , where I is greater than

(say I, =s l/a), the blfcackening

produced by X in a time t/a (continuous) is greater than that
produced by I during the same effective time of intermittent
exposure. Also the blackening produced by

during the time t

is less than that of I during t/a (both continuous.) It is
therefore, possible for the blackenings resulting from X during
t/a intermittent and X,during t, continuous, to be the same.
Weber (^) states this possibility in the beginning of his paper
and proves it experimentally for various wavelength and brands
of plates, various times of exposures and for a wide range of
sector speeds. Howe (5) and Hewcomer (6) also arrived at the
same conclusions. This case would apply to the sector photo
meter with only one rotating sector.
fl) Abney. J.of Phot.Soc.,1^93, k.
«
a) Weber. Ann. der Phys.,45,pp.^01,
1%) Schwarzschild. Astrophys*
(5) Weber. Ann. der

[5) Howe. Phys.Reb. (2) S,
[6) Newcomer. Science, March 7> 1^91°/•

hv
-V"

5^.
In the case of the sector photometer as usiially used and
described in previous pages there are two intermittent exposures,
in one of which, however, the ratio of

exposure interval" to

"darkness interval" is kept unity (fixed aperture), while in the
other this ratio is made smaller and smaller as larger sector
are used. Here it is also thue that

"TF s

S,

T

~r~

of angular openings

and 4

Where I and I, are the intensities passing thru two sectors
, respectively, and produce

equal blackenings. fhis case wasrproved explicitly by Howe
for a smoked glass screen and is also substantiated by the
various observations to be mentioned later. That this is
true is probably due to the mutual working of the Schwarzschild relation and the fact already mentioned, that the
blackening decreases as the ratio of "exposure interval" to
"darkness interval" decreases, even when the intensity and
effective time remain constant. There is no contradiction of
the Schwarzschild relation or any assumption that n in that
relation is unity, since the relation is usually stated

I,

/ t, \I ^

IW

is valid only for continuous exposures or for

exactly similar intermittent exposures.
Comparison with other methods of known reliability is the

onlv final test for any method. It is therefore, of interest
to note the many investigations in which the relation found by

55«
Eom hB.B been proved to be reliable by sudb aoiaparisoii. Martin(1)
found tbat **perfect agreement existed between the results when
transmission was asstnsed proportional to the radio of seetor
openings*®

His comparison was made with the 4bn®y visual

apparatus* Howe and others worllng-with him (2) in later
vestigationa verified the agreement between values fomd by
his method with the Hilger appa.ratus (same as used in this work)
and those obtained vismlly on the LuBmier-^Brodhun spectrophotometer*
Still further evidence of the reliability of this photograph
ic method has been by investigations conducted at the Bureau
of Standards (3), comparison being made with the luimaer-Brodhmi
and Ebnig-Martins spectrophotometers and Martens photometer, all
visual methods and with the photoelectric null method. It may
therefore be said that no discrepancies have ever been noted
between values of spectral transMssioni or similar quantities
obtained by Eowe*s modification of the Eilger seotor-photometer
method and those obtained by the other methods mentioned above,
whieh are larger than the experimental errors possible in the
methods*
fhe investlgatori at the Bureau of itandards(^) have con*
eluded that the principal source of error in this method at
present is a result of "vagaries® of the spark* fh© ©rrori' •

(1) Martin* frans. of the Optical Boo.,IS,pp.36 (1$17)
(2) Howe and aibson.Fhys.Hev.(2) 10 pp.767.(1917)
(3) Bureau of Standard's Technical papers, lo.l^S,larch,!920.
Bureau of Standard's fechnlcal papers, lo.1X9,June,1919•
(^) Bureau of Standard's fechnioal papers, lo.ll-^0, (1922)

56»
arising in this way may be of two natures: (l) That caused
by a displacement of the electrodes, and therefore of the
spark as a whole, from its proper position; and (2) that
caused by non-xmiformity in the spark itself.
After the apparatus has been once eidjusted properly it
is not very difficult to keep it so. This is tested on each
plate by means df the comparison spectra which, if of equal
density thruout, indicates that the first error hhs been
eliminated. The second can only be eliminated if both
sectors are variable thus making it easy to change the solvent
and substance under examination about. Then if there are any
discrepancies, the mean should give the correct result*
%

V
'V

m
, . ^ V

t

I

^

, • .'' V\

^li".
;

,N\NSV

, j , *
n t
i^\'^''.J"v, ' V'^iTt' n? trtif' I

.

:•• V

' <1, f'

T>,tf'/.S!l'

-f/.t

f;

iJJA/'fi

.iJ-l t'f.;jr.v««r» v.! i^'-!

m-'

T>iff W

Uh;m%
1

.

mj-

a.' n.cw

^1% >.n'

\^li

V.

khASfi i^\fOf, w^' ,.

k

'

Ji

/ '

'

'

""r/,.'#

N

, '

¥»

•mV.jll^fWilis'

?•*?

!%t.>.l I " fA'giH ^ L0itp&<

r-WJ.
4-

"

*;•'•«

A ,1;S

'K'' It

$

i )t ;''t'%'^i|:|^, '0i

V Procediore

' /1/-V. MfAj %' k1 ttu'

•<

^

7*

F

'vite

V.

f'

(h

ft-')

jfe

\/<

• 'fiktM tMijSiSi^* •, ; *

4

4 "i.l.'rtpt, i'-iH
' •
•: •••••. • • '!'V;! - • • . .•.,• •: "•• . • ,• • ' •

3i,^»#i %es I'" f M

"••
• • . •;• • •

«fe'',it

"^r (AlV

' '7':v"' ^ -'H:.' iV'.v';^?-^, „•' wv-'^

r^!')'< 4^ P^A

^

,v^

i>
#1

^'

i.a

' ?Xi

,> 4-14,-*^

Y \|v r'^ ''•
'i?!i '5» (i'i-1

, \
n
,

«1

stic, *• '.

/ 'J , "
4

1 i

/

5
I

U,

>•

.1

•^v>
^

'

'

^

n'

'A

'

, » S
\ -

I

•;ii^ 'fti,;#»4.«'->J» KliV'H'
•V-i

' - :• \V'> ^

K >

1

Wl

fS^j

,t-Sy£riS.'Sia;,

''

t"

V

;|('il A,
i \A\

J ViYW

5a
Procedure
After the under-water spark, sector photometer, quartz
spectroscope are all lined up and the wavelength scale checked
by means of a copper arc, the apparatus is ready to use. In
order that both the sectors receive the same amount of light,
a ground glass is held in the place of the plate holder while
the spark is running. The spark is set when both halves are
eq-ual in intensity and do not over-lap or have a fine dark line
between them. When the spark has once been set only a slight
adjustment of the electrodes is necessary since they do not
burn away very fast.
In outlining the procedure we shall go thru withcone
compound, namely, salicylic acid# The salicylic acid is
weighed out .010 gr. and transferred to a 250 cc standard
volumetric flask, made up to the mark with distilled water
and shaken several times diaring a period of 15-30 minutes
before beingiiused. In the meantime the quartz window and cell
are cleaned with cleaning solution aufter which they are well
rinsed with distilled water and finally with the solution to
be put into the ^ell.
The plate (1) is put in place# At the bottom the wave
length scale is photographed on the plate, then a comparison
spectrum is r\m with both sector open, for 1 minute. After
developing the plate if both halves of the spectrxam are of
equal density, the rest of the measurements are all ri^ht.
On a previous plate the proper dilution at which the com(1) Wratten-Wainwright# Pan-Ohromatic Plates
- . . Kodak Co.

vr'v,", 'U'

•

' •

'vv-;

) Eastman

•'

^9.
chosen which will close the band at a sector opening between
1.2 - 1.0.
Having chosen the proper dilution, it is put into the
1 cm. cell which is placed in the bottom or fixed sector,
while a similar blank cell containing the solvent is placed
in the upper sector or variable sector. The longest exposure
is r\m first since this method has proven satisfactory. The
variable sector is marked off in log

W'-"

corresponding to

the readings of the sector are given by tfie following table:

3,J
1,

^, "TO

' ,.

i '

'. ••il'l*'' •
' Jii

' \ I
f • '•

4i'

V

h<
^

>

4.

I';, •"K''
\ '

f

'if

i!

i 4

^ J

A.

• yf'-

'nV H

t

•'lilt; M
-,»

Time

^$"k'

k', M>i'V

0.0

1.00

0.1

1.26

1

0.2

1.5s

1 n

2.00

2

If

OA

2.51

2

0.5

3.16

0.6

3.92

0.3

••' ii'

U(! ' "f ili-* <"4-

0.7

o.g
0^9
1.0
1.1
1-3

' >;#•

4>.::W

lA

,>»"i

:SijP|s«

1-5

16 seo
11

H

31

tt

3

H

10

II

II

59

K

6.31

3
' 5
6

H

19

II

7.9^

7

If

56

11

10.00

10

II

12.59

12

If

35

II

15.35

15

11

5^

H

19.95

15

If

It

25.12

25

If

31.62

31

If

57
7
37

100

II

100.00

2.0

ft

25

5.01

>,1pts «i„''ii 11

1.2

1 min •

,«> '1/ i

II

U
II

' ^ii

'< . WiK.'

in-. ^

,HKL

•i!
' iV

,
n'

,
^!

,

lU," '/,. '••«' ? '

-t- ?4\i

ll' -''.'C

'I#

''

ti'-"

6i

^

After all tlie exposures have heen run, another comparison
is photographed, finally another wavelength scale is photo
graphed. Eighteen exposures can he run on one plate. The
plate is now ready for development#
The following formula has heen used successfully:Water
_

32 ox.

Sodium Oarhonate

3 oz#

Sodi-um Bisulphite

2 oz.

Hydroquinone

i| oz.

;!
'

potassium Bromide l/B oz#
The plate is allowed to remain 3~^ minutes in the
developer to give it good density. Then put into a regular
acid fixing hath as used for X-ray film (1), where it is left
for 1 hour to clear the gelatin. The plate is allowed to
wash 2^ hours in free flowing tap water (65oF).
After washing the plate is dried (Fig. $), Each
exposure is gone over with a small hand lens starting at
the right and working left, at the point where the upper half
and lower half of the spectrum are of the same intensity a
small dot is placed (Fig. 10). These points are read off of
the wave-length scale at the top and bottom.
The extinction coefficient for each exposure is then
calculated from the formula:-SV'I
-

(1) Purchased from Eastman Kodak Company, Rochester, H.Y.

,

62.

ip:
')?U

t/

<

*1

«H-i

If 'i /. '

•H
R-i

s'r
ON
-E.V

bO

.'I"'

Wmm

E r: 1/d

X sector opening x 1
0

where:d

length of cell in cm.

* *

0

gr. mol concentration of compound.

An "extinction coefficient - wavelength" curve is then
plotted on 1 mm. squared paper. From this curve, the curves
In the thesis were traced. The absolute persistence,
jselective persistence and wavelength were all lead off the
<Durve on the ram. cross-section paper.

v

'

, v. • ,

•"•'ft'':
a?:.,,

,

' *
.'r.

.

— r

65.
la addition to the experimental work on the various
organic compounds certain other facts relative to the
absorption in the ultra-violet have "been considered, namely,
absorption due to a blank cell containing solvent along and
the effect of cbubling the time of exposure.
The question whether a blank cell should be inserted in
the comparison beam has not been definitely settled by all
investigators. However, at present, the general trend seems
to be in favor of its use. In order to obtain more informa
tion on this question the following experiment was carried on.
The two beams were euijusted to equal intensity thruout
the entire range. Exposure with sectors setting of .05; 0.1;
0.15 were run with (a) one quartz window; (b) two quartz
windows 1 cm. apart; (o) 1 cm. of water with the following
results:
Sector
Opening

1 quartz
window

2 quartz
windows

1 cm. of
water

0.0

less

less

less

0.05

less

lessi

less

0.1

slightly
darker

almost
eqiial

equal

0.15

darker

darker

darker

It appeared from the plate that the second quartz window
absorbed more light than the first or even more than the
introduction of o cm. of water, relatively speaking. Undoubt
edly the greater part was due to reflection at the surface.
• 4-

66«
The difference is even more striking when curves axe
plot using in one case the blank cell and in the other omitt
ing it (l). When the blank cell is introduced the head of the
band is displaced downward one sector opening, while the
trough is displaced downward as much ais two or three sector
openings*
When one cm. of absolute alcohol was examined, the
absorption was even more striking. The foilowing t able gives
the results:
Sector Opening
0.0
•05

1 cm. of Absolute Alcohol
.less

•1

less

•15

less

•2

less

•25

trace lighter

•5
.35
.

,5

(1) seepage 67.

:

.absorption begins at 2S00 A
»
«
« 2600 A

A

M

i r-.

...less

^

«

«

M

2500 A

M

N

II

2ii-00 A

M

n

n

2350 A

A

20000

'/

u

•M# /I •
I'';-'

/I

f 1
\\

15000

/

E

/

11

10000

1

V

/

V /

r

/

5000

:

//

3000

2500

Procaine Base without blank cell
Procaine Base-with blank cell

^ M

f'

-Tf

6^.

Absolute alcohol shows absorption below 2350 A but when
using a blank cell in the comparison beam the error due to its
absorption is removed#
The second question of doubling the time of exposure
yielded results which might be anticipated. Since the two

(

spectra are photographed simultaneously, the result is the
blackening in increased if the time of development is the same*
If in the case of the plate having double exposure the time of
development is decreased to one half the two plates are
practically identical. The two curves are shown on page 67.

•

Nothing is gained by using an exposure of double that given
on page

so that this table of values was adhered to

thruout the present investigation.

" • • ',' '

KE » •

< ' i'

, '0

.1

};!'
!>

( , -'n

Wm

ti

'
'1

'ti

•/

jsoooo

25000

f

1 E

f\

1
V

1

\V

1
1

• .p nf!« ij
20000

. P[-' .JS ' j/II

1

jl5000

toooo

Ij
5000
A
2500
— DIphenyl Exposures single
— i)iphenyl Exposures double

1

' IfW? ' w

70,

'i i/ U 'It

'. f' t.

; '{/ ,
^

t't

'^4'

'iiifa.i(^;.i'f '#"5 , V k'

^

*1

i'kkiXi,
''i'f ^"\ I'/i^y

,

i

,

"t ,

'

l*'''

''

4 '

i

'' ^

if

'

f '

'

V

I

Wi0:'W# :r«!"'4t''''|il^'Ai.|^ '^'
• '•'' v>i'n; ••} )
'

'•"fMi'. ' '
mfMA
w
'" '
,..K
'

'

/ Xa 'te X

yV

•

-wM
,''x

'

^'1

''

' I ,

*r.

4 '^v^"4 •'•^ 'i

X
itmmmm

)^' 'f

>''''i'&'.l#:i!^li;- zifti

4*v$4k'^y

^'<l »

/X, 'J1

1 '

V

it '4

VI Experimental Data
i'l..
CI'

tf- •",,.
^ H ' -f

fa) Soxirce of Oompoimds

(b) Ultra-Violet Absorption Curves

XiiX '

1. Esters of p-ammobenzoic acid
and related compounds#
2. Benzene Homologues.

1 litcv,\

^40'

"''%• f

SP" S '^V iv •* '

y.J||

X?r\"vX:i|>' •,,Xi''

;.> .'i

'

i I

Wl

AAA'

]ViC<s^MVi)v

V

'

V
;s Ay v I ^

.' vA/
\AvXA,v ' .

. i,

\

^

v^ < • >

>

i1
i> V

;V-:!

¥• X

.

^

W'\.

^

AvHI.V,.'

i A

'

^

^

'

Avy; V'.

'

iMl nV'il A^A' :A:- V. ;

'"

A'"' A/x

\

:

>j/ , .

1M.

71
Soiirce of CompoundB

P-affllnoTDenzoic acid, a "by-produce in the manufacture of
benzoic acid by the nitration of toluene, was recrystallized#
1S6-7^C! (0*F^1S7*^C International Critical Tables.)
Methyl-p-aminobenzoate was made from the acid by esterification with methyl alcohol in the presence of sulphuric
acid by refluxing for 5 hours, after which time the excess
methfcl alcohol was removed by distillation. The residual
liquid was cooled and neutralized while ice cold with caustic.
A somewhat colored sweet smelling precipitate of the ester
formed; it was filtered off, washed with water and recrystalized from alcohol.
M.P. 112°0 (O.f. 112°0 International Critical Tables.)
Ethyl'-p-aminobenzoate, was the pharmaceutical recrystallized.
M.P. 90^0 (c.f. 91^0 International Critical Tables.)
n-Propyl-p-aminobenzoate was made from the acid by
esterification with n-propyl alcohol, by the same procedure
as the methyl ester.
M.P. 76^0 (c.f. 7^5^^ International Critical Tables.)
Butesbne, butyl p-aminobenzoate, a pharmaceutical
purchased from Winthrop Chemical Company.
M.P.

