l

MlinlflHHHl

 

ABS-Q???) Lit-N SPECTRA 0g:

 

‘rlll‘ ‘ I‘ ( ll Illll
i
I [ \I .

 

 

‘|.ll[.|‘ll

OF T“; INFRA—RED AneuRPTIov

SPECTRA 01*" b‘ :13]??th VITn..;III OILS

by

Byron Dustin Field

A TULSIS

Submitted to the }raduate School of Sichiqan
State College of Agriculture and Applied

Science in partial fulfilment of the
requirements for the degree of

MaSTfiR OF SCIENCE

Department of Chemistry

1942

The author Viehes to express his appreciation
for the advice, and iiterest taken in this “ork,

bTI DI". Do To ‘31ir'lgo

H
fl.)
3
CD
E
LR

It was realized early in absorption studies
that absorption spectra gave ingormation concerning

molecules as such, and much work was done bv a larse

 

number of vorkcrs who for the uain part concerned
themselves with the visible ail ultra-violet regions
of the spectrum. The deV‘lOpment of the theory of

ontical spectra had encouraged work in both the lorg

| _.
l

and short wavelength regions adjoining the visible
region and thus sowething was known about it. Row-

land was making excellent diffraction gratinas on Metal.
The discovery had been made that water was very ab-
sorbent in the infra-red and V. m. Gobledtz decided

to study a large group of comnounds, particularly
minerals, in the infra red to see if information could

be obtained as to the state of combination of water

(0

associated with rineral

The importance of erpirical tork in the infra-
red was not fully appreciated, however, until the work
of Cohlentzl was first published in 1905. This work
showed tiat not only could water associated Mitt
minerals be distinguisted as water of constitution or

crystallization, but also that various absorntion

bands which occur at more or less fixed wavelength

could be attributed to particular atomic linkages
in molecules, and to particular groups of atofis.

Tables of frequencies corresponding to particular

gfiroups equi Loads tann3 beeritrjblisizai.2

L

Infrared absorption Spectra are in general more

universally applicable to problens tban Visible or

ultraviolet absorption spectra since all molecules

 

absorb in this region of :he spectrum. Since the

bonninas and tre groups present are wainlv responsible
for absorption, tlis rethod has proved to be a pover-
ful tool in studying molecules of inerfectlv known
structure, and of solutions firbre dissociation,

" n

on, or solvation rave tayen place.‘ since spec-

J.

t"

associat
tra in the near infra-red arise from a weak Molecule
rotation superinposed upon a relativelv strong role—
cular vibration, and since the vibration frequency

fixes the position of the absorption bazd with respect

m

 

 

to Wavelcxujfli in tie spec‘snrm, fine tvpe Cfi‘lnruiing

 

between the vibrating atsus “as a major importance in
the placing of the absorption bamls. In general, for

light atoms, bands due to single bonds between ators

;0

occur betteen 12.5 nd 8.5 nicrons, double bonds

between 5.7 and 5.6 microns, and triple bonds be ween

Bands are hC‘.ever shifted slightly due to other
roupings in tre molecu e. ”0 ever, reliable irior—
nation.car1cfifiurflr3 obtained since in an 1“-o*'.ol;:ous
series of molecules, the stift is usuallv rccfla ar
from compound to compound.

Few biological products 1"ave been cornletelv
analyzed due to tFeir conplexitv and also because of
the difficultv in obtainina them in great €fl0ug*
purity. Vitamin C however, has been investigated in
the infra-red region of t”e scec run from ?.O to 8.0
microns by iI -iams and ROfiGPSS and inforration cor-

cerning its struc ture was obtained. nondinns observed

The object of thi" work ras to ”ensure the
infra-red absorption of sowe naturrllv occurirw oils
and sowe vitanin oils in Rn a+tenrt to attribute
particular absorption bands to the Vi‘i.‘i‘;‘;‘.l?1 present.
‘Wie oils used wanna; cod liver oil, halibut liver
oil, irrwo"t“d erjosterol in corn oil, vitamin a

conc'nt' t :, mixed natural tococ“crols from vegetable

oil, and siwntlet'c Vitawii Kl. Corn oil and oleic

5

bond V“LQ‘~WCit

TU b

 

19 I

m- ,
.. ‘17 U {Ii :3
M

n

g

L.)

of Ronda

 

Bond

A

OOOOOOOO

-./

II I! m H I I

 

 

 

Type Bond Iengtt Vibration
lfircnuencv
X—X 1.55 - 1.545 sec - inoocm'l la .5
See reference 4.
Bond VTGQVt..16i (tunu for Vii min,C
Bond Irequency avelenmth
0—5 5000 on 1 5.30“
C‘:I J'DOU L5 0 03’
"=0 1500-1800 5.57 - 5.57
0-0 1500-1800 6.57 - 5.55
0-0 900 11.1
See reference 5.
Frequencies of Some Con on 5onds
Frequency avel nstt‘fhyri Fr ec1uencv
H asiocm'l 5.46!x C-I 500cr'l
C 990 10.15‘ C-Br 550
C 165 6.14 0-01 530
C 2200 4.55 —T ?250
0 Ketone 1722 5.80 15C 2150
0 nCld 1550 6.08 N-O- 005
N 1053 9.58 ”V “V 5000
0- 1054 9.67 8-H 2500
U 5580 2.96 7-H 5500
See refere ace 2. (also 9.)

'avelenrth

" 80-3
"' 505
"' 308
”ll/Cl:

15.39
4.45
4.65
9.97
3.53
4.00
5.35

went

acid Vere also studied.

Tte Spectrometer used ban a Gaertner L25? infra-
1

red spec trowet—r and monoclromator. ”bis p“rticu

0’)

type of instrument was described bv O'Bvrne.
wavelength range is from 0.7 to 12.0 microns. It
employs a rock s'lt prism in a qodified ”adsnorth

W0

0 * o a - . r7
mounting trich filVCS 95 constant deViation. Wte

prism faces are 55 x 45 mm. Collivatirn mirrors are

of 40 mm aperture and 500 mm focus With surfaces of
evaporated gold, and parabolized about axes lvinq
outside of the surixces to e1:3 i ate astip“atism and
coma. Tie slits are bilatedal. 'avelennth settinrs
are made directlv on a oial scale whic} is ad‘ivalent
to a linear C113 of 1.6 meters length. The scale is
calibrated to read to 0.1 micron.

The therVOpile ‘ssed to measure the radiant energy
was a Gaertner L170 furnished with tie instruwent.
This is of the Coblcntz type and consists of 12 copper-
constant an junctions v.i h a linear, coitinuous, black-
ened receiver wticb has a surface 1.5 x 14. mm. The
resistance is 5.9 Chas and from tVQ Calibration data

.—
L

sup lied, it develops an e.w.f. of 0 .0258 “icrovolts

per wicrowatt pe square centireter of surface.

The galvanometer (connected directly to the
thermOpile) was a Leeds and Vortbrup D'Arsonvsl type
of 1.5 x 10"9 anperes per mm. sensitivity; external
critical damping resistence 7 orns; 8.5 second period
and 18 ohms resistance. The scale was placed at a
distance of one meter from tke gslvsnometer.

The light source 1.1s<3(1_'~;—;s a 10 irc‘b by 5/15 ifs
"Globar" of 7.5 amperes lose and orersted st 115 volts
A.C. directlv fror the mains of th laboratory. mre

"Globsr"xss mounted in position 1'7 or. from the slit.

I‘TL- " ‘11 . . . 11 . " K 5 1-1. . .sw ,- 1 4-0,: ' f! ‘ . 1
has emis 101 curve oi 1,13 SthC0 58 plotoed against

0)

. ‘q " I" ‘ . w. ' ‘. . ‘ "‘ ’3 : 1 J \V\ ,w. ~ ‘ .
vzzvelrrnitn 133 gjlflfifl 1J1 Csixm; I. Tne 4e_issiry1 has

”0
measured in terrs of Ealvsnoweter leflections for
radiatio: tkroufit tre instrument at various asvelenvth

settincs snfi thus iscludes tPe shsorntios o? ererdv on

bassinfi tlrcrgfi 539 prism anfl loss at t‘e reflecting
surfaces. Tme curve a.oroacres tls CViracteristic

form for blaca-body r distioq and shows no stress

Specular absorption is the lfiStPHWBFt. TFe maximus

o ’ o . 1‘ ‘ '1 _ O A .“v 1‘ 1‘ ,ip 1 -
VFlSSlOJ occurs at about 5.1 -1croqs dfid t err ole
'-A' r+im , .savT4wn L» we. +nnm f 050 lfioOO”

fl\41_C'\ J1.J._) fir]. O;..)\/I (1‘. 11—- Dr." Y: «IT 1] ,“ ~/ 0 .' ')\_. - '\_,\’

;

1i _. w B
aCCOPdin f0 tfle .15n lflu.

Cells were split fros orturvl crvsts.s of rock

1 “?e

,- . 1 . ‘ -. 1'- . ', - . .., -- .. ,, ’ .fi» ,
Salt folievl‘g niruct10*s 'figtlllnv Cohiests.
4.1-0 .‘r. «l -... t: .° ‘. .. , - .,, 1.....-‘3
chCkzMfiil of it e 1.1 LVlUlm 1 «legwgz -is SUCorux1_;1 ,lv

one “illifieter. Spa,era were opt 7rom tin foil of

L f
0
d-
.1
O
V t‘
..i
J.
(i)
D
\O o
I
LA.
_1
\
ti)
0
”'3
’J)
.L
\J
:5
"S
D
‘4
.1
'1
~ L
I
' i
O
O
C )
f.)
4

' . E r ‘ ‘ <~ “ : --o .‘ _‘ v " A r!" . . V‘Yv’
' ic.wor rqsg;mv'l'crtc1¢ v.LL)G Hz»
1- ,- .. . ~ ' _.. ,. ~ .I, . 1‘ - ,
m}; Canaritfi of ,le cells wsud xas 4.0. to 0.1 m1.
5- — -. - . v.‘ 4-~ —,,. . . .-~~ - a" '
miter escw rws, t:e cell mus uw :1 part and vs.eo is

several nortiors of di-etrvl etVer prom WVicr tse

moisture had been re oved. 5*e drv plates 9rd shucers

were stored over phosrlorons pestoxi‘e is s d~ssicstor.
fflirb:s Kept ini tris UVQT were iwrxw" to re clewnq eves

aft r sevm a1 montrs of Tse ‘rile ol fies lept omen to
tte rat"osrfi ere suwos.1n:carfii clcnv“v. iftat“s x”“ic”

D

recir“; clxrvri’ fed“ a“vr rfiwusrvl Yflfl“8

L
5
H
x L
:34
O
s
’3
(t.
H
H

‘.
I

‘vss (rint£:" is i s1fi(1inC‘7solr%3r ;g;1sz aJ’so ~ 1~iece
- . . _ H . .- . _
‘ ‘ ' " ‘ .7 ‘ ‘ ‘ 1 ' . ~ w- 1r v ‘x- ’ l-c ‘ n

of rock 831: :or CORLLlenLo In tuis Va] eiz er

could he placed in INe reuw of rsfli tins ifiCiceit soon

n-
r~
D
L-
C

H

,L
0)
Ho
L 1‘

-—10
O
L;
Q

f‘

(

n
L"
(J

.i
I;
(I)
“S
1.
\‘1
CT
*‘5
F4.

\o

H

x b
!_J
D
r
on
3
'3
3*)
3
rJ
7'14
O

0

OJ
C.
”*3
O
F:
(D
1-
Kb
H
H‘
K 3‘

us nearly reorOducl

.” V1 \ 4‘ ”4:” ' - ’1 .. 1 ' '.\ T. ‘. "- ‘M ‘
m;b’ 06118 were .‘~\‘,1)}](.I‘ -.._L {O “-5 151’) C(‘V‘Ll l 0.1.x? 1-]
tine lyzuiss: rfi-ia;111 x>f‘ t‘ is: Pcvlriezs. 11' ttiis ='ssr, or 17r

Inifliaxti_05x ‘3 iiit' 1“"? 133$?seec_ t“ r'07** : L ‘9 a 78(3rflww~*~

.o A o_.-|
nuntcrdxal

Of tfie cells reed v

t‘r

onesxiwgr

" "A ' ’" ' .'.‘.‘ -‘V‘ + ‘ ”“ ..A ' ‘v
‘21,118111‘L F7L (JIM.‘11_

(‘1 V‘

onesijfiT i
.-.._ ,

opening is

N

'.

L..J.

I y\

."t

'1
5
4

Quid

r)
[D
'_J
..J
(’1
U)
”3
Ho
.4
N
(F
e“
:3

Speccroweter is

stield wit“ ose ooeoiw

an“

upoc the slit,

0 1.—
1 Cl :.
07') £3 I‘L. T ‘33 S

4-”
+n e

_,‘_3 'r

pTOtGO

“elps to

thermal equilibrium.

m ‘9“.-

ihe twerv‘or: it:

ynoe‘} (1
~41:

arr? to lme}y:rtic‘v‘nrlv
barowetric Urfsswre '“er

a tie tinfoil St

7‘ - ‘ . . ’ . > \ . x o I

nfiyh LilCh Fella?
('V‘ ' ‘.

, 1,1

1: 7 e 2“ {T3

7:1 C 5?;

another larger

' . v ‘.",_~~J—‘.
bu‘dV fl, ,;_ ‘- .i; l.) _

fourfl

«'5 CT "4“ 3 j +7! 'V 6‘

5.0 cm. ¢he effective
on ofissed (tHe lJFldG
“3c cell holderl as

litmqe enor*4:su3 fi“st tte

cownletelv covered tfe

31', 13‘s 11'” +‘ 5‘». OWI‘CG

‘12“1“? I. Ifltlp“PatlINl, tPe

douhle-wslled c-rdhosrd

peniifi
frettino is

Wes t”e

on ."r'sii
‘-- ‘ .n :;.\H‘ .‘)

(1-1 p j. 0

WRVGlerstw

-.'~(./:'71+ n." at.) if]

..1‘ \J k.» L.) " 5‘ .-

tVQPPorile

‘strwreht case st

to drift

- 11,-. . 1 :— 4-
+.l) 51": 53.111." '30 J

to svcsll (““flrf"98 131

5' 6571*‘cm'r1'31e or

A ‘ ~a-~"r ~ -.
()+ t,‘J"‘T/g;‘v(" 1T'3

Q
C
(1'

Ir.) ‘5»518

suhwfccsuido

        

 

 

 

 

 

 

0*
v d i
2 c ”max;
I. la
xom...
wwvcagé l gwfiiso: .zgou 5
code 1‘. mH .
eases: L. . hub 4.. 25:;
”Jar—W LOLsz
no+ij<
\
. \
\
\ \ 12.14
\ \ \-\ _
\\\ \ \\ I“ l. I \ k /
..mwmnhulfunl; . ,
I II .
3 —¢ /// I” [WI I II...
/
, H : n
x n u
_ .
ruin...
£5
V5.

p

 

FNEOI :mJ.
15m. HayfidxbmcH
Wukdfinz Frayd $0 Edemdzfl

3

AH OFJG.L

 

 

 

///r///

to large extent by serlisi th t‘epvonile bade ksa
packing L~ sysce about tfe +‘errforile titfl loose
cotton. 5he tVer coils case LAE sealed spsisst
orn:ssnire: c?:arufios; inf (EOYVETlJEQ 'ttra ffifio 1t (ostriiriw =xi't? a

tfiin rock salt piste *lics Mrs sealed on yit‘ t‘es'
tax. (”he bsc; of t“: C380 “as i closes "it“ a *icrc-
scope cover glcss clso seslefl on ritk bees' Vex.) mLs
rock svlt plate suV1~d on is t?is fianner mas foam” to
be still unclesdw? s“t r “VHKisirs is t7e Honctiif for
about four flflxtlfl. ,“Vese precautions lessexed he
acourlt of? t7~-e1'-2n10pile drift coisiderarnljr.

Conjection Hires ffiwr"s“ewronilh to vulvssOWeter
vxeiée siiifilrlel '*;u1 sT‘e s‘ iyalxi :21431116ieri. "n(3 lthjt oi'

-. . ' .- _.l.- - , '3 L1 .-~ . .C‘ . . . . , .
1;; a; gas; ;_\7;ti ari' :: ‘xf‘l' r)..L'J . iii (1 -93 L3 ()1, it a: 5:1; rift +‘11t‘n~srei:- 23° \' 6s '63

L—h

. .3- _ , '1 - , . " l . V“ .
also confiscted to t‘e s“.nifi of fi'w co~4'2_-‘.~cti“z'~ ~ires.

. ~,’.. -‘. ...-.;_ -. ‘ H: w o, r _ . ..
‘Vlw; g~qijrariorfgt‘fir stsv.e(; L31 0 rifiicif (if Ly‘Oli. ‘terw hix~céas

._ -'

of CWJPIVHHit”KL cuxw“o0arvi ‘ LC? T“:Siffi3 “rvxi a 1 €‘7WT itwss

'1... _. mp: - 4. .
g~.“"’:,Sf‘-~.. if?) 11" HWY“ r18

H

_J

T'
4
>

, .3 . 1 L. . 0 ., 1-

CTli'wmfP aumnz, “/4 1 (yr
~ A \ ‘ ‘ ' I .' ' . .“ ‘ ' . 2 F‘. fl ‘ . ' " u“. ‘r‘ 1 ‘. “ '

SlpnOPttd of a OJ”"1¢CR iLJLT u; flw- sing gr the hot-

‘iS iii 5: o? {Vipruort;ipor 1f*e

tow1(xF a lfllfifij pet3fi_(‘isn.

~ _ ‘ ..' ' .. -, .2 .l .: 7“ .. -, . ,.
é;::<.1*.r-.=no*:aet<+r LQG l.+ l":S€:“.f~1 a‘lVB U0 \GHA-t' "~ ' “:41? n, ‘53

"so t“e stroi“ viorstioss xere rwoislf H~Wc”3 out. “"e

‘ .. .. ‘ ,\ .o . .V . . .
iglvrgnox"Bi‘wr {and T‘Ts‘. MADUQ“”, Jere C‘erTUF.‘ 1V7 *mifltliffl”

(_1 J

 

“rojectec upoi f WJ'T U7 “W eter 'irror ~nt4re” 'r'
.., * , J... ‘ 4.2 .- -1.."|'\ . .. , , . ,‘.‘ . ‘ .‘ 0 1, ' ‘0 'L ‘1
-4leV‘,c' o row ;; .113”; .lAMp‘ l i‘h‘e s W» ll.