(c.f. 56-7^C New and Non-Official Remedies, I926.)

m

• a ;v

^

72,

Tutooaine, /-dimethylamino -

dimethyl-propyl-p-

aminohenzoate hydrochloride, a pharmaceutical purchased from
the Winthrop Chemical Company#
1£#P. 213°0 (c.f# 212-215^0 New and Non-Official Remedies,I926.)
Tutocaine base, /-dimethylamino--dimethy1-propy1p-aminobenzoate, of high purity, beautifully recrystallized
was kindly prepared especially for this work by the Winthrop
Chemical Company#
M.P. 9^-99®C.
Procaine, hydrochloride of p-aminobenzoyl- p -diethylamino-ethanol, a pharmaceutical purchased from H.A.Metz
Chemical Company.
M.P. 155-6^0 (c.f# 156®C New and Non-Official Remedies,1926.)
Procaine base, p-aminobenzoyl -diethylamino-ethanol,
was prepared from the hydrochloride by treatment with ammonia,
drying the oil first formed and after it has hardened, recrystallizing.
M.P. 47-g®0.
Butyn base, /-dibutylajninopropyl-p-aBlno'benzoate, pxepared from the salt by the same procedure as the procaine base.
M.P.
Aniline, prepared by the redaction of nitrobenzene!
Purchased from Merck and Company# Redistilled at a constant
boiling point of
Tables.)

(c.f. 1^4-.ii-®C International Critical

73

Aniline hydrochloride, prepared by molar portions of
aniline and hydrochloric acid, reeling, filtering of the salt.
Washed with several portions of cold distilled water and
drying.
M.P. 197^0 (c.f. 193^0 International Critical Tables.)
Aniline hydrobromide, prepared pxactly as the hydroch
loride except that hydrobromic acid replaced hydrochloric acid,
M.P. 256^0 (c.f.

International Critical Tables.)

StovaStov^ine, hydrochloride of dimethylamino-tertiary amylbenzoate, purchased from Poulenc Freres, Paris.
M.P. IJ^^C (175^^1 New and Non-Official Remedies, 1926.)
Alypin 2-benzoxy - 2 dimethylamino-methy1 - 1 dimethy1aminobutane, purchased from the Winthrop Chemical Company.
M.P. 93^0.
p^Hydroxybenzoic acid, prepared by the alkaline fusion
of p-hydroxybenzaldehyde.
H.P.210°0 (c.f. 210°0 International Ctttical Tatlee.)
Salicylic acid, purchased from Baker and Company, O.P.
M.P. 157-^^C (c.f. 15S®0 International Critical Tables.)
Guanidine Carbonate, supplied by the Graduate Department
M.P. 196-7^0 (c.f. 197^0 International Critical Tables.)
•

'

(if

^ t

J.

4

f:

7^.
Nitroguanidine was prepared "by dissolving guanidine nitrate
in cold sulphuric aiid, and pouring the solution into cold water,

long needle-shaped crystals separated out, and were uecrystallized,(l).
230^0 (c.f. 231°CI International Critical Tables.)
Aramonitroguanidine was supplied by Mr.John F.Williams of the
graduate department who prepared it with Mr. Ross Phillips for the
first time. The details of the method will be published very soon.
M.P. decomposed with explosive violence at 1S5®0.
Cocaine Sulphate, supplied by the Graduate Department.
[.P. 9S®C.
Cocaine Base, supplied by the Graduate Department.
M.P. 96^9B®C (c.f. 9S®C International Critical Tables.)
Dimethyl-p—aminobenzoic acid was prepared from Michler's
ketone, itself prepared in the usual way by action of phosgene
on dimethyl aniline. The ketone was mixed with soda lime and
heated to about 358®C in a retort; after the dimethyl aniline
had distilled, the residue was treated with hot water and
acidified with dilute acetic acid. The use of a retort is the
second of the two methods recommended by Bischoff (2). The
product was recrystallized twice from 50^ alcohol giving white
needles.
MJP. 235-6 (c.f. Berlstein Tabellen.)
p—Hydroxybenzal dehyde by the action of sodium phenolate
and chloroform.
M.P. 115-6 (c.f. ll6®C International Critical Tables.)
/

(1) Tenney, L.Davis. J. Am.Ohem.Soc.S6S, (1922)
(2) Bischoff. Ber. 22, 3^1-1 (lSg9)

ii VI'

75.

Benzene was piirchased from Arthur H. Thomas and Company
and redistilled at a constant boiling point of 30^0.
Toluene, o-^ylene, p-xylene, n-propylbenzene, iso-

^i

propylbenzene, n-butylbenzene, sic-butylbenzene, ter-butylbenzene, diphenyl, stilbene, quinaldine, and p-cymene were
purchased from the Research Laboratories of the Eastman
Kodak Odmpany of Rochester, Kew York.
Ethyl benzene was prepared by the Fittig reaction from
brombenzene and bromethyl by means of sodium. Carefully
redistilled B.P. 135^C.
Quinoline was prepared by Skraup's synthesis from
aniline, glycerol in the presence of sulphuric acid using
nitrobenzene as an oxidizing agent. Carefully redistilled
B.P. 237®0*

' '-vf, V'''
.

t

"

\

'

''

\' ' ' ' ' '

V

pii

r

...

I s'»'\

fw.

.

%'*','

>• s'

V,

It; if'... •; t
., V

.

'

11 AsiVi?:

'V4 ^

M V 5^
' l.v :'V

t

V ^

.. ^

,

'"5'i^

'A'MikmAMdf'dmpL,#,^u51,.-A:.,

vO \

> 'fCil

76.
Previous Investigation
Altho several of the compounds studied in this in
vestigation have been previously recorded in the literature,
the great majority were rtm before the advent of the sector
photometer and they were siifficiently important that a need
was felt for more precise data (l).
Benzene has been^perhaps^ the compound most often found
but very often in some other solvent and not imtil very
recently has the absorption in absolute alcohol been reported.
Orndorff, Gibbs, McNulty and Shapiro (2) report 23 bands for
benzene and 21 for toluene. However, the author feels that
they are not justified in doing so since they only have de
finite proof of the existence of six whereas in ,tl|e presendi ^
investigation absolute proof has been IstaADlished. There exist
seven bands. Seventeen bands as reported by Overdorff are only
suggestion and it seems very queer that they do not: record
the seventh band the author obtained very definitely. Six of
the bands Orndorff report agree very well with those presented
in this paper. Anderson(3) has had the same difficulty in
duplicating absorption curves previously reported by Orndorff,
Gibbs, NcHulty and Sahpiro(^) on triphenyl-methane derivatives.
For the non-substituted homologies of benzene Baly and
Oollie (5) give a curve for ethyl benzene showing three bands
(1) For a complete bibliography on the earlier work on absorption
spectrum in the ultra-violet see "Report of the British
Association for the Advancement of Science,p.131 (I916) also
Kayer's Handbuch der Spectroscopic, Vol.3, pp.461 (1905)
(2) Orndorff, et al - J.Am.Ohem.Soo.,50,831-7 (1928)
(3) Anderson, J.Am.Ohem.Soo.,50, 208-212 (1928)
(4) Orndorff, et al - J.Am.Ohem.Soo.,49, 1541 (I927)
(5) Baly and Collie, J.Ohem.Boo.,87,1337 (I905)
'

i ,

1.

77.
at 25^0, 2655 aJid 26SO which agree with those reported in this
paper., They also state that the other homologTies toluene, propyl—
benzene and butyl benzene have been foiind to be very siaiilar to
ethylbenzene but no cxirves are reported.
Diphenyl according to Baly and Tuck(l) shows only general
absorption, while latter Baly and Tryhorn(2) report a band at
a wavelength of 2^60 A. For stilbene Stobbe and Ebert(3) report
a band at 29^0 A, while Macbeth and Stewart (^) report a band
at 2960 A. Quinoline and quinaldine have previously been
reported by Ward

j/

p-Aminobenzoic was reported by Magini (6) with a band at
2700 A. The only other ester of p~aminobenzoic acid reported
in the literature is novocains(7) lowing a band at 2920 A.
The same author reports for cocaine hydrochloride a band at
275OA while Castille (S) states there is a second band at 2330k
Aniline in water is reported by Klingstedt (9) who states
there is one band but does not give itw wavelength. Salycilic
acid as recorded by Purvis (lO) confirms the report of Hartley(11)
in that it shows a band at 2So6 A.
fl) Baly and Tuck. J.Ohem.Soc.,93> 1902 (lSS2)
:2) Baly and Tryhorn. J.Ohem.Soc.,107,105^ (I907)
Stobbe and Ebert. Ber.^,1292(I9II)
. ) Macbeth and Stewart. J.Ohem.Soc.,lll,S29-50(1911)
5) Ward.Biochem.J.,17,903 (1923)
b) Magini.Kayser's Handbuch der spectroscopic.3 pp*^7^*

Nuvo Oim. (5) 6 PP*3^3-70 (1903)
(7) Brustler. Bull de la Societe 0|i®mique pp.1527 (1926)
(S) Castille. Bull.Acad.Roy.Med.,Belg.(5) 1930200 (I925)
(9) Klingstedt. Oompt.Rend.A76, 2^S-50 (I923)
(10)Purtis. J.Cheiji.Soc., 127, 2771-6 (1925)
(11)Hartley. J.Ohem.Soc.,53, 6^1, (ISSS)

•

"

•

-

'

I"

' V

,•

20000

y

i

.

1
15000

•• f-

10000

5000

\1
;• Vv.Vrv

3000

• • •

A'

2500

p«Amino'benzoic Acid

'fv'* '

I>-Aminobenzoic Acid

Absorption
Sector Opening

Begins at

Ends at

Begins at

Complete
30S0

3000

3000

2^2^

2290

2955

2t-90

2275

2900

2525

2270

2862

2552

2260

2830

2590

2255

Noni^

Xs

2240

M

2230

«

2220

?

. f/l

2208
2195

The final dilution was .00005639 M, the plate constant
I7IHO, the cell 1 cm. thioi.

.'1

}•;'

u

vi'j

' v\ . '? S,

^

l"-

'.'V
•SiSSS:W

'M H/'V.

•

.- "-r'-v

-

,

t.

2QQQQ

15000

E
10000

•- • ' •' • . '•;

-;.U 3» (M.-.

.

"
-riVs'r

5C0C

3000

A

2500

Dimethyl^p-aminobenzoio Acid

'••

SU

'."4'.

Dimethyl-p-aminobenzoic Acid
Absorption
Sector Opening

f

0.0

1
1

.1

Begins
at

Ends

at

Begins
at

Complete

-3
...... .,.i-,-.,..,,., •,i.>.v.->,-|.

1

.5

1:t'

I'

I •

1
f•

Ends

at

3520

3^70

i

1

Begins
at

.?•••

3'^30
3320
3350

2900

2S25

2660

2i|-60

3320

2920

2800

2675

SViO

3290

29S0

3220

3020

ZkZ]

Honi»

1.0

2l<-20

tf

2IHO

1.1
1.2

. •.

2't-02
ff

2390

The final dilution was .0007273 H, the plate constant 1,375,
the cell 1 cm. thick.

s.^

'.Sfcli:.;''

.'

" •"

> -'" H

' •!, A" '"'4'

l', •

20000

15000

10000

5000

"

5000

A

2500

Methyl-p-aminobenzoate

Me thyl-p-»aininolDen2oate
Absorption
Sector Opening

•,1

|M

£nds at

Begins

Complete

OwO

•J,i] '1

Begins at
3300

•!
e2

3220

.3

3160

.l^

31^

2l<40

2350

.5

3120

21^70

2330

.6

3090

2520

2300

•7
.g

3060

2550

22S0

30lf0

2590

2260

.9
1.0

3020

2630

2230

2930

2670

2220

1.1

2950

2700

2190

1.2

Hone

2180

The final dilution was .OOOO6357 M, the plate constant 15,730,
tbe cell 1 cm. tliick.

y

.1,

• I':

? Ml
V'>>>

"• \ •

.

• N\
^ Is

"514',
'1 ^

I ,

„1

-J

'' i

I

' <' •

:

20000

15000

1
E

>•

1

\

10000

IJf

i

•1

5000

1

3000

A
Benzocaine

2500
,4..-

25,

' & ,
W /' / , .'4 .
r'C ?
•//" f' 4 ' I '

,4j

4. h.J

Benzocaine

mm

Absorption
Sector Opening

Begins at

0.0

Oomplete

Ends at

Begins at

5

*1

3200

21455

2320

.2

3160

2525

2535

•3

3100

2555

2305

A

30^0

2520

2222

A

3060

2610

2275

....

.6

3030

2625

2260

^4l'

-7

2660

2250

29^0

2700

2232

.9

2950

27^40

2230

1.0

2^95
Hone

2795

2220

i

nil
1.2

*

2215

It

2219

The final dilution was.00007273 M, the plate constant 13,750,
tbe cell 1 cm, thick.

• t t\

A- ^ '%4M4 i f

V I.

'•.

•

/

20000

15000

-1

• • ..,1? "

/

1

j • E«n
1

//
/

10000

j 5000

/

/

i

3000

A

2500

Propyl-p-aminobenzoate

«7.

w'mi
" t4 ' '
'M

PropyX-p-Aminobenzoate
Absorption
Sector Opening

Begins at

0.0

Complete

.1

If

.2

3300

Ends at

Begins at

•3
A

3ISO

2^70

2350

.5
•6
•7

31^

2500

2320

3100

2530

2300

3070

2570

22S0

.S

3035

2595

fi260

•9

3000

2630

2230

1.0

2970

26SO

2210

1.1

2930

2730

21S0

1.2

Hone

1-3

2170
2160

The final dilution was •000053^3 M, the plate constant
IS,6^, the cell 1 cm. thick.

i
V._;>
*

I

,

'
,

,

fJ
'1 f

'ii .

20000

^ 5#. \

15000 •

-.
E

10000

r ' '.

50C0

m

/

3000

A
Butesine

2500

1

f

*, 3

I'

Butesine
Absorption
Sector dpenlng
0.0

Begins at

Bnds at

Begii

Complete

.1

3210

.2

3130

2k-30

2390

.3

3155

2^20

2360

3iho

2515

2340

.5
.6

3115

255)

2315

3110

2520

2220

.7

3075

2600

2265

3035

2630

2250

^'1 .9

3005

2650

2230

1.0

2920

2625

2215

2960

2730

2195

2770

2120

;

Ml

,X.1

''!

1.2

;;:;

2930

:;' 1*3

|-

None

11

'*

2165

The final dilution was .00009326 M, the plate constant
10,700, the cell 1 cm* thick.

.• -

_.2000C

P'

15000

E
-\

10000

• •.

•

j

/

m\

/
f

-•

/

•/
/

FiOOO

/

'V

^

•
3000

A
Procaine

2500
"V.^ ^." • ;\

fc#:M
Si.-,-:»2^-:a,s;.

M'-rv

wm^

Tf. A r *

91.

Procaine
Absorption
Sector Opening

Begins at

Ends

•

Complete
3320

3330

1

3270

,1

3320

2kX'i3

3190

2k-93

3170

i 25^^5

3140
3120

2570
2610

3090

2640

3070

2675

3040

2720

3010

2750

2950
Hone

tl.',
X

,'

f

.

2160

,

ii.

# -<fV
^ h'

\'

r.i7'

•

20000

15000

/

J

E

/

10000

/

5000

/

/

3000

A
Procaine Base

2500 .

93-

Procaine Base
Absorption
Sector Opening
.

Begins at

0.0

A

I

Ends it

Begins at
,/»p|

Complete
32SO

•!

''' *' *1

"1

.s

.2

5200

2^1-70

2^^-10

*3

T

3160

2535

2330

A

3150

22S5

t i; L-5

3130

25^5
2615

.6
.7

3110

2635

2255

3090

2665

22^0

3070

2700

2215

•9

3030

27l|-0

2200

1.0

3000

2190

1.1

29SO

2770
2gl0

1.2

None

•I

'

il,:

2275

21g0
2170

The final dilution was .OOOO5S59 M, the plate constant
17,070, the cell 1 cm, thick.
7
I

'"i

^

i

^ if

'nm M

• WA'

^M,V, ' 'I..
i

X:

^

i

7. f;

*<7* 4»

i

1

!vL.

:i|»
Mi

'M
lifi

t'r

20000

• i

.1

\

-

\

15000

N

\

/

1
E

/

10000

/

1
'>5. Iht,
5000

I i u.

-

''i'r

1

/

\

2000

A
Tutocaine

2500

/ '

95.

}'// 1.

f

Tutocaine
ATDsorption
Sector Opening

Begins At

Ends it

Begins at

2'1-60

2360

2530

2305

2565

22SO

2598
2630

2270

2675
2750
2780

2250

Complete

3270
3190
3110

• -.• %

30S0

T"

3150

f

-J- ;%

3060
30U0
2980
Hone

.,

2260
22iK)
2250
2220
2200
2IS5

The final dilution was .0000^-195 H, the plate constant
23,250, the cell 1 cm. thich.
I

? ® i\ V
^

, ^

s

f

'

(

> -i

J!".'.

t

*V*. «

,•

» rt.*r • <J

'<•

v"--

K

,%>

' \1

.

20000

J.-

' 1
- r-:

•

.