- . . V-v‘u . ‘- ‘. ; ‘ ' v - — 3 ~-. 1 J {'1 ._\ . Q'v :- f
scs e woos = ics t L i"\“0 ut~r r- iwctiois \2rc
‘43 Clwfifld 5t . (is? 10 of oim tor Fror t“e «=1

)4 _
I3ific7(32.ai111“ce
‘, 7 v. ' , 3 4.. ii .., .., .. .: . ‘ J... v '1
L/eeSVIrdtxit oi L“ s iJsxufiitios (Mr-c.3ux -ere *w
‘ ‘- 9 q ’\~ 3 - "a - ~ "1' o T ‘ .th‘ 1‘! n "I V‘ . “‘ 4'
0v t m3.1011u 1.. nroce; u-.. ?-/e :lousrw .alews y.
00 VW3Ct‘11 sri t't t ii: V(fiflo aa‘tsi*i s sgtesfiwr tevwiors
. 4 W V ~~‘ 1 ’ ' ' i \" " I I -\ ‘1 'V .' |_ i-v“ .3
uhfl t.H dOJOifi-;Lllbd C IQbOLPd S1lfla ‘33 pllfiwfi

I. . g a ' ‘ . M 'fi 1 - _—~. / ':.
th* Spectronat r. n ClCWJ Cvll zn' soccer o t c
v‘ ‘1 : ~ v. x ‘ v .3 ' J- _‘ . 1—1 . ‘_ ‘ 1“ _
oesireo c .Chu Sb .ere VTJsSeU .One her dfld t e up

A ._
. ,, v _ ‘. , .L 0 . o . . s. . .. ~.
.1ats rawwnnnl to ‘cunw: t e .31L1011 SQ?Ctfi“:NT“99:d

cositiOI :ivinst t‘e otoJP plate. ‘1ou~» of tte 1
to he wseo Ins .ten sliced in fi“a Qo9“{‘* at %“e

4,-

.— .' Vv' ‘1 ,' ,~’ .‘ ‘. . «no L “V 1 ‘, 1‘
so t”ss tTOre gowmr :0 a s11 V ~xcess. W ’ iooer
‘ .\ '3" “ ‘ “ \fi ‘1 t: -. ~fi “ . L”. ' ‘9. " ‘5“ .
room salt plate has P-VLUCVK lu oos1. cc LL soc a

as to svoio ijclosiig all, and

iced ll t cover olste

c ell \n'ss pl:

3“ _ _/ 1 ‘ _| J— 7‘ ‘ ‘ u‘" . . > A) j c‘ ‘ 1
filly SCwSUBQ to..». ' e 00*erison at ca o rocx
.. - .v . . '1' ,, pm, ~. a, V ., on, ,. ,
”as pluCe1.131yxrthion OVer is:erfit;er OOlel“ i“:

11

~~ o -
I 1 r8 ,
. s. 3.2 . 1.1
-)
.> C1
1 L .3

«crap-hm.
'31“.

"18

4“ ~._

[J‘ 14,3 ,

01.791"

VJ .3 1‘?
in

{xiv—1d

67‘114 (3.1314
. ’,_,‘ s I 1’

CBI‘V

cell holder in like manner. W‘e cell holder was
placed in positioq Netweea t.e source all t“é Slit and
type ugvvelxafiytflt dinyr sw3t €1t l..L r icruiq. '“he swalVTwiovfrEGr
is read for radiation tFrUUjK t?e Cell (I) anfl tfironflh
Lne (wy‘fiarfigsflu r}; be (I: aim” visa)? ififl five vzdfifiatiori
co*qihately (Hit ofd?.fr(Wt tFe sfiiit (:zuro ranliflfi). Tie
wavelength drum is tWCq adV$nccd to fi“e netfi seitit:

(ixvvillv igi sterwt 0? C.].'“i0rfilil u‘vl tVQ ‘“°¢CCQVI%2

.4-» . ° 1 . -,A ' - .«_ fl,-
rezcu Cd until I?.3 riflrous l? P030‘Hd.

|-J
‘J
O
6
U
3

l

3
w
('3
, )
\+
(0
w
'7
J.
J
i

1’
T‘
L\

-:ro IN;afii*N: is

subtrscted from t‘e I and I redflifiws and filo nernefit

m
<:
3
F
"D
C)
_.)

tram? ission compufefi as I/Iol X 103.
a: iransmisnion curve is 5L0? plotted 2g9inst wave-
«3 "l ff t l". o

Juri1* +39 brOCH°U 0? +wifi'r71mvliiifs tka " it
were aijusteu s. as £0 Leap t7€ total He‘lentiOfi be-
tween 5.0 and 14.0 cw. wTen posqihle. The 811* widtVS
used anfl the rangm of V2V915“ i” F0“ P"é% frw civen in
Table 2. In all Cases, iVQ cwfirafice an“ exit slitq

-,- r“ a 41-7 .‘v L ".- r: -.—- ’ ’ ‘31.;a .‘ .1
herb) lx‘dnt git we Sci'TJ " -ut'. 111 DJCva‘ to afi‘dl] tre

“i"Hest spenirml purity fiosaible.

12

‘ ’ I
av~lowvfh ”Vn<es Poem at V io*s %lit 11+13

 

4

Iavslenqth “:1nqe Cove red

mmHl-‘OI—‘f-‘m
OWOCTIOOICOIO

\l’fiCfirh-COI—Ji—JH

'O'IJ'JCJ‘ILJJIW-C.)
I

Q33Ulh5ml—‘i-J

. 12,:

K

O
(Dz-Mp. 3900

o
o
1

I
H
":7
.

% ”idth of Entrance nnfl exit slits were Yept
equll at all timijs, since is t*_is anr'fl‘p ,raat-
tic

f
est spectral pulitV is ol,ulmvfl for anv pa 1 ular
slit nidth sstti1j.

15

Curve:
Number

2

G";

10

(‘

sampl£
" ’ ‘ ~
LUMIDUI‘

54410-1

Table III

 

list of innnles USsd
--n-. *- MW M
Olsic “cid (B.P. ?6T

r ,, -1 f H
A' 016404.01.

Corn Oil

Irradiated

Ealibat liver Oil

Lixsd Natural moccphcrols

fPOW Vcéctublc Oil

Vitauin A Concentrate

5Vuthctic Vitamin ll
adficd aCUtflte.

l4

:rqostevol

Vitafiin
Content

53 ,OOJ
D "nits

65,330

HII||I i l

‘.1 I‘III l.l I!!! $1! 9" Ill-ills. *1 ill I! I I I] ll Illsll .Illll ill-ll -.‘ I'll Ill