15000

•s

s

^

/

10000

\

/
y

1

1
f »vB

^'

5000

'

j

1

' h"'

1

/

3000

A

Tutocaine Base

2500

97.
Tutocaine Base

Absorption
Sector Opening

Begins at

0.0

Complete

Ends at

Begil

.1

3200

.2

3160

2500

Z5hO

•3

3150

25it-5

2325

A

3130

2575

2315

I'i. *5

3110

2600

2300

j - .6

3090

2630

22g0

3060

2660

2265

3020

2690

2250

.9

2973

2710

2235

1.0

2940

2760

2220

1.1

Hone

:l;.

f.

1

.7

1.2

t

1.3

.

'

J

/,

i

V

22X0

n

2200

tf

2190

The final dilution was *0000656 M, the plate constant
15,2^, the cell 1 cm* thick.

'-h'l- >v;

vr '' >.

S -.i h

'msi

i'

'f'. MA

Wf'
W:

20000

15000

10000

5000

3000

2500

Butyn

99.

Butyn
Absorption
Sector Opening

Begins at

Ends at

Begins at

Complete
'"f ''

i

i',

•!
'f

I i

2^^-70

2i4-00

2520

23^0

2560

2300

2610

2270

2650

22^

2700

2230

2760

2220

None

2200
2190

The final dilution was *00005005 M, the plate constant
19,550> "the cell 1 cm* thick.

I r I 'J' A f

r

I

. A

1'"'

r •

^ »

V t

.....T-X-i,,- .V...

N

„ Tiji...

I

•
' -

/

-

\'

20000

-

!;"'- • , -«:.•* •
•^•%.- • ;;•• • •-.

'• •'. •

^ ', -

.

. '

j

1
isooto

/
•AZ-

r
S

,•

10000

/

i

1

• .%,• ,-. # • •
1" f" J. ' "'

\

1 ~ L fc'tl

•" '.
.'i

5000

\

/

/

yrf

• • • • -•

•

3000

A
Butyn Base

2500

'

101.

iiiiiiiiiiww

Sf,U

^ 1./^,

«f..

tit-mis'"

^

V

Butyn Base

»

'•"r

Absorption
Sector Opening

Begins at

0.0

Complete

i'

Ends at

Begins

.1

N

.2

3300

.3

3250

2^60

2380

.1^

3200

2510

23i4-5

.5

3170

25^2

2320

31^0

25^5

2295

3110

2630

2270

30S0

2650

2255

.9

30^0

2700

zzko

i

1.0

3(D10

2720

2220

^

1.1

2970

2760

2200

29^

2S05

2185

1
•

-7

'f

' ^ 'I

•f,.v

1.2

' f;

-

2160

None

1.3

•'# ,

Tbe final dilution was .00005^^

M, the plate constant

17,100, the cell 1 cm. thick.

•t?'' :•

is

i.
r i/t

,

, ni' I

„• '

>4. V ^f /

%

^ '^v: '

'if

Z

. ^

i

'' '

<Z, \'

> , >;•'! 'J'
'

;

w^'' ;•'

i,-

*

rntiirrs
-iv," V^'' v'V .-'V;

'it;'"''.-'fV": •

!•

•, v;;'^v >

$s aA«a

^ 'Sf.'is{>.s

if-

-^' • .1

.(\l f

iji

€fiL^c/d^

giaiaaijC XCJ?®©

Cl a^^iqae.'O;^ ^ i.'

D

xx
4c.
\ ^cs

Ayf
. • \'

/

;•/'
; J

t

0.0

,•

I.

!

oef, I i ^-s.

DaZ2
.:•• ••'.

•'.'/ • '• r

ox®

Wil 1@

-li.

•Of.

4^
tf
J) '2ess

c^iZ ,,-/,•
'-J /I; '"•'•,?•
WF 1^'
'-"

eags
ocas,

Ull

O^dS

oscc.

Ofel G~ 0^ CCYS
\i ! •"
CSSS
Q • 'GSTS

040C'

1 OT.f.
;: ^ '' ??s.

ocss'.' ,

1^"

o'

I!

oSis

,,-

? ,-'
•. ,

z^-

. 'O

OIIJF >•-

^ a^r;

5SXS

.3,

-o

ov"

/' 1 '

, >ly^
.J./ *«='
..•.••Yv'.

• • •

v^'i G.X

'• • ••i.i'

A.

X

K*

\

i f

im^mtov $miq ©ii|
I.'

#iif
' 'k '

ioiri# .Jsa X.Ii|99 eifj- ,OCi.YX

r

I( .'

r

'•' y

'A

'

'

W

1

'•

\ '

Z

:'

'

'

M U

• r

/

., i'.'

'

„

'•

'

mM9XI$M9WmX'
i

-

f;.':
r'r

.'.

''V-iti'

,

r'

.1':/,nx

'j •'

A-'.4'4Z'-

^%^:t mtPf'

' ',. \ •• -yk

25000
/

• - •'

i

20000

•

1

•

'
>
." -p

E

».

1

%

1

15C00

'•

• • X -.yk:' :

••••••.

,

\

J

1

1

10000

'

3000

A

2500

P-Hydox^'benzoic Acid

.

.1. r

103.

p-Hydroxy"benzoio Acid

.•',

Absorption
Begins at

Sector Bpening

Complete

Ends at

Begins at

2310

2200

2355

2175

23S0

2165

2J4-45

2160

None

2157

2155
2152

/ ,% ^ •;

2150

The final dilution was .0000'tS26 M, the plate constant
20,720, the cell 1 cm. thick.

'

<'

I

' • y' ' •

'•

s

' 4.'"

'*

it,•

.Cv ^

44• ' '"'l
\4

• '>f

. ..

"

20000
V.i'..4;

15000

E
^4

10000

• #,

5000

3000

A
Salicylic Acid

2500

V

^i

^

J

^

'''J
v., V,
/ f'' ;
'' r

•'

X

105,
%!^' !';" ,

' '

1

Salicylic Acid
f :

Absorption

Sector Opening

Begins at

0.0

Complete

Ends at

Begins at

i ': '•

1 5 ,*

.1

3360

.2

3ZkO

2610

2520

•3

3210

2698

2i)-95

.M-

3190

2720

.5

3150

2770

24-70

.6

3130

2800

2460

.7

3095

2830

2450

:

.S

3080

2850

2445

I?'-

•9

3060

2880

2435

1.0

3050

2910

2430

1.1

Hone

2422

1.2

tt

2418

1-3

w

2410

}

!

' • *1

i i'',;)#

The final dilution was •OOO2S9S M, the plate constant 3A50>
the cell 1

thick.

\''
<)> 1|V

3

s4 '

^ 5
«,

•ii

-

^

• •- : -•N< • •-••

•• •.- . •" v.

,20000
,, ,
_

\^y

. ,

. .•„

;

. . • , *• A • - , • : :,. • . .
•#«.,•: •

•••."• :.' •

, , '•,•#! .
•••.'V.

15000
Hf
t C)--

E
if

'

4"- -. >

., . z,:' •

10000

•' " '.Ml ^ti'LVt%%tyn #
A

tl

r

5000

1

3000

A

Oocain« Sulphate

2500

'

.

107.

MV 'Ji,'J-/%.>

'1

'

< •!-

**wfronp!*i*'»>w

'y^i^

Cocaine Sulphate
Absorption
Sector Opening

Begins at

0.0

Complete

.1

2900

.2

2870

•3
A

2840

Ends at

•••Vj
• f.

26k3

278O

.5
.6

2570

Hone

25^5

If

2535

.7

ft

2525

.8

tt

2520

•9

tf

2510

1.0

«

2505

The final dilution was .000^236 M, the plate constant 2,^15,
the cell 1 cm. thick.

ii
,4'

-•

•<k
%'r ff
4 '\]r
,v

WW**

'1,' ?'

/
('

'

A>'
<1

,h f

"• A'*

>\.

^ ^

/

i- '

f"*

\
1 i, ' i

^

-

4,'«W

45*"fl.' t? M),

f f
4 1 W. t

'

i,'
X

"rt.

,-

X

^

t

'm

Begins at

'.,'V,

20000

15000

E
/

10000
Si ' 3;,'.

.

it 4.^Xi. if I.

• r

\

mt.%:

5000

3000

A
Cocaine Base

2500

:; • I

mm

109^ i

Cocaine Base
Absorption
Sector Opening

Begins at

0.0

Complete

j.^ .1

I';

•5
A

'

Iv

|.; *5
;
.6

Begins at

2230

2630

2535

2790

2630

2570

It

*2

•|- •

Ends at

2935
2900
2260

•

Hone

•7
.g
.9

2560

N

2560

It

25%2

1.0

8530

The final dilution was ,000523 U, the plate constant 1,390,
tbe cell 1 on. thick.

> I

<'•> -<1, "4'K

i

^

'I.

•P'

•;•'•,-IK

' t

V'

-

4 I

\

'

,

h-H t

I,

mi
.1'

-

20000

15600

E

10000
i r-4t...i. d1 l-U11m
S &•!

^

v%;X ?i
-

5000

3000

A
Alypin

2500

~m

'•U '

>

/ ^

t

•-<rm

Al]^in

r^'
^

/

J

Sector Opening

Begins at

0^0

Complete

I

•^/ •

J

.1

2960

f .2
I

2920

•3
A

2S9O

.5
.6

2S20

111.

fir
I

Absorption

Ends at

:y\; • •

2S5O

v'•'

2675

Hone
n

•7
.g

Begins at

2535
2570

2555
23kS

:®ilf

.9

2535

1.0

2525

s|ii
, III

«

,
j

li

ii' ?r'ii

The final dilution was .0005755

the plate constant 1,730, •

the cell 1 cm. thick.

'r

'i

:3i

tea
>•1

•I

•;'(

V

• ^:

h te

'

,

.V,:

!i

,!:li
..'•.•I

's •.' ' ' ^ v¥.>^ ' >' 1'
jt' ' l'\
'A i

'•*m
>
\ \'

•'•'

h 'te

'.

ii
f'>l

'ivki'.v,
.'Av

Sifis

^ilM

?W5
'J

20000
'•0- : iH'

•n^'- f^i**,-

15000

E

10000

5000

3000

A

Stovaine

2500

113
r%.

Stovaiiie
Atssorptlon.
Sector Opening

Begins al!

0»0

Complete

.1

Ends at

Begins at

2950

.2

•3

2900

.It-

2275

.5

2Slt5

.6

2gl0

.7

2790

.g

Hone

ft
4

I

*1^'

2660

" ^

25S0
2560

.9

2550

1.0

25'iO

The final dilution was .OOO6276 M, the plate constant 1,593,
the cell 1 cm* thick#
. *i "

} .. ' r f-}

- * it'

l,t^

1

^

^t
»'f

'

f- .

i/,,;„.*,.

3000
G

^ .-K

A

%::k

2500

Guanidine Carbonate

115.

Gtianidine Carbonate

Absorption
y

Sector Opening

Begins at

f

0-0

Complete

•ft

'A/ •

i

V.

tJ- „

i

4^' "'

.1

3250

.2

2900

•3
A

2770

•5
.6

2330

•7
.S

2te5
2iH0

.9

2395

1.0

2380

1.1

2370

1.2

2360

•|

2620
2^50

The final dilution was #11111, the plate constant
9, the cell 1 cm. thick.

^

v\ >

Mv ..f •

: ,,k.
S-! .>
•• V

^

•
' ,s

r i

vkk&"t.<, ji.l:, ,••
,fv

:; '

•

'9 i-'-"-

. '/•'" "'• • •
20000

^ .4

JV

tC

. '

15000
'•9-

•

•

• "S' " '
;r6 '

-w
•"

,t

. •

•

'--W'..

10000

\

f

' .

•v:

1

1 •'

5000
'
if

•• ••

:• :;.

...
' ' •

'

'

i

3000

A

Hitroguanidine

2500

117.

Ki tr ogxisoiidine

fW' ^'rs(' f( t-*'^«If

Absorption

Sector Opening

Begins at

0.0

Complete

.1

3965

4

#2

2905

•1

.3
A

2&60

Ends at

Begins at

2825

24-10

2270

2S10

244-5

2260

.6

278O

2480

2250

.7

2760

2510

2235

.&

2714-0

2535

2225

.9

2720

2555

2220

1" 1.0

2695

2585

2210

•5

•

i2» # 3»

.yA.... .

'

J't ••
/

*'

;

2200

]^03ML0

«

• 1.2

• 1I-• '

1

2195

The final dilution was .OOOO7692 M, the plate constant
13,000, the cell 1 cm» thiclc.
':^v

:,v.^l .,••

;••.• :•.. •.; ,'i; • ..

\ .

.'. .

.

:• •

..•ul:

i., 11

' ?; / \

f,

f '•,

' 'T'l
Vr.

i'.v

... . '••• ;.vV%'

; ,
J
« i'\

, 'V ;

''
1

X

I *•>!•, " *

.
I.

^

i/j

^
: i\

• "tfc.-tt' •
'y*' V

» sHV> 1 f W.^i'SW

IVvC
|l ' 1

I.' \'' '

J

>

.\j, 5l'4" %iA.i\\t.-hil:

'

200000
-

15000

ti

B
•• . .

/

JO

1

Sfc •

10000

V'

^-V

"

5000

3000

A

2500

Aminonitroguanidine

rnmrnum^

''•if. •"- '4 -"".I

'• 'Z*^ 4(, •#( ^,A "«

WmJH ^v

Aminonltrogaanldine

. '• / ,

ATDsorption

Sector Opening

Begins at

0.0

Complete

Bnds at

Begins at

.1

M

.2

3000

.3
A

2925

.5

2^k0

.6

2SI5

11

2l|-70

2335

.7

2790

f

2500

2310

.g

. '^:

2770

j

2535

2280

.9

27^0

/

2560

2260

;V'
'A

!> '

i'/

2SSO

f

aMw

-( p ^ «iv'

2370

1.0

''i

2710

i

2580

22lW

1.1

.-I'V'"

26SO

I;

2610

2230
€200

ITone

1.2

The final dilution was •OOOO6723 M, the plate constant

'fWf&fgii

li|-,SOO, the cell 1 cm. thick.

'\
•i'' ,

*

'•' X;

" '

'KX •

•• .•

a; ,.r-,:. ••

•:!s

,

^ I '" •;' '

•
.'•

*>•'
•v

1

1

2000

.; ^-1

• '• •,. • •'^. • •' • •

:

•.•• •' •

f ';?/ •

1500

E
•..r - • . • •'

/

1000

•

\

1
•

•; ^#11 1 kMp

500
'i

3000

A
Aniline

2500

121•

Aniline
Absorption
Sector Opening

Begins at

0'»0

Complete

11' •!

•'• it"'

f
M

i:i
•;

i
{
!•

3020

*2

2975

.3

29^3

.5
.6
•7
.3
.9

Begins

Ends at

' '^1
Ay. %'

25l^8

2915

2580
261K)

2520

3865

2695

2505

2825

27^10

24-90
2480

Hone

2472

ti

2465
2455

H

1*0

Tbe f iiml dilution was •00004-132 M, tbe plate constant 2,252,
the cell 1 cm* thick*

-I

J

1,

\\

' '

<

\.

'w

*,

'\
\

%* •

li:i*

i

V1 *

'<5-

' \ V'

,.i

' *1*'

'.

l",

4""
h'

:K>f' ••

«

?
' ""I >

Lit"'. .

i

V '

^ Ix'j'IJ

^yf^v

* •*-

2000

1500
•
V i ,g

"Bi

('.'•rS,

r1l

1000

_.fk

i" \

lii l.vit

. >

n

<

*

.

ili

500

3000

A

2500

Aniline Hydroohloride

!(•

123#

Aniline Hydrochloride

Absorption
Ends at

Begins at

2910

2705

2610

2g£0

27^5

2570

Sector ftpening

Begins at

0.0

Complete
3060
3020
2940

••I:

IT

Bone

2525
2510

.7

2'<-95

f

• IS

21J-75
21J-62

1.0

The final dilution was .OO279 M, the plate constant 352,
the cell 1 cm. thick#

.v.U'r

y

•'

"A?' KiA'.:

.yJiW'

, ':

•I'ih .'-y.

.'
''.A . •-.

2000

."'V"'"'.
1500

^
-

«

''A-••

7

, '

E- ,
>, V

'

.

.

1 000

1

'

—
560

I

..'v-

»,• ' .

i

•

3000

A

2500

Aniline Hydrobromide

;

125.
f. <:/

..a

t/ y;-,'i( l:

Aniline Hydrobromide
Absorption

Sector Opening

Begins at

0.0

Complete

.1

It

.2

2S90

.3
A

2S10

Ends at

Begins at

: 4^

as'w

2680

2l<-82

Hone

.5
•6

,W'

2l|-60

H

•7
A
A

2^25

1.0

2390

211-10
2'«)0

\ -.t

The final dilation was .OOllil-9 M, the plate constant 87O,
the cell 1 cm, thiclc.

1:;
.r

fr

%

)

.>.;
I iti J

• i'

J!

V.

."tp,,*;:! v."m ' ^

.

/iT<
V

t

. ti ^

II

K • .-p.
^

. tc.

J . ^

N"

^

#k(
AiW
*

.'ii! '' .

> ": *,

mm

20000

15000

•

•/
1

10000

1
1

•inkl

5000

1 • -: •

/

:

/

\

3000

A

2500

p-Hydroxybenzaldehyde

X '

^

127.

p-Hydxoxybenzaldehyde

1
^ *9r '• -1

'

AIDS orption

Sector Opening

Begins at

0.0

Complete

Ends at

Begins at

.1
.2

•3

3120
30SO

1;
L.. .5

f

.

3050
3030

'

3010

• i'- .s

29SO

1''

.9

2950

i

1.0

2900

;/ , • la

None

• i

ti

1.2

The final dilution was ,0000^9^^

plate constant

20,S00, the cell 1 cm. thick.
i\

'*1^ ife

'tr t \%A '^1 ( i ^ ^

) ^

's •«. .'V' , V

^ ' V •

't" •? ' .

J-

' 'V

'4

• -.1

^

i -v.
^J
aAi.

...... 5fc -i,W®,

mmm

,

fVXA^' y

Tf i,'".

•V h V

. <

-

.

[

>
200

'• • •

• :'>4- .•••...•/

\ . :•

'-4-4

C'

'>.

1 f^O

, •

• -.v-

*

/s^

• •;.

B

100

c.

1

,

• •.

n

/

BO

K'

_ •

' '^1 '^1 ' •

•rif|-

•

!ri*

R-jiii. •
•
M
'•/%» . « ii- .

•:.r ],.-,^- ••••.

I'Vi?

.

^.'ii

•
;

i.

..

••

•

3000
,® t-ir

,X s',!;j

A

Benzene in Water

2500

•-'X:':

sm
.,.

.>*:?.. ".

4'J.^iiii.diK'o..

iW'.jSwSr

£«S>fcia3«a!ai!a

129<

ta

a

o
vo

•H

ti)
<D +»

m d

, •'»

5d-p

M d
OQ

d

•r-l

bO
(U 4»

PQ d

CVJ
CVJ

O
t<\
K\
CVl

CVJ
CVJ
CVl

o
o
CVJ
CVJ

LTV

o\
iH
CVl

o

ON
H
CVl

CVJ
160
rH
CVJ

o m o
r- vo vo

m
r~4
CVJ

rH
CVJ

H
CVl

l£\
LC\
KN
OJ

H
CVl

r

, • •| .

m
irv

iH
CVJ

^

K\
CVl

O

5

d w d
o

O
00
^

CVJ

Lf\
Q
^
CVJ

K\
H
-d*
CVJ

2
d

'J'

a>
d

/

CVl

\V/

l:f

; ,

> ::|-

GO

CVl

CVJ

CVJ

CVJ

CVJ

CVJ

CVl

cr\
-d"
CVJ

1^
jd*
CVJ

ISO
jdCVI

T60

o

o

vo

n:#

d-p
W d

m 1S0
vo vo
-dCVl

CVJ

CVJ

o

- •:

160
VO

-d*

CVJ

d

•H
Q>

d
d
<D

00

d

O

•H
bO
© -P

po d

ir\

PQ
00

H
LTi
CVJ

*d

d-P
{a^ d

CVJ
m
CVJ

CVJ
m
CVJ

3
M
cu

CVJ

o

CVJ
LfV
CVl

00

d

-H

hO

©-P

PQ d
to

•d

Id
-p

to

d

•r4

bO
a>4»
PQ d
bO
d d
o -H
p d
o ©
© a
mO

©
p
©
iH

&

§

O

o
o

o
VO
CVJ

trv o
CVJ
CVl
vo vo
CVJ

CVl

J
> "I

'„• .

CVl

*«"'
60
<D -P

«< PQ cd

4»

LTV
rH
CVl

1:

•H

M

o

ir\

w

..

CD
Tiii
^-P

o

CVl

o

CVl
ITV
LTV
CVJ

O
LfV
ITV
CVl

Ln
^
LfV
CVJ

LO
^
irv
CVl

CVl
ISO
LTv
CVJ

CVJ
160

CVJ
ISO
LfV
CVJ

CVJ
150
LfV
CVJ

o

LfV
O
VO
CVJ

o
o
vo

o
o
vo

160

CJ\

UfV
rH
VO
CVl

H
VO
CVJ

H
VO
CVJ

J4~

ITV

VO

m
CVl

CVl

CVJ
CVl
LfV
CVJ

o

160

-d*

CVJ

CVl
CVl
LTV
CVJ

5
S
irv irv

m
CVl
ITV
CVl

o

CVJ

CVl

Ll'V
CVl

o

H

CVJ

i-i

H

CVl

f-#

'•
H

LTV
CVJ

m
CVl

o

-=}•

LfV
CVJ

'^'\Q

XI" ^

^

€*

l-«

I :

.ir*-

#m

si^i'

^ jl<AAj^tl\M~iisA ^ ^ J /.^<D tt Tj J'J

Ji5-

a,5; ^/,X^

dJ^/WiAA ^
-drl si-*fe'C#W ^

ily^2>
if^?)S

jj ^

^.J'. ^3

'

4

5'
(f ^ * XfC ^r~-^

u*
.

-

f^-^'$ U : 3C2>.^'1 • ..jV'
%'
f'' )-'l,
r '
''/ * < J'\x

If''

"ji
J

'K

i '

'I

''!

Si»

y

>1

A'

l-vWk-

1,/i

' ''li 'Ji

. »i'',

* '' '(•' /'} ' l'

't
"f .$•:
1^7 io V7'

«

W

»

!<•

O

t9 W !f'

<1

i4-

; g:'

' '•• '''

'" 45 ,

WOT, ,;/. \r't,,,^.'>3- : ',' ';%1

• •"'i-ll.'fe,!,' II;..,.,,,:,

f «., M^ S 9. ,'S
?r} f/!_''f0< m

f"<-

11 >•!

•^'' '

II'I t.II

.f..'

I'j'i.

<'S i4 f4 '

;•

r

^
'

$

Si.
mp

p

i!

ft,
i/

s:
>;u

t

% % I, Yi "•''' :>
fi i4 i4 i/t

i#

V .l'

kA4-b/-

'i

s

/:

V /-;'^,vr
''' - 4^./

Jr-'

-y

iS

ni r4 m
%4'' m vj

iijf

'

'

«4 (.'J

' '• • •

u yffoff'

S'

,;! i'

' '

'!> c>'
O to"

'f V .

,,<1/
i/>

#7

* r>
O to

0..'
' m

a/
m

0/
w

'• ,

^«
, nj .

• /II
''to /li to
H w '1/7, /,n
qy
1^'

0/

IV

<*.v.

;V.to-'
Vi"

i

t..o
.^'''j -y. • ••i''y.' .•'.' f
•
f-'j,

.*•: •
...hf^iy ••

. *• • .. .

*.

. — ,.«

iC^S'

V-.,- '*.••>'•' ,-,...# .,

• .•.J''ft . . v'lwr'.•

,M.. .

-<*^1
.

'.'>

#...
.»

>
•., f .

•>
o

. i''%

i\>

• 5
-

•



"-J

'>1

t. ,

o

- ar^
- /'n-:,'

3000

A

2500

Benzene in Absolute Alcohol
-i,

^ "1^

•mm

131»

o
(D -P

LfN

OJ
OJ
OJ

o

o

IfN

OJ
OJ

hOJ
OJ

o

KN
OJ

IXN
ON
iH
OJ

o

LfN
H
t<N
OJ

o

ON
1-4
OJ

Ol
|5«N
OJ

o

o

r-4
OJ

1—4
OJ

r—

o

vo

H
OJ

o

LfN
1—1
OJ

o

O

KN
KN
OJ

•p
o

ir\
© -P

Hi
©

OJ

o
KN
OJ

o

o
r-

KN
OJ

o

o

KN
OJ

KN
OJ

h-

h-

d
o

o
A
o
o

iH

0)

•fH

-P

ft

T60

O
09

K\
OJ

^
OJ

o

o

OJ

OJ

a\

5

::s

X.5
"j"'

o

CVJ

rn

09

5

o

(D
fi
<D
t9
fi
Q>

m

T60
IfN
OJ

© -P

tTN

Q

OJ

©
td
13

ON
OJ

§

+»
©

d
o
o
©

•p
d
fH
ft

©
cd
•p
LfN
IfN
OJ

LfN

•eo
LfN
OJ

NO
IfN
ON
LfN
OJ

CQ

"d
VA cs5

Lft
VJD
VJO

bO
<D 4»
PQ (d

Ol

in

«
•d

hv£>
OJ

pi? cd

50
© 4»
PQ cd

©
-p
©
H
ft

OJ

©

a

o
o

o©

o

rH
KOJ

O

o
OJ

OJ

o

ir\
MD
VD
OJ

o
OJ

LfN
LfN
VO
OJ

o

LfN
VO
OJ

JdVO
OJ

svo

OJ

LfN
KN
VO
OJ

LfN
KN
VO
OJ

IfN
KN
VO
Ol

O
KN
VO
OJ

o

d
o

•H
p

d

fH

^
vo
OJ

d
d
©

50
H Pj
O -rl
-p
OQ

Ifv

jd*

d

OQ

09

IfN
ON

IfN
ON
IfN
OJ

E-«

IfN
ON

vO

OJ

KN

-=h

m
•

vo

•

h-

TSO

ON

o

OJ

H

H

. ''/"H

•'

I y'f

'

I

ir\
VD
K\
CVJ

00
VD
KN
CVJ

132.

CO
•H

bO

<D +>
pq cd

r<\
cvi

0
•d
d 43
» cd

0
VD
K\
CVJ

m
a

o

•H

5
OJ

bO

<D 43

pq 0$

0

0

cu
cu

•d
0 43
pq cd

,r , ^
'V'*

A4
O
•H
.d

,11'1

43

a
o

•?%

o
a\

t'tt

OJ

rH
I—I
fH

^ cu
cu JQI CU
.sr ^
cu cu CU

0

0
0

cu
cu
jricu

0
rd

0

o

iH
O
O

o

(J\

'H CO
43 0
ft •H
O

LTN

O

CVJ

C\J

m m
^ :=ir

U bQ

<D 43

CO pq cd

,Q

r^
CVJ

5^
CVJ

43

9

••3
0

<
0

43

d
iH
0
0

•5
0

•HI
0
d
0
N

0

0
PQ

0
•d

o
r—

0

» cd

c\i

CVJ

M

CVJ

Jzt
CVJ

m
1^
idCU

Lft
hCVJ

m
h-=t*
CVJ

0
00

0
00

0
00

CVJ

CVI

CVI

0

O
O

0
cd

I—I

•

•H
bO
0 43
PQ cd

iS\

43

!; • • '

0

0

0

0
o\

00
KN
ur\
CVJ

00

00

LfV
CVJ

irv
cu

0

m

LTi
jdr
LC\
cu

m

LTv

0
cr\

0
C7\

0
crv

0
CJ\

fy]

CVJ

CVJ

CVJ

cu

CVJ

m
K\
LTV
CVJ

m
K\
LTv
CVJ

00
KN
Lft
CVJ

00
K>
m
CVJ

00
KV
LTV
CVJ

00
K\
UTV
CVJ

0
rLTV
CVJ

m
V£>

m
vo
H£h
CVJ

vo
ir\
CVJ

0

LTv
Lft
ir\
CVJ

1—1

11

0
cy\
j=t
CVJ

0
0
LTV
CVJ

CVJ

ft

0

0

XI

-2icu

43

' V (1

0
•Id
0 43
pq cd

m
0

•H

bO

Q) 43

pq cd

CVJ

0

VO
irv
CVJ

IXV
m
CVJ

LTv
CVJ

00
KN
m
cu

2

Lft

UTv

LTv
cu

m
cu

cr\

LTv
LfV

LTv
cu

tn
o
o
m

0

o

CO
•d

0
0

vo
cu

43

cd

CQ

0

•H

bO

0 43

PQ cd

0
0

vo
cu

0
0

vo
cu

0
0

vo
cu

0
0

vo
cu

0
0

vo
cu

0
0

vo
cu

•H
43

0
0

vo
cu

•H

•d

r4

(D

43
(D
rH

ft

s
o

o

§

vo
cu

0

KV
vo
cu

m
cu
vo
cu

0

cu
vo
cu

LTV
H
vo
cu

0
r-4
vo
cu

0
H
vo
cu

0
rH
VO
CU

0
rH
VO
cu

0
rH
VO
CU

LTv

Vf>

h~

00

<T\

O

(D

0

O

0) ft
CQ O

o

CVJ

•

•

«H
0

X
B-*

bO
Pi a

O -ri
43 Pi
O 0

cd
0
*H

CVI

rov
•
•
HI I—I

X.
7

!?W-

0

', £>'. s 2'.

4 }

.;

f'i

4

K' 1
-!•

' \ ' \

^ 1 '•Ml

'''i

' 'V n.A,;C'

^ ,v
1

'X^

ff

s*?

C'

PI

t'

V

o
m
c..

'•'(,'

,1

/

% A

!/••

»
hv

1,-1

•/(

' !;

,:;a

# ,!/>

m r'
<'¥
i/t> 'X , i'l

w

.1'
f'vj
r
0

fi

^•j

sa

o

m
ni
jMf

'

f ;?• E
w .' t'

.|;^;

c

iy4,V

rxi
>"!!

rj
0

/>,J

i-'t

.

M?

n
Hi

W

If J

% '/('

r.i

f

Q

o

ijy

• O.'
0•

)j\

i/i

"' - '^'x -«-"

f

'.' .,Cf : . -fx
'
'Q/'
CI
m 'J!'
\A

'^

if?

te*:

w ia M

"t

, ' "i'i

A

«-s-'

p..

I'lj t- t fe,

lA

\' O

J-..

<' f ,/r/

'

Rjf

il-

fv f^s ' <•> • .'Qj;
/J J
•fi,
t/. /4| ^ /"ii'
/lii iS*"
/vj / V
'Vy ' m i^;<'
|/;
^#f¥

; Vs.

iX

>!*(»

,

i'f'

P r I'',." 'i'

s^, I"''*

,.',(»

lii

fi'

C'

;rf;.' • llJif..;.

s.
f '

'¥1

'.Irt

''•.' •<"'! •'-! '***' •' •>

/

iV
' ^

1 .r
A;-

f'J

'

th

/ ':|'f.;y;S
yf'i

f > ,15;

i

4- t'

(^ f' •

,? ,v M H

rV}

'A'"

't

f>]'\

*-iV

jfy

!•<»

*,

"i

•p ' CJ

-. ' ., •<*

- 5'

,

i'tf.
fittJ

• t V5^

i

, ' '

I y H
_ / «

a

'

yj-

v?. P

% '7 t4

,•

iX/''
'f-J
V"' UXfi*

'

& &' ' S*^

'.0 '"'t"' !s;

'

' 1% ?3

A\'l

^A'

' K*

<

nt

". „"',i;j'''' •',l,,,r.

/\y

to''

''

'i

" HM '

!'

s>r

% I y: 3^3

>•1^.

0-,

rj

1$

i4

;i/?

' p,
o JK
p |>"'i
p ' iH m
1^*
i)lf
f/)

tx "
W

!/•

M

E f:
0 ' :#
0J

0,.'

v.'

|.'V

• fQ,

0

a
,

t:-

f " •.

C

r

i/.'

ri,

XX

^ '*>

AH

*

A>

&:5.
a
^ H
f~.- o
$ U

-P m
O

't,/

I

2500

5000

Toluene

13^*
fri jp-

ip

» 05

4.-1 . ,

J: f '
'*-4

,,^.,^,.,.|{.u, .

*

0)

ri

•H

.! - ,

J-.V f;

/*) i'' 'f

" ' ,; ;

A , f

o
m

' }*•*', '

VO

O) -P

m (d
0
O

4»
Pi
M
O
CO

CVJ

o
a\

CQ

TJ
PJ "P
» 05

iTv
CVJ

•H

K\

0P

VX)
CVl

£>0

0

rt -p

p cd
H/'

0

o
e-*

p

A

CVJ

ITv

bO

©p
PQ 05

VO
CVJ

0

o

"p
pp
m o5
OQ

bD

«-p
PQ 05

t^v
-=^

VO
CVJ

VO
CVJ

CVJ
rH
VO
CVJ

VO
CVJ

CVJ

m

VO
CVJ
CVJ

rvo
CVJ

CVJ

m

VO
CVJ
CVJ

r-

VO
CVJ

CVJ

m

VO
CVJ

CVJ

r—

VO
CVJ

LTV

r--

VO
CVJ

•P

0
rH

P

§

s

9

9

'9

9

O

CVJ
fH

K\

CVJ

CVJ

h-

O
f^

VO
ON
VO
CVJ

rH
ON
VO
CVJ

CTN
VSO
VO
CVJ

ON
160
VO
CVJ

KN
ISO
VO
CVJ

r:fliil

-=t-

K\

+»

§

a
o
o
0
+»
o5
rH
P

43

0
,C}

PI
cd
P.
fi
o
o

rH
160
160
CVJ

o
o

Q>

0

o5

O
0
Pr
0

O
0

0
p

p

•H

H
0
O

o

•H
p
P5
rH

bO

P
P

O
Pi

•p

•P

•r-i

o

0

,d

-P
0

.

p

a

LTv
CVJ
VO
CVJ

K\

-=t-

•d

fS
<D

I—I

rH
0
O

f^~-

QQ

PQ cd

o

s

o

O

o

o
o
o

+3

CVJ

r\ ^
•
•

tf\
•

vo
•

h- w

a\
•

o
•
rH

H
«
H

CVJ
H

H

o5
P

•H
«W
0

CQ

iOim

fiVuM A

V '';'- ', »
illSilli*

*•

^€A^. f . £_/

ci
f ..