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

I I v . +
w . . I I I I ,
v- I I . . , . n . .. . . ,
I+ , - ..0- m I . - + ..... I -. .I . a . . w , .w w N w I + .
I I - I ..-... - . I- II . I
. u . a I -..r -0 ,0... ,. .7 .I- . H + I _ . + I I I I
. I . _ . . . II}! K II . ..II. .I . I . .
VII-II III-.04 IIIII I... +00 . LII AI _ II H u m .- . I IP I H w m w . I 0+ 0 I I.” .00 . I lit“- +. m . +. I I I
I III I ...... . 101.0III .II I V‘IIE . - 4 . I F I . . 0 . I . .0 - .l 0 . I 0 .I _
I _ fl . 400090.! -.IIOIIYII- ‘IIIIM .001._.III . D m I _ u + I . I a. ~ -.. I- o 4 I.»- IW . -
_ . . . . _ I . ._ ...- III-I- ...-I- I I I _ I _ I . .
1- I I. _ . I I I - . I I. . I-JIl-IILII0IJ T1130} LI. w _ u . I H
+-.- --— --,. ..I 4 .. I. . I. I + . I . 4 I .l. Kilt-0.00. IIIIr “ . I I . .
. .I . I I . .. - - . - . .I I I. . . I I II I. I. . --.-0+..II- -..-0-.-}... LII-.0 I
I . I _ I I ._ -- . . . I _ _. I I _. . . III-... ---I
I: -I . . . . I I I I . I I. .---l I. . I- .... M I I I I I
viblllbs . I . . . . . all ’.0Il - — . w
I I I I . .-.. -.-I- $10.! ...-0., . .. _ I . I. I I + , I . C. M T. , - - ....-, I. _
. . I I I I a If- --.I.---: ::.-.---------:---.-.-..--I-- I I . I: I . . I . I I .
. a ..0 I I . . I . ‘II |I00 IIIIIIIIQ‘III b . . . .
I In I . . . I _ I + + . . 0+ I I Vii! IIIIIIIII ...-III II _ w . I I. m
I . . v I - - H w I I I H . . I . W0 I’IIIIIIITI...III. ...I-III .
I I , I . I . I ..... . - : . . . I I . . I . .I I VII-0:11? - I I
”III-II I. I . u I M . _ I o 0-..I -W 10.... - v ..... 7 k 0+ I . w . a J
0 IIIIII‘ - o . I. + . .‘0 I! I I II . n
I I I I I. :3... I. - - --.--0 . . I . I I . I . I I I -..-...; . -.-- ISL ....... ..-I--.- I . I
I I I . --I-III I-I. -..I- -. IIIII- . I . I . . I I I . I . -. - -.- - ..
+ . _ . fi III-I040... l I I . I +
. I I I + . I ll. ....Iir ..... .. I-IIII -- .r H + I I
1- - I - I - - - I I I I -I - -- -- 0; .IlT-IIII I _ I . H . I +
_. . I . . u. . I . -... + H k I . I I ._ II'I’IIIII I010|III.|I.IIL[IIIIII0|.1 ..-
. I I I . . - I . - .. .... - I . . . I . I I I . _ I «...-II -..
_. - -1. :I-T--- _ _ I .+L w . I I I -H. I: -I -I -. . I . . I I I
+ «I I! ;0 AH'III II .1500 . I I . . I v . I 0 0+ I .1 III .
I . . . -I:Iam-z-7i -I . . I ..I I . I I: I , u - I - I
. _ ,II Iol‘lVI'l-III‘III I u . -
F . . O‘IIIY III-III III! an it It I . I 1 + I —
. ..m 9. v \m .- l .I -+0.Ivv‘l I. I’VI I . _ u . . W
I I . . .-- - III I I . n . . .. w 0 I-.Il+0ir0.0xI0l0+uuoz0.IIsl_ .
I I . . _ . -. Ea _- 1 I . I I I I 1.13:...- $1.. --.-.I
.1 - - .- - I I I . I I I - . . - . . . - + . I I I . . . I h
. I I. ’III. \I .9 0 III: _ p . m . 0 n I» .. III... 0 . . I. r
— . _ . IV -IIIurII.0 LI 5.0 I I III . I W I s 4 c I m. H. .00! ..I- . w +
. ...-I0 .- I0000.:. . I - I . 0. . .0 - .-
.fi + m _ _ ‘m . "01).lial00i-0i I 1,-I I 0 ILII- k u . . I . .I I w m
. . I II I _ _ . ------ I- _ I _ . . .
- o . . . . . + . l‘I-ll..+0-0n ‘00 IIII 0.. I . . .
I . - I .G _ . . I a _ -. - -. .
. .I .i I .. - I . .. . I -01.! -0 I 0-.
”....- - . - I. I ox . I?) . I I - M - I. . I u I I I
00-|»I ..1 I I. 0 LI 001 . w 0 . u . .. I + .
00-.|0..I . . I . _ I - I . .
I I . u ... OI. l.n _.II 0 III. IIIIITIII [out-II .I.7 I . w M I .. . 9 I I I v . .
. I _ _ I . u. n . -.7- if 3-1-...- - . . I. I I . I
r _ | I. n. I 01 I F - . I. m . . _. . «I. III In III 41 7 .. It 0 l6 - . l' 0 IIIIII 1 a .IIO w. u I - M + u
_ I I _ . m . .I I .- _ I . I . I , . -, .--.--.-.- I
. . . I - a . I
I - --. I- . n _ _ I . . - . . .I . I I _ _ I
. .I . I I. T I II 000 I-qul |.l.0...II..I0-tv.0.II-I - H . u w . u I n .4, W. 0+ 60 .H I . .I _
I I I . . I I I». - -..-1.. ,- r . oI . I . -. I
..- I _ I . _ I . .- ... I! I i- -.-01 .-. ..-- - U I I _
. I -. _ . I I I . I _ I 55:31.0 0....11-0-1 . I. I I I
I I I I I . : Ir - . . -. I I . MN I I51. .35.. 1:...- f- - -I
_ . . ----I . I . . v
I I _ . . . . . _
I ...1...I £1... I I - _ + . . I .- _ .. m ._ .I +
. u . . . . .0 I«IvI .I. I 110 0 III. I ...-I0 .0 If I — a I . . I I IIII . I- m. I i 0 :60 + _ u
I! xii-VI I . I . ~ 0 (I
P . a .I . fl . _ III II 1|.- I.I.WI- II ‘I 0%) 1-00 I it! . I. M . . . A _ fi . M 4..
_ . . 110-001. III] .. II I 00§ )l I . . . I .
I . I ,. I . .- . I . I I...0.II-I+I0!9.0...0.0._00II-- ... -2.--,I. H + .
I . .- - .. . - I -. ..- . I , I . Iv ..- 10. ...-3.1. I-» iii-.... ---I-..i I I
I I I _ .. - I. . I I . . . . . .-,iIr-t-I- ---I
.- i I _ . . . I I -- . - .I - I- I I I . . I . I I
I l. .05 0 .I-IL III -IIl.-IIII-. .0- I . _ . .. 4 . I a I ¢ 0 I I u. I
-000.- 0-0r _ _ . . -- -: . I
. . ...... .0.- 0 1.10.00.0l0u000 _ . I I . e . + I“... p .M L. I u .-
+ . I I ..--10-1.1l010. 0---00..00-0 I I I I m I .. I + . . -. +
I ~ I _ I . _ . - '1'-I’ I: 1" II I"-.—'“ 0“! I w I h .
_ 4 - .I f . . d . . n I I .0 ‘00.. I7.- I..Y.Ol .l-I‘IOI -Yq I + n + +
. 0 I I . . . ...-III»!- I . I v
. I . - .1 -. u. ._ . .I . m . I H I I . I . 4 ...-01$ 1-- “ u
E _ I . I _ - .. -I. .-u - . . . _ . _ I I . . I a --- III.
. . I I .- .- . I _ I _ . I . . .
+0. --l.0 -II- I -+.- I I I I + .- u . . . I . ...: - - 0 I. I , I I I. H H I I
.. .. I I I ..II-ITII. I- II -. . . I I I I I I. I - ...r - - -I - - - I
_ _ . + . I I ILIIII. I... [III-III 00* III. lullaIl. I I . . + + m . .
.. -. d. + I m w . .I . _ I . ...0 IIIIII Iv}. III . ...0. I . N . I
_ I . + I. I I 0 . . . . I . I . v \. . -T-III.0II.0II I~ 0.0.1.0100-.- +0. I! w . .
I I I I I I . ”-.-- I - - .... I . I I I. . I _ . . IIi-I-IIIlI-I-II- I...--i-+
. . I _ n + .I I I ...... .a :0 {I I I. H . _ . I M _ .
TIIl-I- I...IJ.0- . I . . .. 1-0 -I- -- I .
I 0.. 700-..0 II I .IIIII I . . I I I . I . - ..I 000 Ip- . I ._
. . 04:"- IIl-I. I . .
. _ . . u . . . I‘Il."|.0¢".’l..|lsllu.ll+l I|00 r . _ _ . _ .. .
¢ I w n . . . . . + .I I I'lit II I! 00 .Ill III“. -0- I I I. . . -
-0 a I .~ + u + I I + . n u . .IllIvTIll 0' n
_ — . I .0 In I .0-. II. I "I. I. _ v _ . . . . _ . . w “- fiIIIT'AAIIII-ITI}II1I.-I- +
w I. I . m I I I I I. .... -. .. . . I. -. .1. I I . I . I. . I .I.
I .- IJIII-Ii-If: . I .- . I . I I I . _ I - I - .-I-I- - . II .-I---.I- .---I .
I . I I I .m w _ - - - . , . . _ I . I I . I I . I . . I
I . . 9 . I 0 . i» . I . I . . I
-.. .. g _ . m _ a. w I . . . --- _ I I I
P I I. . I I :_- fizz-ii-.. I-.. ... . _ _ I 01 III-IT-.. I M
. I . . I + as 3.0. _ . m I I . I + .
III-I-I. I _ I I . I _. 3.9 fl»- #3 Egg-J - :I. . . . .I . I _ . I
I A .-. “ I. -+.OIII'|',.I 0 _ . _ - _ . — _ _ . .... 3|: .. 4 cl . 0 §.+..I¢ 0‘ .. a I-.. . II“
+ I I r 0 000-. III I I I + . I . I
. IHIIIJIII'II“IIII.If§’I » + + . + + . . +
I . I g I - Yul). A‘IOi..L|IIII-u_oll.’...9 CI _ . .._ . _ h . + ‘ . . .
f I + + . . . + _ . + . .-.-60.1; 9i‘ll'r9. ‘FIII III! tloul .4 . . I II + I . .
..I +1 0...... u. . . . I + .. + . +I 400.100... 4 h H . +
. .. . .I..I, I I I . I. .III _ I I . I . I- .
_ I _ .I . 0 I . . I. I. 0.. I . + - . . . . . . . . I. + .~
. +. I I . + I + I... --+:-._-. -..I I: --1 - -.-I-. -I . . I w . I. _. +. I I.
+ H + b . I” “- .H . + I M w . + I. - 0.0-1.5. I'll-IO- |.I. III ..
p I I I. I . I I .
. . II I - I I. .I . I . _ .. : ..
p . w} - h

 

 

L

 