V
j} S~1 i^e44Aj^&q, I

V?

'"f

e
o
v)»

5ii>,
t|.

I
W

j;

«4-

fv

l4

xj?

P

' f-

'&•

C!S.

fe

C'

«4

M
O

e
&K

Al' ;

1»

QJ

45

mi

* W

/n • /m

??
t
w 'm

O

k
o

i

vo

<L4v

s;;
<•4

3>

s'

-

i--,
vC'^

g

iff}

!/)
/y

-0.^
l/,>

CI/
ifif

(1.:

t

C4

,'

' A' .-

W,
Ai
0/

•'

&1
,

^v

?i5

«% 4i'}

WD

^ #3

.I-4 ,>r

1

Ci

Ci

0

t:
IL;<
f !•

I—•

O

pi.
"4

M.

jr«-»

0«S

ns
CM

m.

m,*<'1

0/ fe/

m

'

•Of

mj

4J>

m'

di

la'

m,
Hi

s. ^

10

/c?
l/i

t'7

/•V?

/%
CM
4.0

O
.^1

H

¥^

t/i

O

«#,

fe.

S
,4/15

«

,•

HK.
®

H?

CiJ

rj

w

tr-j
«#i'f

§

g

-k"t

»', "•/*

•O'

I*-

m

•O.
O

•;Hi- • •"'.

^4
C/'

1-4

^ 5

'•i < !

"
'.'

t:

HI

'y

' Mi

•o
o

<54^

X, i'
rj '/

7

3000

A

2500

Ethyl benzene
It

/
tp>,

fit""

) "« t' " '/

M
o

•H
•p

o

K\
K\
CVJ

ma
d
O
•H

+>

PI
R
O
TO
d
<U

o

CD
•d
d -P
N d

5
CM

CD
d
Tt
c©
© -p
pa d

'

' .•

'f,

CM

o

KN
CM

cr\

p—
CM
CM

to
CM
CM

CM
MO
dCM

ON
rH
IJCN
CM

m

C)
CM
NO
CM

f^

o

rH
VO
CM
CM

•b

O
P-

(D

iH

4»

+»

NO
CM

©
d

CM

vo

H

KN

iH
NO
CM

NO
CM

-P
d
d
-p
CD
d
0
0

•• fip ?•

'k' i"

©
-p
d
rH
PI

i\*;
1. 0
>4"' I',

CD

.1. • ;•'

d
•H
bO
© «P

o

ITv
NO
CM

m 03

m

LfN
NO
NO
CM

•t3
d -P

m d
TO

d

•H

bO

© HP

pa d

©
-P
©
H

p^
dhCM

i
o

0
0
pCM

P^
CTN
NO
CM

LCN
ON
NO
CM

O

m

NO
CM

o\

NO
NO
CM

H

cy\
NO
CM

'

©
d
-p

>

NO
CM

rH

o
R
O
+»

©
d
p

«

d
p

TO
d

rH
rH
©
0

CM
0
0

LCN
to
NO
CM

d
o

•H

d

o
©
m

KN

^

m vo
•

•

pw

ISO

CTv

o

r-l

r-l

H

•

O

iH

TO

d
d
©

k

d
rH
fit

•d

d
E-«

K">

d
0
TO
•rl
R
d
PI

r^

d

CVl

3

R
•P
0
©
PI
TO

B

•rl
+3

o
o

•

s

0
0

CM

bO
d
©

' «

h-

tq

d

rH
o

/

1*''' ',

d

d
o

rH
©

CQ

(t>

s

o

d

©
R
©

d

i. L3f.
V

4,1^1 ("l"

f>'" ,;

«>{- i,p

f»'(
«!

^0'm

'to.:

'^fl'V.

wi
iS/'

,W\
I^''»

v:
•'ft?,!'
is?
SI'

to

-'m

• '^v

0'

0

f-/

<Jtl

..r«#

il
flH.
•i>ri-

t.j.

O

m

O/

A

C)

ns

f'i

0'

tj.

5-4

f'

o
c>

j;"»
-1^

0
f«<w» ,

•mw,

|;i

0/
i/3

ht

•<1
to

/o

Cv'
iCi>'

1/5

Cf

#/

•.)i\1,
,

O

.

Ci'/

O'J
tuV

/'W

fn

tr^

OS

QJ

io

'

, V

n,?.
}"t

# • s«

s

l-r

*/

«!<-

4?'
V'

t/l

,fl'> !
ilty

<i,t.

a,
o

0*

to

h""*
PS

i:t

H
is
J- t'iv

i»>y.tf

f-n

ro

r»'

-1 ''

'

//.'

O

o
O

{If

u
I'-P
m

"fife
?7r'M,

4c

-a

3000

A
n*Propylbenzene

2500

13&.
;'-'V •

•.'jV^

'IJI:
'f;''.';'-1,r

iii
.',.A.-

i. .

.

./ ^

,/?.,. . ...

,

/AI./.

;1^''
i. . ,^

M
o

•<4"'«s:i##fi?-«MW>i'«i/fi

a

I:

o
uLUv
CO

P

in

•H

PH

hO

m

<D4»

m cd

CVJ

-p
PI

h
o
GO

§

TJ
a -p
M cd

CVJ

p

vo

CVJ

o

CVJ
CVJ

CVJ
CVJ

CVJ
CVJ

r-

H
©

o
©

iH

o

in

in

CVJ

p

KN

m

CVJ

KN

CVJ
CVJ

§

vo

CVJ

in

fH
VO
CVJ

P
©
V

P

o

O

©
P

vo

P -P
m cd

Oi

cd
rH

vo

CVJ

PI

©
P

50

k

CVJ

160
CVJ

m cd

iH

P4

CVJ

•HI
bO
© +>

©
{3

O

160

P

(t)
P

>>
P.

cu

in

«)

GO

•d

rt

KN
CVJ

CVJ
C3V
CVJ

o in CVJ
in ON H
-P" -rJ* in

m

<D

o

p

CD

a
o

in

P

© -P

PP cd

1

o
rvo

P -P
W cd

•H

o

CVJ

CVJ

<T\

o\

©

m
P

CVJ

m m
vo vo

CVJ

o o
hvo vo
CVJ

CVJ

CVJ
O

o
vo

o
*

CVJ

©

cd

©
P
©

KN

rH

^
9«
©p s

f—

o\ vo
r— h—

m cd o
o

CVJ

CVJ

o
^<^ o
r-j

o

cvj

CVJ

h-

CJ\

r- vo
CVJ

LTv
•60
VO
CVJ

LTV
160
VO
CVJ

p
o

LTv
160
VO
CVJ

p
p

cd

^4
P

P
©
o
p
o
o

bO
P

g
5-

o
o

CVJ

KN

-=J"

iTi
•

VO
•

h-

160

0\

H
«
r-f

OJ
*

X

M
r—I

P
O

P

p

A
e^

©
CQ

rH
HI
©
O

©

©

o

P

•H

P
CH

O
P

©

A

P

©

u
©
A

&4

-/

t.."i..';: A

"W: i.'.. x...

t.

"• V..^li'i.'v.^

..

. .

'

3000

A

2500

i s 0 -Pr opy llDenzerxe

llH5.

• If"

/df

o

-A'

0
0
Kv
CVJ

/ffr

'J ,

t"

r-

TSO
CVI
CVJ

Q

LTV

vo

CVJ
CVJ

CVJ
CVJ

JT'i

m
CVJ

r-l
K\
CVJ
CVJ

>^J
'V

0
<

•

OS

XI

43
5fiip

o
0

0

CVJ

CVJ

r<v

.!<• 'A -'jf'/ - , ^

I* V

•H

r •

a\

CVJ
H
Lfv
CVJ

v'i'i

rH
iH

rH

0

o

0
X!

a
f:i
bO

43

0 43

ur\

0

o
vo

ma

CVJ

KN

o nd

«H j:j43
43 Pr| <e
PI
F4
O
0 0
;Q P
-H

m
CVJ

LTv
CVJ

43
0

P
o
o

0
H
VX>
CVJ

bO

© 43

a>

o
zo

« cS

0
H
V£>
CVJ

0

iH

vO
CVJ

0
r-l
VO
CVJ

0
43

p
|H

Pi

a

0
IS]

a
0

5

•ti,

P 4»

ma

0

, ''*1
ri; !

.P

T60
K\
VO
CVJ

43

>»

P4

£
hca

VO

LC\

VO
CVJ

VO
CVJ

w

>50

0

VO
CVJ

VO
CVI

bO

0 43

fQ ai

(J\
CVJ

o
o

0

0

ir\

43

cd

m

VO
VO
CVI

p
VO
VO
CVJ

p

o

"H
43

P

0

0

P
bO

0 43

ma

43

0
iH
PI

5

t

CVJ

0
rH
hCVJ

0

0
CVJ

0
VO
VO
CVJ

tso
VO
CVI

43

H

rH

P

VO
CVI

VO
CVJ

P
o
o

0
O

O

H
P
P

bO

P
P

f4
O

P

0

Xt

43

VII

P

•rl
rH
H
0
O

§
iH

P

O

P
0

P

0
!4
0

«H

0

<§•

0
T4
f-l

O

0

p

*P

g

o

iH

o

f-l
4>
O
0
PI
0

o»
o

CVJ

KN

JSt*

Lf\

•

VO

•

r-

-CO

C7\

o

iH
«
H

CVJ

0

r4

43

O
0
CO

rT4fe:
•f

H

i#
XV
iiiii

.:i ^4,'iV'sX..

M

rn^.'

H

m
• '•ii

;T'Vlvr:v''''S
' h'k \\ "' '•^'''

«.«. *5

. ifi' ''i

«4-©

n ^-k
(it tx
f ^^
CA- O

o
OT-, , €¥
rtf
/I!

w.l

w>

•Y' , ,< .,|f;
0

t>

in

r.j-

''%;i 0,' ^ C;-Y
0 M

p/
i' )

^

• •W'^y.

»•: • •.

Q

,

^"4

•! f S'.

,' j

I

'J' I

<'>.

' •"«

'i- W'

K:. AX-

f/Y'

p

M

tZ^S0')
( '

'Hi.

^ 't
;o.>

>'i 1''

n

f/i-t

i| ,4

1-n

4^i

,.'t",.

rj •;

'.1^'
,.
•ifJ 'jj I,1/:^

O
O

I ';>'

f*i •'

. >\

l>

. • , • ••vlwf-

(|,>

' ,4 " f

^

•4

'J

',- i/ts

h
la't)

jNw •
fciff.;

0

•• 'lIVil' 'V,''''

I

7)

fttaj ^

a^'
i/>

*"?

^
0

O'^

>"
- ' J'
y

ri.

m

4/
v(t

a;;i-.t*

^ ,a

H,

Vi to

O

»•«'«

WH
40-

fx.

»• • " • » • • •)»•' •' • •
J. .

"I
I .

f-,

a'

#•

/'ki

, ; , A' •. ,•

•;•»••' .•.••,*•,

• • ••

»

<>

<n
- 4?^!
-Jv. • ih",yi'r

' ' ''*'''< > ''

I. \ J. J i« K

/f.,

,

;((< 11 s
^' V' t

IV

'4

i/'i

J"6

f

m M(, • i'

h /'
' f, *1' ' '' '

«
o

o

M'f, ••

m

."k,,
^

c

IC
.«3

#r
..
,T.., •.

-'

:500

3000

n-Butylbenzene

r

V- '
t ''

lk-2.

m' '^.v

'"i '' /•••''

J

M
O
P

B
o

CO
{::

bo

0P

pq (d
ca
'd

• •: ;• • • ' .•; , .•

pj 4»

cd

0
O
-p

P,
o

CQ
jot

09

• ',

w
<D +a

a
Q

CO

o

ir\

VO
CVI

o

a\

K\

CVJ

CVI

CVJ

CTN

CVI
CVI

CVI

CVJ
CVJ

CVI
CVJ

CVI
CVJ

CVJ
CVJ

m

K\
CVI
CVJ

fH
iH
0
O
0

fCj

h-

P
CVJ
ISO
KV

>

CVJ
CVI
VO
CVJ

• Ji'y-t "'••

-d

o

o

• f

<A
<D
i:S

H KN ^
ifv iiK

«)

•H

PO d

vo

CTN
CVI
1^
CVJ

ISO
p
VO
CVJ

P

CVI
p
VO
CVI

%

P
at
Pi

o
o

ISO
KV
VO
CVJ

PJ -P
W tsJ

0
P

cd

Pi
i-l

>>
•P
0

t

09
Pi

0

o

eso

VO
VO
CVJ

0 -P

m d

m

p

CVJ

iH
VO
CVJ

LTv
VO
CVJ

H

m

0

CVJ
hVO
CVJ

-p

cd

m
el

•H

bO

0 -P
P) cd

0
P
0
rH
Qi

r—

VO
CVI

CVI

h-

VO
CVJ

CVJ

1^

VO
CVJ

o
o
0

•;

B
o
o

o
CU
CVi

o

H
i»w
OJ

o
o

hCVJ

K\

cr\

VO
CVI

o

CA
VO
CVI

o

(A
VO
CVJ

Pi
o

0

o

o
o

c\j

-=i"

irv

o
p
o

VO

ISO

ON

o

H
«
1-4

Pi

o

0
P
Pi
cd
Pi

B
o
o

0
p

d

p

o
M
H

iH

O
Pi

•d
H
(d

ei

o

0
Pi
0

p
p

0

U)
Pi
•H

PI
P

Pi

«M
0

0
Cd
0
0

0
CO

J
: Ts

V . •

t;#

mm

a

-

ii^fa
V

''

11^

3000

2500
sec,-.Butylbenzene

' 'f i

t '

»

Ikk-.

f'

CD
PS

rma
bO
© -P

m

n
PS -p

VA a

Vt?:

PS
•rl
bO
<D +>
PO 0$

§
+»

P4
fH

o

CD

5

P
H
>»

a
4®

I

o
0}

CO

LTv

o

OJ

CM

O

hCM
CM

o
o

m
CM

O
VO
CM
CM

CM
rH
lf\
CM

ISO
JdCM
CM

O
J=t
CM
CM

O
CM
CM

-

''

' •; T";• i\.,"
Y4 .. ..
,•
'

ISO

in
CM

CM

O

B

o

'• f

m P

ir\
-=t

•
P
P

rH

'

rH
©
O

tn

CM

©

P

'

o

VO
LTv
CM

+>
cd

m

VO
LPk
CM

P

\r\
m

VO

.'•

CM

,' i'

O
ur\

KN

!

P

©
PS
bO
© -P

03

•d

VO
CM

T60
iH
VO
CM

o

O

K\
VO
CM

M c3

m
p

VO
CM

S

P
©
PS

O

P

VO
CM

o
o

©
p
05
rH

vo

Qi

CM

©
$

CD
PS
•H
bD
© -P
PQ 05

O
iC\

vo
CM

iTi
VO
VO
CM

©

•d

-p

o5

©
PS
bD
©P
PQ o3

©
P
©
rH

Qi

i
o

LC\
O

O
O

CM

CM

h-

f^

LTv
CT\
VO
CM

LTk

O

VO
CM

VX)
CM

LC\
VO
VO
CM

O
OV
VO
CM

VO
VO
CM

LP*
TSO
VO
CM

m

TSO
CM
O

O
h-

o

VO
CM

©
05
PS

o

o

160
VO
CM

p

u
o

CM

o
o

-=i-

m vo

p

o

©
CO

,,

feki'

o

©
Pi«
©

g

0
©
p

u

1
o
©

,cS
P

PS
P
r-i
©
O

H
cD
PS

©

«H

©

©

©

*r\

&

U
P

O
PS

bO
PS
PS
©

• -k

rH

'Jkf .

PO ea
(D
PS
Q
N
PS
O

O
T60
CM
CM

'

m

m

CM
O
KN
CM

X'

. ';

kv ' ' k '

?'''V;

vl

h#

xo

o\

o

H

CM

H

rH

H

•

o5

•i

#

J

4

•

5^' '

, .iyiUf, •,- ••,- •

.•> <

f

!

•••f ' • '»,[
pt"

M

%

i "J

<•

to
4)^
/

)

•'0^'
i>4

'.1*^

H''

•:# 0,
;#•

ix

ni
0/

<!^r

m
Cb*

I'n

CJI

0./
:\-xm-'

•t.4.,

U

m':

O'

'4«r

iy ' &.!

J

.to

w

•l..'

-#v.

'O'

m,}

yf'

.'O"''

,i'^

1" •.'?'^''<i'sfe-

<4
& M

0,
m 0
1& #. / u

W'

«%<;•,•

• •'1^
'i

}r,>

'h'.
^•4. ®

"'' ^'1 '^•'F''

-';

;o

m

^ ,0^

0'

j' I'

to

f ^ V/f '

in
! ltf*C

. ^ ' •" ^

try

•m , to

Mr::

"•M
W*"

••H
,®

y^iSi'''^'- :"WX.

M-i

'p ^

.to

O-

': :M-

•

»5|-'

«^ •'

f|

i';

o As>'

ft £ s

••

•, • iiki-

iS •

to

?- V

f».,

'<%•••••»

r"»

>'l

.C
¥

. i"

•^f

0F

r?
'44.

O'

. i4

©•

ir

'i>

' '/ •

i..

(...

'o<;

•

.Vf>.4"'^

<f/;'

>4

W'
-P;

«4
O

'' F"f,'/

o
w

m.

m .«

3000

it

A

2500

ter. -Butylbenzene

l'l-6.
0
d
•H
bD
0 -P

o

o

n (d

K\
CVJ

0
•d

o
xo

+>
d

t<\
CVI

CVI

CVJ
rH
K\
CVJ

O
O
KN
CVJ

o

o

CVJ

CVJ

o
o
m

CVJ

CVJ

LTV

CVJ

o

ON
CM
CM

O
rH
CM

o

ISO
CVJ
CM

in

vo
CVJ
CVI

M
o
p
fd
P

n

o

o

cvi

CVJ

r_|

H
0
O

0
d
4-4
60

xo
m

-d-

© -p

m cd

CM

;i y'-v.j

xo
m
CM

160

160

iTk
CM

ITV
CM

0
»d
p
150

o

•H

0
•d
pj 4^
tA cd

O
VO

m

wiiisJSii

Qi

U
O

CQ

5

0
d

CM

60
0 4S

m cd

VO
iTV
CM

O
VO

m
CM

o

r<\

irv

p

f^

d

CM

0
p
0

d

Lf\
rH
VO
CM

•H

o

O
rH
VO
CM

O

o

VO
CM

CM
CTV

m
CM

o

*

0
p

p

(d

rH

0>
d
o>
N
d
0

0
d
d -P
1^ (d

rH

0
d
•H
60
0P
PQ cd

4^
d

m
1

n
0
+»

0
d

5
'

VO
CM

:

o

0
d
p
60
0P
PQ cd

VD
VD
CVJ

B
5

o

O

O
K\
VO
CM

VO
CM

.d

m

o

VO
CM

VO
CM

VO
VO
ISO
CM
O
O

0

p

o

0

G5

VD
VO
CVJ

VO
^0
CM

LfV
LTv
1^
CM

o.
rCM

o
o
CM

iTv

vso

VO
CM

ITV
150
VO
CM

d

0
O

d

<§•
M
O
P
O
0
C»

o

oj
•

t4\ ^
Lr\ vo
h>•••*•

ISO

C7\

O

CVJ

0
td
p

d

p

0
rH
O

o

d

1—1

0

cd
d

•r4

o
o

M
d

d

60
d

B

f4
P

cd

LCV
150
VO
CM

cd

P.

H
rH
0
O

o

d
0

d

o

p
p

o

s

0
Pr
0

0
P
f4

•

p
cd
0
P
0
I—I
P4

P,

u
o

p
tp
0
jd

cd

0
p
0
EH

V
if^

11

O

o

34
O ' C>
'
O

If*^; • • hn

O-'
i/l

oi-H

fi
o,

"

NS'

o

/^'•S

cv
mk
^

1

'

'•- U

; ^ ;' ' ', ;

f, 1?

i ' „

' '

<3^,

'( 1 ,

-

'

'' - ' ./,!
i

'

'

' ' ' ' !

.

OV
•'.jf' i;.

m

m

Si:v s,a-^
i,':>

U''
m

g

^'-T
?/'

-n

r"

8

' (JT)

S
•rr

.'M

.'

^•

O-'

*;'»

/''I

'"

'

500

1
155
-'••fl'i-: '

•••"'-••,•••;.•:••-•

W'
JU 4

"

1
-

1

400

E

300
•• • .

•

- •

'• i

•'
: ';• • • \-m • .

. Vf

. : • •' • • '

m

•: /,-• •

Tt.

••

S

'. . • . • . • • »;-• <

200

•

*f<'i

;

, 3- ,

•J *

O"
~
O-> '

>'

*

-- -,-

,...

. • . •'• ../I:--

:•

. •• ->

'^1

•'

r-i'

J':-. .-

s5--''
•V

"vyiy

.«,

-

J

;

•,

•

• • -y;

r

3000

'

A

o-Xylene

2500

••

^

|.,4

llLS.

>1,

(0

P

•H
bO
<D -P

o

r.

VO
K\
CVJ

pq fid

LP
CVJ

CD
•d
P -P
pq cd

CVJ

o

rH
IP
CVJ

o

o
o^
OJ
CVJ

o
CVJ
CVJ

o

VO
CVJ
CVJ

o

LP
OJ
CVI

s

CVJ
CVJ

LP
CVJ
LP
CVJ

H
LP
CVJ

»
M
o
•H
P

s

o
CO

•V

rt

:

m

•H

LP
o\
LP
OJ

CO

Pi

o

•H
-P
PI
PI
O
CD

5

*d

P-P

P
<D

0
,d
p

O
O
VP
CVJ

ON
rH

LP

: f;

(0
fl

P

*1-1

LP

LP

0 -P
PQ d

VO
CVJ

VO
CVJ

CO
'd

T60
VO
VO
CVI

bO

W oS
0

r-J
H
0
O

rw
LP
(M

bD

<D -P
o:) 03

CO
p

§

P
0

d
o
o

p

0
p

o
xo

bO

VO
CVJ

0 -P
W d

o

CO
'd
rt 43

ON
VO
CVJ

m cd

I

0
p

H
cr\
VO
rH
O
O

o
o

hCVJ

0
0
d
•H
bD
0 -P
pq tA

0
p
0
H

P

a

(d

SB

'3S

S'

O
O

LP
KN

LP
CVJ

o

o

CVJ

CVJ

hCVJ

h-

h-

CVJ

CVJ
CVJ

o
CVJ

d
o

CVJ

p

d

•d
•rl
d
0
PI
O

H
cd
d
C\J

K\

o

^

m vo
•
«

ON

*

O

CVJ
*
H

*'4

0
E-«

o
o

-p

0

m

: t?:-. 1:

J", '

^

\, V

w \

'

' V-

*

• 500

2500

3000

p-Xylene

150,

^4$- •

o
vo

K^
CM

m

ISO
CM

O

KN
CM

CM
CM

cr\

o

CM

CM

O

KS
TEG
CM
CM

O
TSO
CM
CM

LfS
CM
CM

m
r—
CM
CM

M
o

•H
CQ

•d

-p

CO
S3
•H

/V-

bO

0p

§

ITS
X50

OJ

CM

o

O

-=3"

CM
ITS
CM

r—

ITS
CM

W\
CM

S3

•H
P
PI
S-i

•p

a

o

o
CM

C\s

rH
©
O

VD
CM

PQ d

o

o

ON
ITS
CM

©

LfS

CO

•d

J

^

. r. r

ITS
VO
CM

ITS
X50

o
vo

VO
CM

©

CM

O
VO
VO
CM

ISO

TSO

vo

vo

vo

i

CM

W ctJ

P

o

O
LfS
VO
CM

o
CQ

0

p

's

'!l:

irv

•H
bD
0P

VD
VO
CM

PQ cd

m
o
S3

<0
rH

>»

t

••' • ,.•

:: ,

.

LfS

:.:ij , ;

r—
vo

S3P
» cd

CM

o
vo
vo

hCM

CM

JH

O 0

© m

p

o
vo

td p

rH O

ft ©

CM

•H
© h

,P cd
CO
S3
•H
bO
0P

5 V''

, k

.

O

o cr\
r^ vo

m ci

CM

CM

m

Ti

CM

TEC
CM

N cd

CM

CM

m

0

d

•H
bO
0P

PQ cd

bO
S3
•H
S3
0
PI
O

©
P
0
tH

o

s
o

o

o

LCS

cy\

T60

r«~

CM

CM

CM

r—

LfS
OS

ISO

o m o
r^ vo vo
r- r—
CM

CM

CM

vo

CM

o
KS
r-CM

ISO
LfS

crs
vo
CM

o

KS
hCM

ITS

CM
LfS

CM

CM

r^

CM

LfS

LfS

o
^ o

CM

CM 0
CTS ^
LfS P
CM

crs
vo

vo

o

m

CM

KS
pCM

gv
hCM

§•

LTk
GTv

O p
•

O '"H

KN

EM

iH
© rH
cd ©

^ o
p^
o p

O
LfS

•H Cg
-P H
d .Q
H

rCM

^§
H ©

cd cd

5^
O

CM

m vD
•
*

h-

ISO

o

ON

ai

H

u
o

p

o

0
CQ
ii

« in ••
U.

^.-v;

V\

;A

1

pes

jst*

H

rH

«H 0

© 0
cd ^
E-« E-«

''h

Av ^ - JfTl
Q • "J
Ai
.^•';.5 .. . :tsA'
in 0 0 /"} i'H
iiy. 0, . 0 , m , te ^,.0

in
in

m

Oii
iji-

. ' i?f< *

& i>i''

6

''-J

'n ff ,"}

f'

U'
'

Z'
///:}
V

"

/•S.

/

ij.y • • • k'i

prr i^'v' »

C^»

U

•;.? &

O

',, C-'
o/ 4 Oi/
.1^,1- 1;/J

<ii

XJ"

. Iri-";

j;r<wVf
r-f J

n':'

it

<

fX>

/t>

Yxi

'i;

k

ti a i
o
4
iS '
L^,?'

,

/W' 't/li

<xx
\n

/o
C'y'

p

4/)

/t)
i¥'

• • .• ^ .• €">

o! A4
o
m
/VI
AI

/•>!

0'

J'''

wA' .

id

i/;

•..Xv

a* o
o
a''
i/>,
in

/t>

u. •..'•w'-^fl'

iW '

«7

J

Ai
, i^}

.. 0.
v'iX:'

/'i,f:.

f'W

: r:i

/.I,/

i/>'- :0: , l/V

/;

"XfV#

l"

r; r//r;-^

b'j

j/VviQ

]/i.

•• »Ji'4

4i«

•' l-v
1^ •

OJ."?"'

i-

t":. 0.1

w.|

/t

/ # ?:;

fi-;

\
r/

••41

f*.

'fc,
»•

• :• ••

• iO .
••* ' •

•*'

14''"'
c'/\'. v;4v4':4:

'ttr^ ••

- 3 tf

l/ldA

kl^'iT}^ ^ 7, 33/ / i/tsTj

7^0000
•• •;••

•

•-•

'.C .

• •

•. - • •

.•••.••..•

.

25000

E

!P^'
20000

\0

'

'• -

j

•k , ,

. /

15000

• :•.!'• ' ' • .•
•

-

:

•

30C0

A
Diphenyl

152.
/i

Diphenyl
- .ft

AlDsorption
Begins at

Sector Opening
.

•

Ends at

Begins at

22IW

Complete

0.0
.1
.2

A

h-- •5

.6

2630

.7
.g

2650

2225

2605

2310

2220

2560

2365

2200

2520

Z^13

2190

1

.9
1.0

•, •;!

• •'''•• 'i

(

1.1

1

1.2

'

2180

None

2170

The final dilution was .OOOO396S M, the plate constant
25,200, the cell 1 cm. thick.

-•.\,',i

ft'wi

;

I',/ ,

vc.

•
]

< '

li.

•

40000

35000

/

1
E

/

30000

/

\

7

25000

t

\

1

'

3000

A
Stilbene

2500

•

=^' I

^UQm

•JMA

i

ii0ftl

\--

4 • •;*'..

.V

SfI«'!»;.VtW.lli(!6S!Ma«*lfJI!»^JSW»T^

i''«1?'<«i";«l»«?(>««»^««<K««IIlWail««!lJ(SBiailf«wai»^

^O0o

•iif^

iiyjj"
jr--

3r:'.:^2'sd

15^.

Stilbene
Absorption
Sector Opening

Begins at

0.0

Complete

Ends at

Begins at

.1
.2

^7

3390
3235
3235
3170
JXko

.6

3030

A
•5
.6
-r;:'

•9
1.0
1.1
1.2

im

:

•

2550
2730
2870
None
ft

liiii

'''h'VV" '••
'

''

r'-

V

i

J

^

The final dilution was .00002222M, the plate constant,
^5,000, the cell 13cm. thick.
There was no blank cell in the comparison spectrum.

.Vi. f,NM' >

h}' '

-'
1

4.;-

'(

-

•

,•

WM
UJ,.^ f I,

fSsSsi

^ ,

r .

131

witii
. '

^

'

^

.1

'

800

• t-

6QQ

E

Sm""'"

400
.•kil' •

15"'
if *'

•K>.it:^

3000

A
p»Cymene

2500

'!yS'

m

15^.

!®,

GO
PJ

bO
© -P

h-

vo

0

TBO

m OS

cu

CU

KN
CU

10

0
iH

TK)
TSO
-zd*
CU

ISO
iH
LfV
CU

«c#

«-p

cd

CU

m

0

cu

KN
CU

KV
K\

cu

uc\
vo
LTV
cu

0
•50

m
0
vo

LTV
0
VO

0
iH

^<^
CU

CU
0
K\
CU

0

cr\
CU
cu

CU
TSO

cu
cu

0
J^

cu
cu

•

m
cu

M
0
•H

-;r4

0

©
•H

bO

© 49

CU

PQ cd
m
•d

0

^ "P

5

cu

(d

O

49
Qi
U
O
OQ

0
K\
VO

B
o

cu

0
K\
VO
CU

rH
iH
©
O

tn
vo
cu

©
rC5

49

o
irv
vo

©

CVJ
LTV
VO

•H

bo
© +9
m c3

cu

O
m
vo
CVJ

+9

§

49

o
vo
vo

©

xS

O

f3+3
M cd

CVJ

o
vo
vo

i.

OJ

o

o

h~

vo

o

P3 cd

CVJ

O
r4
hCVJ

©
49

cd

bO
© 49
PQ cd

©
49

©

ft

Pi
0
©
•ri
PI

cd

©
PJ
•H
bO
© +9

©
P!

49

o
o

(I>

o

©
Pi

©
49
©
rH

0

vo

ft

e
o

XO
CU

o

ir\
r-

1^
CU

0
vo
r-cu

Lfv

m

i^
CU

a\
CVJ

r-

m

vo

CVJ

rH

CU
rH

CVJ

cu

O

r^

0
LTV

r^
cu

m
jztrcu

CVJ

w

vo

CVJ

LTv
iH
hCU

Lfv
hCU

o

©
fpt
49

T60
VO
CVi

V50
rH
CU

s

cu

0

cu
cu

50
1^

cu

cu
cu
1^
cu

Lfv
K\
h-

cu

tn
cu
hcu

vo
KN
m
rH
O
O

CVJ

©

cd

r—
cu

fS

o
•H

49

P.

bO

P!

PI
©
Qi
O
f4
O

49

O
©
CQ

o
o

H

CU

KN

LfV

VO

h-

ISO

CTv

0

iH

CU

K^

H

iH

rH
T- i

iH

•

«

•

•

U

O
©

ft

cd
ft

1
o
©
49

Pi

•H
H
iH
©
O

I
rH

•r4

xS

O
PI

rH

©

cd
Pi

^4
tH
©
,P|

E-»

cd

©
M
©
EH

.•• •

•,

20000

-I'

r,

15000

; ;• • . ' ,

1

10000

1

5000

-•

^'4
1:-=-

• - •
y,-i

•

,

^ • r-T^.

• -4#^: -..-v-.-, • ••
(*-S.

• H' '

4";., . -.

" /

3000

A
Quinoline <

2500

'i

''vl(0fK
J ,(»•' '
L'

/

15^,
'. 'i'if
i 'I ".v-

CO

0
bO

ir\

•l-l

ON
K\
CU

<D -P
PQ d

m

CO

h-

rt -p

CVl

0}

o

T50
^<^
CVl

ir\
ON
CVJ

CO

o
vo

bO
© -p

fi

m tA

o

H

o

K\
CVJ

KN
CVJ

r— vo

^0
UCN

CVl
LfN

CVJ

CVJ

r<N

tf\
CVi

K\
OJ

o
CVl

ir\
CVJ

o

ON
CVl

KN
ON
CVJ

ISO

ITN
ON
ON
(M

LfN
ON
ON
CVJ

IfN
ON
ON
CVJ

H
©

CVI

o

o

•H
•P

P4
M
O
OQ

Q

03
-P

M ce

©
J0
-p
160
KN
NO

tn

,4>feik

©
p;

IfN
H
O
KN

•i-i

bO
<D -P

m cd

LfN
H
O
KN

•>!:

LfN
H
O
KN

"P
cj
©
0
O
o

N
-p
O
©
PI
© 03

so

03

&a cd

•P

K\

© 0
H O

(D

0
O

0

<§"

«

© n
3

Qi m

/
,/ o
CJN
o

©
•irl

bO
© -P

m cd

KN

©

'd
&a cd
©
P!
bO
© -P

m td
bO
Pi
•H
Pi
©

<§•
P4
O
-P

o
Tso
o

o
ho

ISO
H
H
KN

ISO
H
H
KN

KN

© H

Xi ©

P 04

•. o
^ o

KN
O
CVJ
H
KN

LfN
CVJ
H
KN

©

h~,a

O
KN
H
KN

h- p
H
O PS
O -H

o

• H

©
-p
©
r-4
p<

O
CVl
KKN

§

o

o
o

rH

*

CVJ

O
JA
CK!
KN

K\

O
H
KN

^

LfN
VO
H
KN

LfN

o

O

ir\

H
KN

NO

O
LfN
H
KN

h-

LfN

-©•

1—1

KN

"CO

LfN

:©•

H
KN

ON

2

JIT

H
KN

(0 ©
© O

5
H

PS 'g

KN

O ©
•H H
P p

CVJ

KN
•
HI

^
•
H

ITN

•H PI
•O
©
H ©
H ©
«H
©
© P
P B-y
E-i

©

m

...V V,
J,

V '

15000

10000

5000

3000

A
Q,uinaldine

2500

160,
m
f=!