/.f

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

H . I I I
.I . I I . . I I I . . ..
I . - .. .. I I . I I . I . _ I . I I I I I I . I I I __
I 0 00 . 0 0 0 ¢ .0 . I . I . . I
w . .0 0w. . v r .0001“ 0 t . 0 000.. 0 I. .410 0 I .0 0 1.0 k . + . M o. w I. _ . U
I 7 .. I I I _ _ .. I. I I I . I -.I -..-I. ......I _ .-I - :I-LI -- I: 0 . I- -
+110II001.001101.01.\ I I - I I I I .. I. I I w .I u . H 0 ”- I I I . w _ w . .. .I
I . .. -. 10111001140011 1- + ,w - am I1II I .- w I .. . I I . I I . I . .I .
. . I _ 014 I 110 I1- 001110.11 -
I I I I m I I I . . . - .. . I . 0.0.. I .. I I . .40. I . t - 4 . 10-11. . .1H10P101fI-119000-101.0111.”.1100v00110-
... I + . I . I I I v M w I I . + .. + . a - _ . r ‘- u I. I + I II . I . - - . I. -
v 0 ...I 011 a . .900 00 I.- .. — I I _ n . . r .
I _ I - .- ...1-01. . .0. 00 -..- I- 00. - -01010-.- 0.-. -0-0 .0 . I _ + I I I . . .I
w . I . u I I I. I m. M0 . I. I“ I +- 4 "00 .10014... .10 -.AI-I -- . 01. ...-.1 0+1-- .0. 0000 +100 0 0 1+1- .0 ...-0.- .0--.0L- .00 I 10..
. . — . .- - I. I w . - I . . 0 v 0 0 I
«010100 -I0-0.0.._II--O I. -011 00 010010 I I“ .v I”... I I. If . I . . - .I I_ + I I H . _ .I I . . _ . I
m . n . - I0. .011 | 00 0.1 . 110‘ 01.00.10 - 0 111.5 .. . 11000 ’00L v.01 ..... 5.00.111 .0I IILI 01.0! I10 I I ”II . . _ M . I . . I
. . - ”II I ,. I - . 01 .I _ I .... I101 ..1-01.+.00..1-1- 000...-- -11. 1 - I - . .
I I . I .m. . I I.- I. I I i .. I. . I I . .. I I _ I . A . I 11.+01011
I: ..I- .--IDII-f . I- . I. I I - I . I _. I I . I . . I I .I I. I
. I _ ._ -. I--:.-- I .-I ..-- -. 0 .- ..I -. I- - - . I, _ . . _ .
m I
I .40.. I I I .. . I I. I I I I - .-- ....-.-0--00+ -.--0.”!- 1 I
I - H . 7 . . I m I .u I .. _ . .. I I .. I III. 1 - . . a I m 0.... .... 0- -I 00 0
+00- 0 1-. -11-D0m-1wdbfii .01 1% . . I - I - I . I I I . a. m + _ I . I . . . . .
I 0000 00110010! ll‘l'to" 1.1.01. ‘ . . . I 0. . I . .
C I O .- . 11-1 41 0 0|-.00111. 91011.14 0 10 ... 1 0.0110. . .. 01. - - 0 0 L I .0 I I +
I _ 0 b. . . I _ I I I 1 I _ I _ . m _ I _ . 4 11 - 1111.0.
.0 (o _ .I H . . - . I _ ‘I . . I I H I
.. ..0 . .. . - -... 0 - w 0- ,2 r ..._-0. -.Y ...-0 I . + ._ H 0 I - I . - . . .. I u
. . . I + M . -I - - u 0-. -. I -. .-h. - 0.0! .. . . . -I I I w
_ _ _ . . . . I I - l 0 0 ...010...0 01 0.0 .0 .000T00 00 4.0 - I» . I -
w r... .m . . _ . . I. I . . I I. .10.... I .- . I; .
. I
I.- -1- ..--11,. ------1--..--.I--..-1..-.-. - - . I I I I .... _ 1. I . . I . I. . I
I I . 0 1101110.!!! 11101-0.-00 10.111.110.100 I1...0"00010 - 10 .0! .1010“, . liI
H ..- . A I I I All . W 000' I‘ 011“ ‘00 .I ‘1L011411L01'lt1 1+1! 0100p . I1H11+l¢11§0 I 1 00%|. 0 00
I . . I . I . . o I I . . ---.
...-I.--“ ._ ._ _. I C _.. I I .I I
I . I t . .- 0 0-+00.. 0 ..0I. -. . I.- . - I .... U s 0 0 .. . .- ..-” I . I I I - H
— . . \ _ . I W t - * 1o .. Q.‘ ‘.n0 .0 0.0 «.0 li I .0 . 1 I
_ I. J m I w + . I+ . . . . . ~ I . M I W W _ $ .— %.. I
v0 11111111 0.11- U'001- 0.010.- 0- . . . . . I . . . .
._ . . W . . 0' l0.w00d- ‘91.I‘.‘ |.. 1.5.4-101" .IIIIII'Irbnl‘I.1I014-lll.ll 1+1l1.0050011.0- . C + w M o . M . w
I I I . . . . _ . I 0..-. ...-1.01101. 1-1-1-0 11.11.11 0071!-.- -
H . I _ I _ I. . I I .. I _ .. _ 0+ I I. .- w- 1-.101- ..-I
. 0 - III 0 .I. I 0 .0 0 .- _ I n I I u I I I I - m I I I .
I + m M I I I .I-.n- . .I --I..,...-“- I. w. -W- .h H- _ . I I .
I. . I I I . I . I . I. -_ I I I I . . I: .. - I ...... I .I- .I0rI- - -
T00 1 ...- ...I ..0 0.0.01 00.70.00.110011II 00 1 _ - -.I L. I _ m I I I I + n +
u . H M . . . fl 04.1 n 110 0- 10 *L‘IIOIIIIKL IIILI 0011111 9.00.1101 0I0I0h1lllt-09100I-w0011h'011T .1llu..u.|-0 I, N
. . I. . . .01001 0 0. -0. 010 0.0 0 0 - 010.01 .It I1 .010 I .00 010
I I I I I _ I . I I I s. I I I I , I 1
I I . I _ I. . - II . .- I -..-m ..... I . ----- I - H I I I
I I I - _ - . I . b b 10‘ 0 .00 0.0 000.1 I I -
n I I M I + I h I . I . .H I I . IL _ w I . . . .H + 1 M .- .m. 0
+01 .00 111190.10 . I a I . I 10 I . .
. 110-0000 .-.... 0...- 0 -..-0.110.... x -.1 - 000-. I . - .
_ I I 1. II- . .. I .- ---,..- .G-I-M-t-E-I1- - ,1-.--.---1 -..-i...- I . I I I I
— . I . o $ - I _. I . . . I I I . *1”. . WI .0 . ‘11:]?! 1‘11 I
.L I a n _ — a I . . . I
I. - I. - I I 1.. . I . I .m I I I I I. I I I. I I
. . . . . I . I-.- . ...... I: . . .. I . . I .. I
. . I . . I ‘ 4000-. ..091 00100101 ...-101 010 .000 .1. t . .
I. I I . I I I . I I _ \A I . I I I I . I I I . - -- 1 .
r 00-0 11.1.0 _ _ . . . . . I ~ I .... -
. 1-1.1 3-1- . . . -- I .0. I. . _ . . _ ; . . . _ ‘
. _ . I d 1 0. 00 0.0000 0000 I0I 51011 r0110. L -0 0091‘] 00 0‘ - . L . . I I.
_ _ I . . I . . . . . .1 . 000.001 - . . - -0
I. I .I .. I . I . .I I I I.- ..I. I II I. I I I ITI 0 - .00 I
N. . I. 0 0 01. 0 .I 0 I .0. 1 0.- .f. I 0-».10-.0m . .1 H. . .-..I 1.00 . 4 00.0- . .. . 00001 0 . +10 m + I . . -. + I . I
M . I I + . . I _ + .. . a - h. 4 0.. r. .10 .---1+ 0.. 1 #0.. 0.10 .. 0 0 k 00%. . - 0 10.1. 4.00 00 -
— a m . . * _ —_ I . A I u . I .
I I. _ . I -.
701-000010I00111al11100- 0 h 0 I I + I I u .
. _ . I q .00 1 - 1010. +1011 - 0 010 I I I - . I
I . _ . I I I . I I I I I 101 P1 I . .
._ I . I . I I I I _ I I _ 0 1 I 111
W: . o 0 . v1.0 0» I. 1- . I o b n .I . I v .
. . I 0 0 -. ...0 L... . I I . . .
M .. m . I I _ I . . _ —. .i....0...?|0|0lo: 10.0..110”0C0000+1l0 9.100.001.0101 - I
I I ._ .... ...-4 --0---+--.
_ I II I + I .I m . H - H. - . b a ...I + I -. .
I .1 - ...-11.--.-.11. . - _- I - I I .I . I I . I I
. I I. I .. I. g I - A I 4 I I . I -
- I + I I . . 1 . .001 1.1
I I I I I I - I I I .I . 4 - I. .4 4. .
.I II. - --I- - -..-I11?- . -..-...-.I11- I I .I I I
m . H . m . I 0 I M W .+ m M. o O \I 0 V . 1 0.“...011 0 v . I 00 9.0.000. 1 {III 0 .1 I w... I0 I
I . L I I . . .. . . . - .
I.-0000- ...0111II0000-10Lf0i0. III-..- I I0 I.-. .1 I M I I - _ I
I . m . . . . .1. 04 . . . +
I I I . . + ,. I I I I I. . I w H __ 1I1 .1 .
0.1 0 - . .. .... 1.10-»-1. 0.0 0 . . I . I . I .
I . I . I _ --.- .-.--.,- -.I; If. -. I I I I . I .
m . + I . + + w. . w . w ...-.10 i 11390010011101 00.00000 000.00.. «0000-0.T.00|0
. Ir . ... I. III M .I _. + I. -I + I I.
m w . r 101 . - I I - + I I . - I .
. w I w I w. .I » I ...11_ I. _ I -.
. . . . . .I I . .. I. 4 . 4 0
.. I I, --.-I. .-. w z w _‘ v . .... a - I.
. M I I I I I. II .I _ J .+ . tI I
. I . I .. . 0 1 -.-0 III..." . ’0’ I}. 0. .010. 0. 0001.1 ...-7.00. 0 0.- .0 0 .50.
I I I _ . . I . I. I ..I 17. .-I
.. I - _ . + “I . I . I .. I. . I
I 1- 11.. I . .. I . I .. , II
1» .I I .I I 01.10010101I
_ I I 4 1I I I I + I
I I - _ . I. I -I - .I - .
. - I .101 .1 110.00 0 . .01 .011 00.0? 001 .1 II .0- ..Il000 I100 §. I101 10 A
I I _ _ + .... I . I
I L I I ... +- ... . ... I I . I I
.. .I I .I .- II

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

12.

11

10

. 1"“ f

l

 

“r“.

LEI;

-i,-
‘ l
- Jim

I
‘
Y
I
—. -.q”

 

fl

 

“I
l
J
z

..~

.

 

‘0' -l- ..-- .—

t

LJ..'.-- -

 

.‘ r .I . "
ill I I‘ll! " ‘lu'! ' .III- I!" II . ' II 'II ill... I 'I nl II. I III ,II III! Egg F I'l II I. I . I I I lit II

 

00*... -o

«L—

--.-6..--1

 

 

 

 

 

 

 

 

 

---.,----
I

 

......uu,

. 4 0.....— :.r I . a.cn..3. \ \ x ‘
...-In! )1- I. .In \-¢'C--i . 0.05-0.00. uh .I

 

 

 

 

 

 

II VIII .II. IIIII I I “IIIIIIIII I1IIIIIVIIII1II 1 I “I ‘.II I. . M II «I . III III Ila IIflIIIIJ s s
.. _ _ . Am _ H w . a . . . ,. .. L .g . I“ m _
> . . . . . . . .
, _ _ fl _ . . . . . ... .
p . .. . . r I. L- . . _. -I -.rt I» U . .1 . .M --.- ... -. I .. .fii . 1.1+}: .1 ..L. -,II.._I. I
. . . .. . d w H u I . . _ _ . ‘. .. .. ~ H ..
n . _ . . . a . . . E w _ . M . _ o
. . . . . _ M w . I _ . . . . . . . a b
III III IL III! I III.I. III III I II I O I II ILIIIIoI III I II III. VIII II; III III IIII III IIIIIIIII.III IIcIII .II I. .II IIDIIDIIIII II b 4 II
. . I z. . ‘ I . ._ . .. I 4 . . _ . . . If]. . _ . . _ I.
. V _. . . _ .
. . . w . ,. w w . . a . q A M ., . w _
”I . I? P I I)". I ‘0. In“ “ I v .x I v. I I « v IIIIQI , IIIL .I IIII‘II I
. . - _ u
_ — k A _ H “
. w . . ~ _ W H . q _ _
III“ IIIII I I I I 9 III II I; III. I l I I III I I +I III II III 'I‘mI I...III IT I I IIflII III IJI III II“! IIIIIIAIII I IIIvI IIMII II II I II“.1 II I I I ITI‘ III fi' IIVIII
. . M . ._ . . I. . . . m
. _ I . g H m h u
I § _ .x ,. I, p 0. It 0 .iI ._ I II I I I» . I _ I
. . . ¢ . . . .
. . _ _ M _ .
I I I I 0 III III ,. - I I III I I. IIoI I II I I I II I IIIIII I I II .0. OK! I! IIIY .0 IIoII .III If-..IIIIII1I IIIIIIIII. «IIII,III I<I I I I
K m _ . V , . ll. _ . _. _ . ,.
. A . _ . _ . _
. . _ u , .
. n a O . ¢ . I . A
m . u . , H
. ..II-IQ.. I I I u. A I I I. I ‘.9 III- LI I I I . I I I II I
_ ITI. ._ _ ,
,I ,
K V .m _ . _ _
. w 0“ m ‘ .
. I I
I I II t.-m- I #5.. - - I LII: I - -
u a. _ H
I . P” I v In
J _
I I I I I I l I I I I .I 7 I
m p I o
. m
I- - . I - - - . , .6 .HH. . --I - -I . .1. l1: -
. _ w 7' 0 o w. I .. I
a
, h . A n ,_
_
I I I III I II .II I I I J |. I I If. *5 IL I! I. .II .9 IQII‘II I .ALIIIII II. II I «III! I
. * _ .
_
_ _ . .. .
— _ _ . . H
u I I» .l I I I- II .1 III I- I, I “I I I 1.. ..II II .AqIII II I III In. IIIIIII IIIqu II? I III I; I .. I
V _ r . . _
, .. _ y _ m
, I . I I f 4 a ... II . o I . I 4
. . .. a . w . * .. . ,
.. u . .
, , , . _ . . .
I II - I - I II: I iI I II I IIIII -LI I I: I I I- I II- . I I I .-I I I I I- 7 1,-IIII .-IIIIIIIIIII I -7 II ...I
. . , . , J. J M _
_ . _ . *
. _ . u .
. . . . .
. I . . . , k . . - . ..I :..-.....I . . I T
. . A, . . . . 7
n . _ W . . . .. . u _
I I .., I0 I “V. I II C I II.I .. II 0 I I I I I < I4 ITIIOIIIfiIl: I. II‘II I I I_Q I I..I\dI¢.I.Ia IIII H. II: II I. I III
* M ,. _ v _ . . M .
.r I M .— * O I . t H 4
u n . n _
. o — _
I T l I I 4 a I It .I 9.0 III I I II IIIIIII WI III .4' II I l
. . .
. w w W w W M 0 _ . n
.. . . . .. _ I .. . IL I _
.. 123:: ”5;. #d «93% . . . . w , M
m w n . m . a H . k w
I F IIIIIII. I IIIII I I I . IIIIII ,O.I II.‘ . . .. v I a IIII I *II ‘ I+I 11.0 I I‘l 4—“ IIIIOIIIAI II I I
w _ . . _ . t n _. r
. . . _ v . .
. n ._ . _ ; u .I 2 h. . ." .-It. I- It, .. - 4. - .... ,
u . n . W . . . . . . . . . a . m
. ., , , $ _ _ . _
III Ir H b L . V _ h . I - _ p L . p ._ . ~ h . I w w . r _ .

 

 

 

 

 

 

 

‘IA

To test the reliability of tFé co dw+¢q vnlfi%s

I-I }‘
1..

of t

‘1

(:3

fll'infl, é ssrlcs Of Fefid‘flfis Len fiken on

U:

p

1 0: l of 0.336 mm. t ickness i

at a wavulemgth of 1.05 microns. Savanteen rundinés

‘
i

VJCZ‘B 1‘ £371. 170‘:- ‘j."t:se COHi‘itiO'WS 4.33%; war-M1 *3?"—1!‘,S’“7189“0n

’ V" 1 " o n "
was 99.4 3 and t8 Stélt’lferI“-.. Ciri‘fi:'%t10'f1 or re~:.:ar-‘1-'wn from

. .l
.. -. ‘ .. ‘- . r‘ ‘1 ‘ ,‘ ‘ . ,- ,_ . ,~ r'
the we“ 2'1 ‘ ’8 CO ‘-.“‘._*:'-:d to be .4 “>11 ”we: rawdi 1: ‘. 45

seed to BM in "Peat error, Pfiv 1f tHis one w?~fl€1:
'v".‘flS (Ti-321mg;r1165, t‘b :‘3‘v3'~"1r“-_a1'-r¥ r'w-:vi-uh':io=w bag-WM: 1.70".
mkifi is j“9fifiable Cinnc tWQ Pnrve is ”rflwn in SHPV
a.~unwner tfiw t poirnxs obvixxufikr fallfi L? off t1w§<NIrve
are not included 0? it. The probable standard dev-
iation Of the ”man CO“DWted foe tfiese seventefin refid-
i’Z'TS from ‘tr‘e fir-1‘1: 'Zii?i."7, 372117: onwn‘tfl‘xl to he ’1 ‘3‘?
From +30 ‘etkod of conwmtiqi fie *rnlsrissiow,

L

.. .~.~ n. -.- -
it Vi1‘*.f [, 363.1

v
\L

srw$17, ti: err-0r Tweclr" s jL-7w*er, 5%n(r Mlx'o {us tVW9 SWfiAS-
.« . . . ._, . _

sion of th¢ source bcco Gs flWbllGT iw iqfedsifv tFe

.I‘obable err fir- rif- t3.‘i~lf'lSTi’.iSC‘lO*1 rewdiirrs hecows (51“.3fifif3r.

21

--.-
l
O

- 1*...— a“- -
f
I I

 

-—-——. -F-hv c—T—w-o ~-—-v-r
t g I

...-...-..q’ .,._.
n
I

 

r —q—-———_.~_—-—..- _--- u.— w— .—‘.----.-g
I I .

l
d

I
l
I
i
i
g If

.1,
T

‘_
fivv

3
.1 l J
*4
l
f
“f
12) Hi
I

5.’

..-.l-|. ...... ...-.4131... . . -,. . . . -
. v . . E1-ll-l_""

l
I
I

[1
L

J l
T -
I

L
fillI E; 11:11, All;
. ' [I . t :
‘ l

T?

l

I

1

ll

 

41;

[UL

 

I
-.-l

I
Q O O O
. l
- I
‘ I
4 _ ‘ A I -
V I l
' I
3 .
I '
I I
I
I
- ——

it
‘

 

I]
I
IJMLfI‘

_ A m LMIcmns ,.

I fi 1'4 I

,I
"

VI
"' I

 

 

'l
1L1

l

lllll
7

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

"' . .2 J‘ '2‘ .
.Jl30181L01 oi mealts

 

 

oince several of the Vitanin Fréoarctiofis
stuoica coqtuincd vematable or ndiNQ1 oils, it was
cinema-“1 ";L—:C<;€3:3r:1'jf to st'ltljw' the j! ?‘ ‘2I’3?"17J'“1 031 of se\.r.»-,-.r-1]_

'0

0318. A commercial preuerfltioq of Corn Oil (”Iazola )
”Pis oil consists Wainlv of oléic cod
lifiolcic flcid and was associatofl wit1o 1t a svnll
amount 01‘" sttcrols of“ *.'»'?*ic7‘*, C.r"01*1.‘.t33“01 is t?-~e 011V

Dru: prw3scr1t 1T1 bgr)rc;,isfl)le iv“CHFut. “Fee Sdffijl? IIS'nl

was NCCantcd from the too of a carol? w"ic3 had been

Stfitldlfvfi in a.1w35ri+¢3rutcu‘..or SMIwe deqrs. 371 this TJXJ

the sterols were for tFe most pfitt sct31€d ovt. “P9
curve obtained is given in Curve III.
This curve s‘rzonld be con-Ural with Curve II for

purified 0101 acid. T39 maiq difference is a Vida
barui"itl.'caxirmr“ absrnv3+i0t {ft 10.63‘tiC1qug nyvr?¢rifioj
in olcic acid. Soverql of tte other bands are Sniftqd

sliggT'itly. foizwoltsic acid Cu‘rtl‘tazj'. 1F} +7.0 donhl’? hooflg and

oleic acid one doublc bonfi in the side chaifi.

H
LII
x:

i4
.1:
H’
.3

It should be noted at this point our
mind in the discussion of all 0“ the following curves

with the exception of synthetic Vitawin F1 and mixed

natural tOCOpVerolq that tke credofiinating fortnrcs

L

23

of these absorption curves sh_w mainly the absorption
of tke various fatty acid oils in utict the relatively
low concentrations of vita ins are dissolved. ”$9
vitamin A cowccntrste is abowt 40: Days and slo"s

much more fine strrctwrs and cilgersicss from t*e

curves for t‘c MOPS oiluto isfi livec oils whicl contain
ttme szv‘e tritauhlrl. Ira? 1W38‘t1fi;73 (SWTVVES lf‘e'léfirfi' t1%3

cu1nfes :for iflfie ~\.rit:.~:‘.‘.i-ioils :13 smict ~u1o vat fflwo c‘nvves
for the fl‘ll‘b‘ Vltii’ilf‘li) t‘r‘_cvfisez_

livifixytiono CH1 3*" int PprwfixvtiOI of fltzmsils, arm? t‘e

CUTVUS presentfid coonot be comolctf

l

(L)

0.
C 1‘
Ho

interpretr. (nma of tn
in hlV 33399. hecanse of ttc iwoossihilitv of koovisq
exactly Wrat imowrities are present and in vtut coo-

centfation, it is ionossiblc to get an absorption curve

I

of to: cure vita in oy plutiim tVo imourities owl? in

a comovrisou .cll as is 00%“only ions in succtroohoto—

.£ . I
\

wetry tectoiqucs to cancel out t‘e e”

3"5‘

act 0? i“otrities.
Wle vitamins PPB in t evselves more cowolex tlcn wow
compoun S for WVict corplets Enfcapeo analysis Ias boon
Carri ed out .

Curve V stows the aosorttion of s refs once cod
liver oil containicg 5,200 *it: in 1 units ctr ”rm .

T“We CTLFVtB tl~lrcxpctwa it: eSLHBQVfi’IllfT I”??? ci‘ t“? ‘Fisl“

l I

oils proscnt.

l

.5“

rm“ 1;)
' v

corn oil is gi

cmf-ve for- i?=1":5;('li:3_t<3(i eY‘_TfORtE‘.I‘O1 dissolve—3d

'1").
L,

t.)
.‘J_

v “ ii Curve IV. This oil contéiis

a

500,300 Vitamin 3 units pf? grow. IVs curve fiiffcrs
from ttat for COTH oil only in the dent? of ttc ab-
sorption band at 6 nicrons an“ several sugdsstions of
bands appearing at 4.1, 4.4, 5.5, and 5.6 microns.

”“51 (’3

I

is given in cu

contains 65,00

VII 86,000 per

7..
tltv

plainsd by

O

the Citrves ;";iv

oil.

Curve VII
absorption of
purified fPom
1y to vitnnin
aruwultic

8. fl .1171

however is sat

‘. < \ J. /‘ . .m.
Tinsel t‘HI‘C; tad sin

3i 0 S 01"

ptiOI of chrsqt tslihut liver oils

I‘VGS VI and VII. “I“? 051 Of‘ Curve V

I

n
I;

O A units per gram, and that of urve

gram. Tte difference in corvos is ex-

3
J

difference in thickn op

z)
'~/ (.3 S

n the difference in vitnnin cocccotratioo.

he s

p

Y can seen between tocso nd

01171KTE'5‘S

on for corn oil and fits rsfcrctcc coo liver

I for nix:d natural toc0ptcrols is ttc

:5: 116:;LI‘1V pill“: Vi t:J.."‘-1]'_‘:‘1 S::3‘r*nl3 loic‘c tins
vcgfidxflmlc oil. ’W is vita i.1'hss, sfirwilsr-
A, a long slipkntic ctsin sttscicf to
clsus. TIT-’3 Chain 0;” tle tocon‘werol
urutsd, “Mile thflt o? v‘tnmin A is

d t‘c donbl: hoods occwr conjfigatcd to

.
1

each other througrout the length o? tre c“uin. ’%e
band of the flouble baifled curbOHS appears at 6.3 “icrons

in vitamin A COicertrste (Curve TX) tron

(D
*S

such strofig

for tocopnerol. From the spoesrsnce o? the cnrve, it

seecs probahle t”at t*e o‘rified vitamin oil contflics

a residual of fatty acio Irow the crisinol veretsble

O
9
...}
f)
s
:f‘
"5
{:1
of
{U
1')
Q
-,.J
C—f
r:
H.
{j
H.
,J
’ 32
t0
‘0
CJ
(.1
[1
b
C)
C)
O
0'-
R.
,3
J.
.t.
Ln
(3
\D
}_$
I l
*3
C.)
E
O
‘ ‘3

n {\t

approximately iof pure vitncid L. Tris curve Q‘t s
31 ruin}? JJIIV’tI‘ échNifrt (if flfifi' sitr11c+uwrw3 finsyi tine ~noywe
dilute fish liver oils. W e csrbOn to carbon sinfile
bond band appears stronflv st about 10.1 VICPOQP.

n8 vwritionflilzflwove, iflce CEIWKI? to csrlumw doutflfé‘bonfl

band is TUCH stroneer in tris case ttan for tocooterols.

(_)

I“

- J ' :1- ' 1 I! §v ‘ ‘ ' 1‘ Y ' v .'u ' \ -~ ‘ - ‘-’ -
'W”e bLTMI'DTOMJCtIIIX‘ tne rjwirOXJl :mxnn Jpei;¢:» eekly

|._J

at 5.0 microns. Viis will he discwssed ater.

The curve for synthetic vitamin K1 (2 ”ethyl,
5 phvlvl, 1:4 naphtraquinone), is given in Curve X.
This vi,nnin was dissolved in a swell amount 0?
auritic acid Vflwni ohtsirvxi. Vere, {rs ir ttrecrsse of

the mixed toconherols, re ere dealiid With a loos eli-

phatic chain (with one double homfl in tVis easel

26

atta.ned to a nspttnaquinone nucleus. “90 pronounce

1s. 0i? c1“ firra

f—lo
(I!
4
O

slnaorqaticm1s zqucxgr ext 41.0 Euld /.S .
strfimrhlre agugesrs tilt xtmd(er.

In order to discwss tre Rita as a vhole, refer :0

CD

may "e find-e .,0 figure 11 Roi C") contains 3 condi’L-itsed
recajitulstion of tho absorption curve . ”e wav no»
consixbsr g‘weritsrmfiétion.lnnuls (tie tF>if1nctirNTxl ‘mezos
for-1719 rluole :nmvuo CH“ cc“fmmirds ‘isedJ

The CurbOA to carbon sinvle wood occwrs at 13.15

. - - ..‘_ . x ‘ . u‘ 1‘
:‘icrons :Z‘CUTOITL‘Gs.telff and ‘ (10-1117 L01" "t7 “1‘0”:

5.14 T""lCl‘OTlS. 111 (If *3. CO“?)<)‘:1W(1" used 001‘tfl'5fl'1 the

siirfle 170211 anfl ttus tmfiid cocc‘u7s r‘ trigi 1i Tits (3? ffi“or

r-J'
")
’3
L
1-5
.
“i
._)
T
D
..5
m
Cr
5+
.4
\

ccwniourmis Inivi31> =s 1crip afilin'14t
acid oils such as olcic and linoleic acids, r315 bwnd

is not very strong. TVs double bond occurs once ii

tte bard appedrs s“ 6.0 ricroqs. Wfls onrd is slig‘tlv
deeper for corn oil cries cost ins some lisolcic acid
than for Pure oloic soil. Irradiated ergosterol and

all vitarin a contsiiins oils “For this bind st wave-

5-,-

lengtrs frov 5.9 to 9.2 microns. vit Win A1 Costs ns

3 conjugated series of four donb1~ bonds in tle sliotstic

to
<1

side clisin. synthetic vi timin 1’1 contains oolv one
cnrflron fUriblxe‘bovmi 1Y1 tin; c t;in :;nd *fl"e (toriwasntyyiirnr
barv‘ is vendc.

The -0-“ groupinh occurs frO‘ roowt 5.3 to 3.8

. q
F'lf‘-(‘l"0.lf§"

and this bflld occxrs stroxslv For 011 lisrids
used at wavelengt s fro“ 3.7 to 4.1 "1C?019. ”fie
wavelengto Pf t is bxnd "grvs considernrlv fro” co“-
fiound to co oomsd.

t 9.87

.'11 ' . .. . .. .- 1- .'- . - ‘ 1, .- , .
ine DJJU o-ua I) cue -C-U- ,nwyu).13o;sgs u

Ifiicrwnis. ‘Wfiq Sfiwyit :uwwearw; foriijw; fafflrr aci(i and.

U)

most vitnnin oils coitxioinf fottv acids. T%19 is an

eVioeice of lvdro

ea bordinq since this Troup would not
sppcmas in tfiue castesot on.?onicoxvl.ggcoup (Hi the currbcn.
Th,s will he discussed more fullv in tre consideration
of tHc *vdroxvl group. Toccoherol contains 9 0-0-0 group-
ifu; in Tflua srcvnxtic trini {sad time bsryl sprflr rs {it 9.4}
micrOis. Ire =C=O bands for acid and Vetooes coresr
a‘:".02 auri 5.80 rdxnwons resrrwétivelv; M~e acid Tvnqd
occurs strongly for all Oils containihfi fattv acids.
Vowever the bands for the ,srboo to carbon double bond
and the cmrbonv] group Overlap one to +10 low resolvtion
of the instrument. 7V9 xeto e carbonyl grouo occurs

in svnthetic vitamin kl and tiers is no associated

28

oil. The band here appears at '.2 microns.

p)

The band due to the_hvdroxv1 group is probably
the most worthy of consideration. Tris ban should be
verv absorbent and should appear st 3 wavelenqth of

2.96 n

E
O
03

ron Within very close limit.. Heroes, Ronner,

. C __ . _
and CondonJ have reported that fottv fiCldS are polv-

merize esnecisllv rken in the liquid state at ordinary

' ’

temperatures and that even in tre vapor state more than
50* of th amount oresent is present as diners or rich-
1

GP polvwers. These oolvmers are formed throuoh nydrOQQH

bondiny ytict effectively destroys the vibrations due to
tye kydrmxyl group and the bend at 9.08 microns snoesrs
verv mucr weaker. Gordy5 rag verified this observation
and tfis used the decrease in ghsorotion Qt 9.06 wicrons
as a measure of tre amount of HydrOgen bondins taking
place. These factors expl in the absence of tte Evoroxvl

D C
q

“and 171 "7.80.1“1V 62.11 Cf:s+-:s OhEEQI‘Vf'Wi i?“ +1.19 “'erwti Tflti 0Y1.

In 1’10 119‘1id use-d i148 tRere forum :mre: t‘vcn .0 verv weak

bend or mere indication of snob a hand. ”Vdrcden bonding

beoirs in tfie fattv acid series zit“ valeric scid 33d
C)’ ‘ ' - -- ~
increases mitt increasito chain lonobr as #nflic ted

k}
above. Connouods need ore of tfiu loo? aniq lenftr

C 1?; S R (.3710. ill :3 ,1 '3. {‘3‘- OS‘. (ii 0 U? 7‘01]. W11", C M“ 1‘32; in]- g1 no E"vjrr7r-fl;-jj,rl

{‘0
{O

“' ‘ 1" ' .3 ;_.- ‘ ’1‘£.:rr-\ I‘ -'\ ’ ' ‘3‘; I "J ....» . . I '1
ésliod'p, r1.\.'r‘ 1'1“ (‘V'Ayk’ ‘1 'rj‘“ (*1 ~'" '11]: Riv-143 O '_'_1f\,lP'-’T‘[C’. 1‘ .C'J {I l “.

L.
l

73531:“,

1-“

c1iL4r13J t1) “Witwwfijw . c<wncerwtrm he. “(a e (ww77r 9
very weak band occurs at 3.0 to 6.1 ”fi0r0“3. ”Wig
13:1yxri *_:f 1113 5“:r=(>r;g;<3:1 1" $131 't1"<% }T’1YTF3 r.§1lw«3r13<3 r; r { v. 13*nae H,, )rfijqi
“[100033T693‘013 '-""“_"..C‘.": 0175*" in __O VvflrOYjarl i‘fj‘()"-F:)‘3 in +5.39

tocoorerol rolccnle. T“i9 awn]? m~ourt of 9%

1')
[J
-e
d
‘ “9
.J

; J-
A
[J
, 3

90111” Vein”? 00‘7“”95VM‘1Y 91'”.va from '3 s:lif""‘t Wimfr‘iwml

woisture re filfllfifi 1r fite oil.

T*e verv lov uosorhtion at 2.98 microns tHPOVQh'

es of CO.‘"‘CO‘J:‘.L‘.S need 19. crwnI-g (évifleavme of

9
d‘
('1'
:3,
1T)
0)
CD
“S
...].

tr e 1" i r“? r? a; Irwae 0 f‘ :‘s. s; 1'_ :3. t"? O or nor-"Y" Peri 2: e 75‘ no
I 0 ~ .. _‘ ‘ - ~ v, . , n .
OCCTTTi‘T 11 hzcw olecLluw \oi.Ht co olox COIUOJHdS

when even one rvflrole promo is rreeent on tte molecule.

1

C»)
O

Sumflurv
W

1. an apparatus is cescribed for secnriwz the

infra-rem absorotion Spectra of oil

3.
2. A fiiscussion of erpgrinehtel details, dif-
ficulties encoutterci, Lid OPGrutirr tecroque is

~1-

Fiven.

\ I
C

3. The absorptioq curves are given for the
following vitamin oils flfid fatty acid oils from 1.9
to 12.0 microns:

Cleic acid

Corn Oil

J.

Irrediated quostcrol in Corn 011

Reference Cod Liver Nil

LLil’Lbll—z i'ivt’sl“ “ll (2 'ngY‘nlg5BS)

ixed.ifizturn]_'“ocoo*&nwth from \hxtetukflfé Oil

v-‘0 o f _-.4
Vitoml‘fi. .L-~ Concentrate (“bout 4IJ~ p1_:re A)
a "1+ 'af'lC‘ Vi ta .131

4. Cocsiderution of curves slows trot severnl
inter—atonic linkages ray be identified from trese
infra-red absorption soectru.

5. Chmmsidorafflxr: of Elf :Jfieorpticnl band (tie to

tre hyfiroxvl

CO
..4
f)
\a
J)
§.
’\
»

grouo gtat lrdrozen boifiiro occwrs

to e righ Ce
/
cowymmrrls of

an hydroxyl

~ ‘ “ ‘ “. - "| 4— ‘ 1 ‘ '1: "r1,
The althor wishes b0 dCKflO\1Bu;

rendered by

m
'I
’b
|._J
(D
U)

thi s i 11‘.’ r: s; t

of natural and sthretio v

" “ . ' . v ' o v " _

{SI’Ub 1Y1 13-” .7 (131(1‘3 mxl
- ‘ N ...| ’ ‘ _ . ”A

large holnglnr Mglgut

\ I‘ 0111;} o

)

.L.‘ 13 , j *\_ , M -- ,I
one IfltrfixrtguVlJS Ccmronsnr

"—Jo

t;£1tfi. 0:1 0

(,5;
{\3

US

F-l

6.

8.

9.

Coblentz, "IMVestign‘iofis of infra-red

Carnegie Iist. Of'"2ufifivutmq, Pnblioation V'

(1905), To. 65 (lQJB), To. 9” (1938).
Erode, ”CleIiCul Spec
go? York, 1989. Cluptcr X.

Gordy, J. CVeW. PTVS., i, 749 (1958). gee
later publications.

Barnes, Fmflz.i7ci. Instrxmoqts, V, 265, (195

a
__ .
i

—0

t.
H
i.)
ya
y
’x
:3
’3
( k.
l J
C.
v
' 4
0
O
J
s
O
Q)
.1
O
O
3
\fl
:3
w

(1957).

V v v T “\ -: A ~. 1 "7 I” "'
()'..‘_)‘fr.1U, L. o (Ejt o L)‘\JC 0 4.1.1.. , Ct), 96, (1E7()())o

z
D

rJo

.ldsutorffl‘, I”: 1:. Laqg., (5) £59, 34€3 (lifiiél .

also Reference 6, *p. 1&5-167.

3_ *0 7“.
‘ufllflnt aner

7

urewsfit of

C3

Forsytre (ed.), jag
“CQPRW-Vill. ”CW fork Ter'Vork, 1957. p 5.

BurnGS, Bonner, emu CUlLQl, J. CVe . Prys.,

7'72 (H.356 ) .

55

also

6).

H
.p.
{\3
PC)

{7“{7
3

A

l:

 

  

QTRIANGLE '
0 MWW \
fig‘u’gp
% \fi

\

 

T544 F453 143865

Field

T544 F453 143865
Field
A study of the infra—red

absorption spectra of sev-
eral vitamin oils.