1^
rH

tiO
<D-P
PQ d
CQ
'd

CVJ

ON
O
UN
CVI

-p

bO
(D +»

m «d

-p
p4

o
CO

5

160
160
KN
CVJ

CVJ
160
K\
CVJ

o
r<N
CVJ

o
o
r—

•
M
o
p
p

CVJ

o

o

>50
CVJ

CVI

H
H
©
O

rH

©
Xi
P

•j'.ilr:

•s

o
o
o

P! -P

KN

UN

o
o

KV

CVJ
H
O
KN

CVJ

rCVJ

VO

CO
p{

so

•H
bO

© -P
PQ eg

KN

ITk

OJ

O
KN

O
K\

P
d
cd
p

o
ro

M
P
O
©

©
p

©
PJ

K\

Or

•H

©
P5
n-l

*d

® -p
PQ 05

O

UC^

iH
K\

o
K\

UN
K\
H
K\

UN
r<N
rH
KN

o

bo

;',i,S,r:lift

cr\

•H
If.i.M

5 •p

d

m

pj
•H
bO

©P

pq o5

©
P
©
H

P<

i
O
o

O
rH
KN

O
-drH
KN

UN

jd*

rH
KN

O
UN
rH
r<N

as

as

CVJ
r<N

H
rH
CVJ
KN

O
O
CVJ
KN

UN
ON
rH
r<N

UN
ISO
rH
KN

O
160
H
r<N

o

160
rH

o

160
rH
KN

a©

p

O
O

iH

03

rH
rH
©
O

UN

o

•r-l

P

0

rH
P

bO
fi

•#

o
o

CV]

KN

*

LTv

o
o

p

VJO

«

h-

160

a\•

o«

H

CVJ

1

CJN
UN

•

rH
KN

©

Pi
cd
Pr

iH

\o

o

©
Xi
P

Cd

O

«
3

©

a
o .
o

.s, A V

m
xS -p

Q)

i.'

*
B
o
«H

OQ
Fl

o

CVJ
ON
r<N
CVJ

S
o
o
©

xi

Pi

xi

O
PJ

H
cd
P!

d

•H

«H
©
E-t

•:

©
rH

TO

©
IH
©

Xi
6H

©
0}

•""''-xj

> > ^• .
V ,fe-

•'I
^ -'^1
..

bkiX:

.. Ci

Absolute
Persistence

Relative
Persistence

Oompovnd

Band

p-Aminobenzoic Acid

2710

llSOO

9700

Dimethy1-p-Aminobenzoic 27^
Acid
3130

1000

550

1300

goo

Methyl-p-aminobenzoate 2S3O

IS5OO

13300

Benzocaine

2S5O

ikkoo

13400

m-Propyl-i)-jaminobenzoate
Butesine

2S3O

19900

15100

2S5O

1^700

13100

Tutocaine

2900

20000

igooo

Tutocaine (Base)

164-00

l4600

Procaine Hydrochloride 2S9O

21S00

15600

Procaine (Base)

2900

I9SOO

15900

Butyn

2S65

21000

13500

Butyn (Base)

2S60

21700

17200

Aniline

27SO

14-30

gio

Aniline Hydrochloride

2SI5

230

110

Aniline Hydrobromide

,2735

320

100

Stovaine

2730

1300

Alypin

2750

1100

350
400

p—Hydroxybenzoic Acid

2500

17300

13900

Salicylic Acid

29^5

3SOO

3400

Nitroguanidine

2630

llwoo

9700

Aminonitroguanidine

2650

16700

10700

Cocaine Sulphate

2710

laoo

400

Cocaine (Base)

2725

1^0

600

p-Hydroxybenzaldehyde

2S^0

21900

19400

Guanidine Carbonate

'' 7'
SMS

' J .

\

''

i'

'' '-^ ,,,-^'
'. i'/

^

<:MX£

Ci

X'-JX

i'

'

.:r.ifiii,io!^

' '

4- (IMM

-vi-Ycrfi'ii
i-k'

,r

COXt-l

G&ll-X

(\'i:
.SJvtt'TA^WC

,'-cet+'i

,001cx ,
c-ccax

, 0(;8S

t,c«m "

^FfcefS

OOcW-i.

' , '
,"'

•

•/^:T44©o#f/A

• •iWiS
t4<

^ •

; :;;.C!C«ei;

OO^TX

0€.C

(rsm0,
if'CiirH"

OCTXS '. X

'•" •'%

cix

llg0O

' OOC'X'i

OOcCi-

Qil

J

' ' 1

i'Xki
<itk.il

r-- ^

v>

b.h4> oJ:0sff'iil'-..ijufj~

, tfx\i
(mi .

ettfx

0QB

',

oxvs

>'• ^"''i.Wr'v,'

/^^'^s'•;''

, isn-e

»• .; ; tt'f'riO

T'

' '

i ! ' , >v»

oaTfv

tyOc/^i.
it

: Mi

, i^bim>rdp ti'ifi erx I i lir^ ^

or.ft

X'

'(-ni
OOtit

ILV!

dOii

'x-ms
'rm
'

•

aiciviA

XX''' /'.' "v. :•' •^'
'eF- -;T

b t $M:' 01c,7.

^ J'

fi 'X

•"•' ' /4;,;'>

^ruM

»ww'.-ji?'»* iw|r.

pm^.

4,-^x

CC^iS'

OOTC^i

• 'J"0T4i

C'J'.'i*

004^

„ OCtiV.

UXTS

COo

yoi'x

?;•
;^f'•''

13 Jt L
m.tbt

1.1* i; ^0 JT I mA

'!•*/;.'• *'
' ''

, J. ",U .. ''A ' ... F)

11 i;71 ^

$^BdqSMPi

0O4^Sir'i

x/i>
..v. ' . .,',!( r/<
l!» ,?M'

4"!^'F ft kf

'''1

rf

,'; X'if

F

AX

'

?' T -

162,

,'''

Band

Compound

Toluene

r. .

•> •

Ethyl"benzene

51

2530

132

77

2^70

112

2^5

73
^5

55
16

2690

8

11

5

166

14-2

25t-5

2kk

Zk-t3

220

150

111

36
66

23^0

96

2335

32

2675

^20

196

2650

391^

54-

2600

k30

254-5

-J

Jt ;

;

2630

356

102

261»-5

326
396

52
82

v.;l - .

n-Propylbenzene

Selective
Persistence

105

Benzene (Water)

Benzene (ATDS# Ale.)

Al3solute
Persistence

3k6
2675

360

130

Z&^5

318

52

2590

376

3S

2530

356

1^

^ ^\ r- f

"'v-

*t

0X

.

* •' -v-i

•
•'
• # ';.

eex'

'ii '_

, tja •

»••:>,' '•
}
;

**

V

','¥'

^ .X'^'

i'" '

"' •

''M

0?;<!<
dT''^3

'i

*'

•

A'i

feeds''

i;5l

Q>3&S

or>s

Si't's

Ul

0C4i$

ti05

•

3^'

¥1

. 44.''' • •
3c
sa'i • • •

I't

,'i',

.•

a

'

' '

' '"}'• {1:f,4i^t| tr,Bt tt^'^

sii
sxi;

\ ^

• .

X' \

•'«!} SiKT'.^

' " *

eniK
at '
C'iK

' #I4»

,' s#

,

:•• '•• •'•• :•" •-•,•!••,•-

•.

•iCy

1 ••''

'' •

' • /'• '• Si • •' •
• '••' •'••",.• SI ' ' '

f'l'. ¥1?: •'-. '¥:•¥•¥¥::••{ y,-

;" ui

on •' '.

03f
•

fee '
Si

' • '•:

.{''l

o;|-?d5;

V

I

1

,/

C^

•' Q

ii6%

~

&\yi'f aS'tiSvMM.

go^l'
©"'"S'

<Jt;'!

ly I • ;•' ;s )C I

o1"'.' -«r

' ,Siy,

Ml

^ Clef's
^''i^

' 1,

I

i

X /' >X'''
•i'J, ;,
f %im7iiy4 J 'I

^ji

4:
fAZS:

•' ,('

163.
i

Compound

Band

iso-^Propylbenzene

267O

N-Butylbenzene

sec.-Butylbenzene

ter,-Butylbenzene

Absolute
Persistence
332

132

286

60

2590

352

72

2520

312

2660

328

152

261«.5

260

50

2595

328

46

i-H

2675

295
3llJ-

154

2635

263

72

2590

346

120

2530

33s

110

2675

310

26ho

344

95
84
138

256O
p—Xylene

o-Xylene

Selective
Persistence

2535

4o4-

2740

530

256

2690

524-

142

2655

510

98

2600

455

43^

2710

520

132

2680

460

86

2620

486

84

2570

435

33

r

J

? U^.

1

, 1

^

v'4«'

' , - 'K.

I'hU.K^^nA

i ' hti il

%

,

S^i *4

s

S

%

;

" %t\

c%

CYS?

Sss

OJ^'d®

5<'t

\.0€$S'
^ ' '1. ^

ftii..

OS'MY

C
7i ^t
-.H\,

0?

\AMm .,
^ Ic^

,, iai.'t-

^Vt.. f

i!?S,

4W

4IX?;

t-'\ i

54i| ^ ". -

eees,

Oi-t i

5?C '•'

0<;v'^5

cir.

<!T3Y

fc#^'

^ i', '#?; • •

65X
•!i^l

. «!c4 '

'• ^ _

'•'., 1-W'-'".'
"/

£4

.• .'•• V».;-.

5;?/,
38

siT^ ??

dI

• (}M

•

'•ii»«# ,
^'' i

a

cef
Jt i ,'r)^

'•

•

• Y .•••

• • .'• •'.•••.ri

OiifS,

*m*j' ^

• 0g-^

. ;?ea.<
' coas
OXYS
J 'it"

, CS<J«i

osss

4i«

CC

iM

cas ' •

4%

'h^

(5t'iS

^ 0??3

;^

V" '/V
•V
p] , /'>//'
•//.

0,
,

t '

' ,V

'Xt:::

.'4,.

'

' i

' '

r

' . ' V /,

.

,

't <•
', . ,
r '" i
'' ''''» "tC '"'fXi If. t
r.
V. «. // '. '.,. AJI . XAxM' ix-. At

'fi

«

Absolute
Persistence

Selective
Persistence

Oompoimd

Band

p-Oymene

3730

si+o

5IK)

3670

6i)-0

130

2614-5

625

115

2600

5140

Diphenyl

211-60

26200

9700

StilPene

3110

39200

114900

6700

3I400

1?

Qulnoline
3050

Quinaldine

900

3000

6100

1200

2700

6200

2000

3020

5000

650

3025

5200

10140

2950

5650

500

2755

5750

700

3160

mi

<{&

' 'i

W''' '

^Sll
j'l .

J': i , s

'^y
.iX

X'4 p.

, )

i/'» ^

r-* .I-,, r r-t

165.

^.

' vti v . '.

'at?
H'' ' >,a'

^-j,-

i; /•

i

•.h# tiUlli.^k'I.eSi?"''

k• 4

A®,if

i«-

.1.. (''*

»

1.., f^.;

;<>./•,'•/ n,,;
* '''ii'^r't

^'

•if-

4'-

.. 'W

<. ^.4f,./

" V ' «v

^?'l'Vv.';, fi,' -'.

,^tL'\,

il/ir '•\-0A'U

it:

T. ,

^ :. •>

.

s'-,'x/,"i'fJr

? 4\'.'A|I; ,j%l» U,v*i'^

» • THIr V'-t.

'

',f'(

,

iC-

t

;ri

»V |<<l .

W 4.k -.\^i

f

fff
»f i

,'t I'y

t' -f.

-•i

IV'V

, ',' !

f

'

>.lJi0ri^f- r'V'??' Cf ^f«;. v.;.-.'"iW{S, at ,s^4»<iJ
',1,",..!;'^ ":1!-' r, •S;i:C;fti7',\-j¥
,

A; i* 'I - vai'a-

.:,•• »VJ

Wi-l-'f'i 'If

''.t a..? fsC,?."?!,. .;. 'tf, ;,?•« fi#pi>R-«H»;,.
Kl4U>
f.!?.

A,.I.'!

,5^, >''1.

--"

r

r /

\

' 1'4
K !.,(,

»"',•(

*}

v'V^ W)M

,
M."' U-'-U

v'^

it;

If ^

t • .,; >f.

, S'
I

,y44'^'
•fm
>; i^"\7 \ u ••\

•httk

'

xa :. •

v>,#,

nrs s,4f,:.%i
,

v'v

-"KI

''

to

ty -"'H^ i-ASx."
\

'

;

,iX

•>

'

' ^V.,.,A k^fA'Slki..MMM4'k .

v' Lki'. x;

mm:

hXilh

166•
Before going into a discussion of the results obtained
in the investigation it might be well to stop and consider the
mechanism of the absorption of light. When light enters
solutions of organic compounds in some cases a particular band
in the ultra—violet region is absorbed while in others there
is only general absorption. Hartley has stated that only
aromatic compounds show selective absorption, infering that
alephatic compounds do not. However, the author has demon
strated that aminonitroguanidine and nitroguanidine show even
more selective absorption than such aromatic compounds as
aniline. At present we shall concern ourselves with those
compounds which show selective absorption.
The light as it goes thru the solution causes the solute
to change its molecular or atomic structure. The energy re
quired to do this is fiirnished by the light of wavelength
corresponding to the band of absorption exhibited by the
particular compound. Since each compound gives bands at
different parts of the spectrum, it seems possible to assiame
there is a difference in this rearrangement caused by the
groups found in the molecule of the compound.
Since the tautomeric form which the molecule assxmes due
to the passage of light is very unstable it slips back easily
into the form as we generally think of it as being in. In
so doing, energy is liberated in the form of light but this
time in all directions whereas the beam which passes thru the
solution has one direction. Then if given time this light
will eventually darken the plate to the same density as the

167.
comparison and thus the "band disappears. The gradual increase
in "blackening can readily be seen in the plates of benzene.
In this type of work the point at which absorption begins is
relative, but since the comparison is always of the same in
tensity, as regulated by the sector photometer, this value
remains constant. It should be remembered that this tautomerism
takes place only when light is passing thru the solution other
wise they would be self illuminous in the dark. The absorption
of light is comparable to the vibrating of tuning forks when
sound wave of their frequency impinge on them.
It seems possible that there are two different types of
tautomerism involved, one molecular and the other atomic.
The molecular tautomerism giving rise to the broad deep bands
such as we have in the case of the p-aminobenzoic acid and
eaters; the other, atomic tautomerism as shown by benzene and
its homologues. It may be there is atomic tautomerism in the
p—aminobenzoic acid bodies but it is overshadowed by the other.
With this idea in mind we shall try to jiistify the
absorption of the organic compoimd under investigation. Before
going further in the discussion it will be necessary to define
two arbitrary terms, "absolute persistence" and "selective
persistence."

Absolute persistence is taken as the height

of the band as measured in molecular extinction coefficient
E, the ordinate in the absorption curves. Selective persis
tence is the difference in molecular extinction coefficient
between the peak and trough of the curve or the distance

V

L

I6g.
thru which the compound shows selective absorption.
In the case of p-aminohenzoic acid and esters a tautomer
can he formed hy assuming the shifting of the hydrogen of
the amine group which is para to the carhoxyl thus;-

c-oH

It must he remembered that there are very few of the
molecules formed as represented on the right hand side of
the equation. Once they have formed they revert to the left
hand side*

If the hydrogen of the amine group is replaced hy

the methyl group (page ^0) the selective persistence drops to
about one tenth the value given hy the unsuhstituted acid#
p-Hydroxybenzoic acid (page 102) also shows remarkable
selective persistence and the tautomerism can be represented
thus:-

'lit44

C-€>H

•4

mm

-mm

.

0V

tSfiW'teiJfa 4
-•«;'.••••,

.,• •

yv ; •' ^

.

'^tr

:C' ,: ;m:;:

'hm tiUik

• . •/ •• •"•••..

•<
,:••••• '. '••:•

,

-' • ..'7.

^

'' 1 ''
,v ^
'
,v';,-.,v,, ".'.^ : ••.'^r- ^ • V
4-^

~;aifrf4

01- r

XV^
i^'. • . .

' • v7

t:^.x n:

• • •' • -v ,' • •-- . •• ' ' .• ••

• :• ••.,'.

7.:' ' •: - ^

, |;"5

fmii

'•\"n

{

arJau;

'-i:

(S '<1 • •

.

' f(.

' '.c-

•', 0-

'T;

' '

/

't

If
"

i'T) f

'

'I

''

l^rr/^xf tt.f. i;5

•#Al

fv/yt ''{y-fif

*{4

ti"

^

/

/

y^lrjor-^ojf

i^Fyri

; )' ,/ • ^

milws'

o;- KXfotr^ min:'i$e

1

;/{/ (iH

lo

Mmi
%ii^

!)eSx!'i'if3'<fi7S'>%U>>init VK' Mvi:;g;©4f4"^?:!V f-rfi' dtrrs# 'djio Sx/€<fr
'

BmmM

^ ' ,; ; H

'?

f

>i I ,•

i-'t

?
n

H

•" 'ii

t'

:.'

. ' ."•:l
'f r ^

'

c=c>
{

o
H

However, in the case of salicylic acid (o-hydroxyhenxoic
acid) the selective persistence becomes 3^0 as compared with
13,900 for p-hydroxybenzoic acid. This can be explained by
the fact that para bodies are as a rule more reactive than the
corresponding ortho isomers.
p-Hydroxybenxaldehyde can be e:^lained on the same basis
as p-hydroxybenzoic adid. While the latter has a selective
persistence of 13,900, the former has a selective persistence
of 19,^0. This is xindoubtedly due to aldehyde group in place
of the carboxyl.
Alypin and stovaine at first presents a difficulty not
only beacuse of their complexity but also from the formulae QS
we conceive them offer no tautomerism. However, they both con
tain asymetric carbon atoms the rearrangement in the orientation
of the four groups abodt the asymetric carbon atom which give an
absorption band. Whatever the circumstances the rearrangement is
not great as both show little selective persistence (pages 110
and 112). At one time we might have all four grol^ps lying in
the same plane and at another two in a plane but at right angles
to the other two#

170.

o
i(

"

C
\

0'

d)
K

^^/A-

A\c H^ - '^(cf^sli-teS

\ /

•C

<^2H^'

Alypin (1)

Stovaine (l)

Aniline and its salts presents a still harder prohlem
than did alypin and stovaine. We might expect from aniline
a curve very similar to benzene as aniline has only an amine
group in place of a hydrogen. It appears that the nitrogen
exerte enough influence on the rest of the molecule to change
its absorption considerably, nevertheless, there is this
possibility as Watson(2) suggests, that color is possibly due
to a hemiquinoid structure. If we assiime that this is possible
and this assumption seems logical, we have the following re
arrangement:
i

fi-

(1) Henery. Plant Allaloids
(2) Watson. Colour in Relation to Chemical Constitution, pp.3-^*

iil
'M

4

171.
Giianidine, nitrogxianidine and aminonitroguanidine form
another very interesting group,

Guanidine carbonate shows no

selective absorption in the ultra-violet region, and requires
a very concentrated solution to even show general absorption!
Whereas aminonitroguanidine and nitroguanidine show respectively
selective absorption of 10,700 and 9,700.

Kitroguanidine and

animonitroguanidine both are capable of undergoing rearrangement
as f ollows;
NH
d^NH
\rH-i'NO,

Nitrogtianidine
i i

c
•/VH'NO

fi

Aminonitroguanidine
It will also be seen that guanidine

c

/>//4

cannot under-

go such a transformation and hence has no selective absorption.
In regard to the absorption of benzene and homologues
the author favors the idea of Baly and Stewart (l) in prefer
ence to the electronic conception of Fry, The hypothesis

(1) Baly and Stewart. Trans.Chem.Soc.,^7, 1335 (1905)

172.

of tlie latter held the homologues of henzend which were in
vestigated in this work should show seven bands just as did
benzene. Even chlorobenzene and bromobenzene show seven bands
similar to benzene. The molecules of methyl benzene and ethyl
benzene are no heavier than chlorobenzene and bromo'feenzene but
only show four bands. The idea of tautomeric rearrangements
holds better for the higher homologues of benzene than does
the electronic idea. As the benzene molecules has the methyl,
ethyl, propyl and butyl groups added it is less able to go
thru all the tautomeric changes that benzene did and so show
only four bands instead of seven. Benzene in water (1) shows
only five bands undoubtedly due to the inhibition which water
offers to the rearrangements.
The introduction of the side chain offers a resistance
to the rearrangement in the ring and as a result instead of
seven bands only four are present. Possibly the great draw
back here is the fact that we do not have an adequate idea of
the constitution of the benzeme molecule. Even with all the
theories on the subject there is still something lacking as
to its internal mechanism as displayed by its absorption
spectrum in the ultra-violet.
On the question of benzene homologues Baly and Collie(2)
state: "We may consider first the spectra of the non-substitu
ted hydrocarbons of the benzene series, in which a single

1/

See page 12S.
^
.
Baly and Collie . J. Chem.Soc.,87, 1357 (1905)•

173
hydrogen atom has been replaced by a saturated alkyl group.
It is probable that the motions of the benzene ring are less
disturbed in these compounds than in any other type, for we
have the single hydrogen atom replaced by a group that is
neither acid nor basic, but neutral, or as we would prefer to
call it, prefectly saturated. We have examined the spectra of
toluene, ethyl benzene, proply benzene, butyl benzene; and find
the spectrum of all these almost identioai.
Diphenyl and stilbene are interesting homologues of
benzene, altho quite different from the rest because they have
two benzene rings joined at one point. Still more interest
ing than that is the fact that they show one large band with
considerable selective absorption(l). Kauffman(2) suggests
a combination of Dewar*s and Kekule formulae for diphenyl.
f',

Dewar

Kekule

Diphenyl

The one band exhibited by diphenyl and stilbene can be
explained by the following eqiiations.
.'.V

I,

• \ "t' f?

|lj See page I5I.
Kauffman. Ahrens VortrS.ge, pp.^5-50 (1904-).
I,.

"V

The vibration of the benzene ring as previously e:^lained may go on but are over shadowed by the above rearrangements
and are not recorded because the single band of diphenyl and
stilbene are exhibited at much higher dilution than that at
which the bands are obtained from benzene.
p-Xylene and o-Xylene also show the same four bands as
did the other homologues of benzene, but they have a greater
selective persistance. p-Xylene shows greater selective
absorption than o-Xylene as shown by the following table.
Again strengthen the statement that para derivatives show
great selective presistence than the ortho derivative.
Band

o-Xylene

p-Xylene

1

132

365

2

S6

IH-2

3

&k

k

33

^3

<9

i/r
r

p-Oymene another benzene derivative gives fouf bands very
similar to the Xylenes. Quinoline and quinaldine show bands
slightly different than the other benzene homologues. True
enough they have the sharp narrow bands characteristic of the
benzene homologues but in addition there is a broad shallow
band (l). Also the absolute and selective persistence of the
(1) See pages 157 and 159-

.

175.
bands is about ten times that of the other benzene homologues
Quinaldine shoi® a shift of its band to xjiscr.>€^.
Band

' jj.'' ij

,

.'

Quinaldine

Quinoline

3160

3130

30go
3025

3050
JQQQ

2950

2700

> f!

' f

<

2755

5

In addition to the above theoretical discussion it might
be well to see whether selective absorption is a constitutive
or additive property of a compound. This can be best studied
in the p-aminobenzoic ester. The following table brings the
necessary data together.>
Compound

Mol.wt.
of group

p-aninobenzoic acid
Methyl-p-aminobenzoate
Benzocaine

Band

Difference (2)

2710

15
29

Propy1-p-am inobenzoate

-

2830

4

2850

Ito

2830

120

Butesine

67

2850

1^1-0

Procaine

100

2900

190

Tutocaine

111)-

28l)-5

135

Butyn

133

2860

150

* "i }\r

•^§ t-

(2) Difference as taken from p-aminobenzoic acid.

ia

•H',

.•

r-

176 »

'"•If
The difference in \wave-length of the esters from the
acid is not a fxmction of the increase in the eiter group.
Therefore, it seems teasonahle from this data to believe that
absorption in the ultra-violet is not an additive property but
rather a constitutive property. It should be noted that all
the ester has their bands displaced to the longer wavelengths
with respect to the acid.
In the c ase of the benzene homologues the f ollowing
table gives the data. The band selected to detect a shift in
is the first one except in the case of benzene where it is
the second one.

Compound
Benzene

Mol.Wt.
of group
-

Methyl Benzene

15

Ethyl Benzene

29

n-Propyl Benzene
iso-Propyl Benzene

1^3

nf^Butyl Benzene

67

sec.-Butyl Benzene

67
67

ter.-Butyl Benzene

Band

Difference

2605

-

2675
26S0
26S0

70

2670
26^2
2620
2675

75
75.
65
77
75
70

Here again the increase in the Side ohaln does not
an increasing shift to the red altho it is further to the
red when compared to benzene. It should be noted that the
isomers are different in themselves, the straight chains compounds
/

(1) Difference as taken from benzene.

177.

"being further to the red than the forked chain ones. There is
another point which should be noted in passing and that is, as
we go higher in this homologous series the last two bands become
broader and increase in selective persistence. Possibly if
we went high enough they would fuse and as a result there
would be one large band.

m

\' ,

'

IV'
h ''k'j/i.'i

,

' AO i'

• ."T'O"

•
'

V

V "l Nv'^

M-4

' •,

•

V

•' '
V.

':i:l:

''• •

.v/V'

: • -'/

'.ft;;'•:••:• ,ft'.':;ft-'

rji.

r:

:.v>;

, ft '

^ V .:t .'/,

\'/.ft:.ftft:

€•' .
O>:K >?••;..'• ;;.'

ft|^ftr^,ft';(;ft.ft.'ft;ftft:.;ft^

ft;;ft:;; i'/'ftftftftftftft!;

'I w-".. ."li:','.';. ;ft..':

'••A.

Vft.,.

••ft!'ft'';ftft"ft::::

''m: •kky^ kWk

• ,ft

VIII Siaimnary
%- ift;. ,

u
.'V ft.

^ .
..<

:
''ft ' ... ,A....„>

' :

ft

ft , ft-'ft.-

'i •'

.'A •-:••;
'kk'-'V:'.'

• ' , '•

:
^•fti;;.ft,.ft.ftft;ft'ft;ft:

X ft ft'
.

•v

> '

'k:i-xrM
'

..ftSlftV.ftit';...]''' f'

A'

T;"\ft

179<
Siammary
!• The absorption spectra in the ultra-violet region
have been reported for the first time on: benzene, dimethylp-aminobenzoic acid, methyl-p-auninobenzoate, benzocaine, npropyl-p-aminobenzoate, butesine, tutocaine hydrochloride
and base, procaine base, butyn sulphate and base, alypin, phydroxybenzoic acid, guanidine carbonate, nitroguanidine,
aiamonitroguanidine in aqueous solution^
2. The follring absorption spectra have been repeated
using a more refined method: p-aminobenzoic acid, procaine,
aniline base, hydrochloride and hydrobromide, stovaine
salicylic acid, cocaine sulphate and base, p-hydroxybenzaldehyde in aqueous solution.
The absorption spectra in the ultra-violet region have
been reported for the first time on; n-propylbenzene, isopropylbenzene, n-butylbenzene, sec-butylbenzene, ter.-butylbenzene, p-cymene in alcoholic solution.
The absorption curves have been repeated on the
following compound using a more refined method: benzene,
toluene, ethylbenzene, p-xylene, o-xylene, diphenyl, stilbene,
quinoline and quinaldine.
5. The absorption of compounds similar to p-aminobenzoic
acid and other related compounds in tiat series was explained
by the tautomeric rearrangement between benzenoid and quinoid
forms.
6. The absorption of the benzene homologoues was explained
on the basis of Baly^s theory of isorropesis rather than fry's
electronic theory^

100.
Summary (continued)
7* Tall narrow bands being due to distortions of the
molecule while the broad deep bands were attributed to
migrations of the hydrogen atom.

......

mSm

; ' ' iAS ' i
' v'

: , \y^' % '

•i-l
'M: ;

iiftS
, ^

' 'v

/, y

1

>

»

'

'

.

_jj —
•'•x-/.':A'-' ]•'

'liBBiTO'' ' n' '""

Bibliography

Page 7

|1| Miller. Phil.Trans.152,^61 (1^62)
(2) Vogel. Practische Spectranalyse. Julius
Springer,Berlin,18^9.
Page 17
(1) Fresnel. Ann.de ohim.et phys.(2)17,190 (1^21)
Page 1^
(1) O.Kruss. Kolorimetrio und quantitative
Spektralanalyse.00.230.Julius ipringer,Berlin.
Page 19
[1) Lambert. Photometria pp*1759
2) Hagen & Robens. Drude*s Ann.^,^32 (1902)
3) Bunsen &Roscoe.Ostwald*s Klassiker
6 (I6B7)
Page 20
(1) Drude .Lehrbuch d.Optik.pp.335Springer
Berlin,1900.
Page 22
[1) Debbie Duder.Trans.Ohem.Soc.,S3,6l2(I903)
2) Ba^ly & Besch
"
"
w
^5,1092 (1904)
[3) Stewart & Baly
"
w
w
89,502(1906)
[4) Baly.Edwaxds, & Stewart. Trans.Chem.Sec.,
29,544 (1906)
Page 25
(1) Baly & Desch.Trans.Ohem.Sec.,85,1092 (190^)
Page 26
(1) Baly & Stewart.Trans.Chem.Sec.,87,1335 (I905)
Page 27
(1) Baly,Edwards &Stewart.Trans.Ohem.Soc.,89,
52^ (1906)
Page 31
(1) Collie. Trans.Chem.See.,71,1013 (1097)
Page 3it
(1) Brlihle. J.pr.chem. (2) 50,21S (1S9^)
Page 37 ^
(1) Fry.Electronic Oonce-ption of Valence, pp.193>
Longmans, Green AOo.,New York,1923*
Page 3^
(1) Fry.Electronic Ooncention of Valence.PP.95^
Longmans, Green & Co.,New York,1923.
Page ^2
^^1) Howe. Phys.Rev. (2) 8,67^^- (I916)
Page
(1) Adam Hilger, Ltd.,catalogue. "Sector Photometere Jan.l9l6.
Page 51
(1) Schwarzchild. Astrophys. J.11,59 (1900)
Page 52
(1) Howe. Phys.Rev. (2) 8,67^ (191^)

If.

/

.

ll.

Abney.J. of Phot.Soc..4,502 (1S93)
Weber. Ann.der Phys.,45,501,(191^)
Schwarzchild. Astrophys.J.11,91 (1909)
Same as (2)
(5) Howe.Phys.Rev.(2) 8,678(1916)
(6) Newcomer.Science,March 7,(1919)

("

-t-am

'• I'.'r. j0

Page 55

(^)

Page 7^^
r #•

Page li '

Page 77

Martin.Trans, of the Optical Soc.,1^,36(1917)
Howe & Gibson.Phys.Rev.,(2)10,767 (1917)
Bureau of Standard's Technical Bapers.No.l^S,
(1920)
Bureau of Standard's Technical Papers.No.119,

(1919)
Bureau of Standard's Technical Papers.No.

(1922)

Davis.J.Am.Chem.Soc.(1922)
Bischoff. Ber.22,3^1-1 (ISS9)
Orndorff, et al. J.Am.Chem.Soc.,50,S31-7j(192S)
Anderson.J.Am.Chem.Soc.,50,20S-212 (I92s5
Orndorff, et al-J-Am.Chem.Soc. ,^^-9,15^1(1927)
Baly <S:Collie.JlChem.Soc.,S7,1337 (I905)
Baly &Tuck.J.Chem. Soc.,93,1902 (1SS2)
Baly & Tryhorn.J.Chem.Soc.,107,1956 (1907)
Stohbe & Ebert.Ber.W-,1292 (19II)
Macbeth & Stewart. J.Chem.Soc.,111.S29-50*
(1911)

Ward. Biochem.J.,17,903 (1923)
'-)) 6,3^3
6,
Magini. Nuvo.Cim. (5^
(1903)
Brustier. Bull.de la Societe Chemique,1529
(1926)
^ ^
(6) Oastille. Bull.Acad.Roy.Med.BeIg.(5) 1903
(1925)
Klingstedt. Compt.rend.,176,2^2 (1923)
Purvis. J.Chem.Soc.,127,2771 (1926)
Hartley. J.Ohem.Soc.,53,6M (l6^S)
Page 170
Henery. Plant Alkaloids.
Watson. Colour in Relation to Q hemical Con
stitution. pp«3- Longmans, Green & Co., New
York (1916)
Page 171_
(1) Baly & Stewart. Trans.Chem.Soc.,^7,1335 (1905)
Page 172
(2) Baly & Collie.Trans.Chem.Soc.,S7,1337 (1907)

:

' -•

• 'J

, •" ; : . • •
i.J

i:r,/

is;"'.;,";: