An attempt to separate from petroleum spray oils the portion which is injurious to plants
by Jesse R Green
A THESIS Submitted In partial fulfillment of the requirements for the Degree of Master of Science In
Chemistry Montana State College
Montana State University
© Copyright by Jesse R Green (1932)
Abstract:
The purpose of this Investigation Is stated In the title. It has been conducted on the hypothesis that
some portion of petroleum spray oils is especially injurious to plants. On account of the great number
of compounds in petroleum and their close similarity, the identification and separation of any portion la
difficult. The complexity of the reactions of the compounds of petroleum with those of the plant has
made it almost impossible to solve the problem by purely scientific method#. Thus, in the absence of
strictly scientific means, the cut and try method was used with the aid of whatever scientific knowledge
or methods that were available.
There has been considerable speculation regarding the compounds that cause plant injury. The blame
has largely been placed on the unsaturated compounds, but there are other possibilities. Sulfur and
nitrogen compounds may be responsible for injury, but it has been shown in a former Investigation that
the part that nitrogen plays must be very small(l). The oxygen compounds in petroleum are also among
those that may be considered. Hoerner(2) has proposed the use of sulfonated oxidation products as
insecticides and gives data showing practically no injury to typical plants. It la generally conceded that
these compounds are efficient insecticides, but their effect on plants is still an open (1)Green, Jesse,
Chemical and Physical Properties of Petroleum Spray Oils. Accepted for publication by J. of Agr. Res.
1932.
(2)Hoerner, John L., A Report of Progress on the Testing of Sulfonated Oxidation Products of
Petroleum for Their Insecticidal Properties. Vd.
Agr. Expt. Sta. Bui. 310, 1929.
question. Until more Knowledge Is gained regarding petroleum compounds and their exact
physiological effect it is best to with-hold opinions.
The causes and nature of plant injury have been discussed by Kelley (1), Swingle end Snapp(2) and
Knight, Chamberlin and Samuels(3).
In the course of the work oils were treated by over 120 different processes and then applied to barley
seedlings to determine the Injury they would cause. The barley seedling method of testing spray oils
was devised and used in a previous work(4). It is carried out by applying the oil to be tested to 10
barley seedlings that have been grown in quarts send with nutrient solution In a small earthenware jar.
several more than 10 seeds are planted and when the seedlings are 6 to 8 cm. high they are thinned out
leaving 10 that are uniform and that are near the height of the seedlings in the other jars.
The oil ie applied to both sides of the seedlings with a camel's hair brush. At the end of 3 days the
seedlings are cut and weighed.
Their weight Is subtracted from the same number of control seedlings and the difference in weight is
computed to percentage of the weight of the controls and called injury.
(1)Kelley, Victor K., Effect of Certain Hydrocarbon Oils on the Respiration of Foliage and Dormant
Twigs of the Apple. 111. Agr. Expt. ate. Bui. 348, 1830.
(2)Swingle, H.S., and Snapp, 0. I., Petroleum Oile and Oil Emulsions as Insecticides, and Their Uae
Against San Jose scale on ,each Trees of the South. U. S. Deptl of Agr. Pul. 253, 1831.
(3)Knight, Hugh, Chamberlin, Joseph C., and Samuels, C. D., Some Limiting Factors in Uie Use of
Saturated Petroleum Oile as Insecticides. Plant Physiology, 4 : 288-381, 1928.
(4)Green, Jesse, Chemical and Physical Properties of Petroleum Spray Oils. Accepted for publication
by J. of Agr. Res. 1832. AN ATimPT TD SEPARATE FROM PETROLEUM SPRAY OILS THJB
PORTION HIGH IS INJURIOUS TO PLANTS
BY
JESSE R. GREEN
A THESIS
Submitted In p a r t ia l f u lf illm e n t o f the requirem ents
fo r th e Degree o f f a s t e r o f Scien ce in Chemistry
MONTANA SiATE COLLEGE
APPROVED:
'Chairmen Graduate Committee
Bozeman, Montana
JUne, 1932
Content#
C onsideration o f Error In Metliod - - - - - O il# U s e d ----------------- ------------ --------- ------------D i s t i l l a t i o n o f O il# - - F ilt r a t io n o f O il# - - -
- -
- -
- -
- -
- -
- -
- -
- -
-
- -
Some Chemieal Treatments - - - - - - - - - Sulfonated and Other Chemically Treated O ils
O xidation E ffe c ts on O ils
- - - - - - - - -
Treateient o f O ils by K leetroIys i #
- - - - -
E x tra ctio n o f O il# With V o la tile S o lv en ts
E xtraction o f O il# With Ammonia
-
- - - - - -
D iscu ssio n - - - - - - - - - - - - - - - - Summary
- - - - - - - - - - - - - - - - - -
F igu res
--------------------------------- ------------ --- - -
Appendix - ------- --- - - ---------------------------------
- O- O
43224
AH A T im tjT TO SEPARATE KROM PETftQLKPM SPBAY OILS iHE
PORTICH CHICH I S I tJJUKIOOS TO PLANTS
The p u rp o se o f t h i s in v e s t ig a ti o n i s s t a t e d in th e t i t l e .
It
h a s been conducted on th e h y p o th e s is t h a t some p o rtio n o f p etro leu m
sp ray o i l s i s e s p e c i a l l y in ju r io u s t o p l a n t s .
On a cc o u n t o f th e g r e a t
number o f compounds in p e tro le u m and t h e i r c lo s e s i m i l a r i t y , th e id e n ­
t i f i c a t i o n and s e p a r a tio n o f any p o rtio n i s d i f f i c u l t .
The com plexity
o f th e r e a c tio n s o f th e compounds o f p etro leu m w ith th o s e o f th e p la n t
h a s made i t a lm o st i: p o s s ib le t o s o lv e th e problem by p u re ly s c i e n t i f i c
L-ethods.
Thus, in th e absence o f s t r i c t l y s c i e n t i f i c m eans, th e c u t and
t r y method was u sed w ith th e a id o f w h atev er s c i e n t i f i c knowledge o r
methods t h a t were a v a i l a b l e .
T here h a s been c o n s id e ra b le s p e c u la tio n re g a rd in g th e compounds
t h a t cau se p la n t I n ju r y .
The blame h a s l a r g e l y been p la c e d on th e un­
s a tu r a te d compounds, b u t th e r e a r e o t h e r p o s s i b i l i t i e s .
S u lf u r and
n itr o g e n compounds may be r e s p o n s ib le f o r I n ju r y , b u t i t h a s been shown
i n a form er I n v e s tig a t io n t h a t th e p a r t t h a t n itr o g e n p la y s
a a a ll(l).
u s t be v e ry
The oxygen cor pounds in p etro leu m a re a ls o among th o s e t h a t
nay be c o n s id e re d .
H o e m e r ^ h as p ro p o sed th e u se o f s u lfo n a te d o x id a ­
t i o n p ro d u c ts a s i n s e c t i c i d e s and g iv e s d a ta showing p r a c t i c a l l y no in ju r y
to ty p ic a l p la n ts .
I t i s g e n e r a lly conceded t h a t th e s e compounds a r e
e f f i c i e n t l n s e c t i c l d e a , b u t t h e i r e f f e c t on p l a n t s i s s t i l l an open
O ils .
t 1^Green, J e s s e , Chemical and P h y s ic a l P r o p e r tie s o f P etro leu m Spray
A ccepted f o r p u b lic a tio n by J . o f Agr. R es. 1932.
( 2H to e ro e r, John L ., A R ep o rt o f I r o g r e s s on th e T e s tin g o f S u lfo n a te d
O x id a tio n P ro d u cts o f P etroleum f o r T h e ir I n s e c t i c i d a l P r o p e r tie s . Md.
A gr. L xpt. S t a . B u i. 310, 1929.
-
q u eatlon .
2-
U n til more Knonleuge i s gained regarding petroleum o o ^pounds
and th e ir e x a ct p h y s io lo g ic a l e f f e c t i t i s b est to w ith -tiold o p in io n s.
he ca m es and nature o f plan t in ju ry have been d iscu ssed by K e lle y ( I ) ,
ho in g le and Snapp ' ^ * and K night, Chamberlin and
am uelst3 ) .
In the course o f the work o i l s were trea ted by o v e r 120 d i f f e r ­
e n t p r o c esses and then applied to barley s e e d lin g s to determ ine the Injury
they would cau se.
The barley s e e d lin g method o f t e s t in g spray o i l s was
u evised end used in a previous work(4 ) .
I t i s carried out by applying
the o i l to be te s te d to 10 barley s e e d lin g s th a t have been grown in quartz
sand w ith n u tr ie n t s o lu tio n in a sm all earthenware ja r .
se v e r a l more
than 10 seed s are plan ted and when the s e e d lin g s are 6 to Q cm. high they
are thinned out le a v in g 10 th a t are uniform and th at are near the height
o f the s e e d lin g s in the o th er ja r s .
The o i l i s ap p lied to both s id e s o f the s e e d lin g s with a cam el's
h a ir brush.
At th e end o f 3 days the s e e d lin g s are cut and weI, bed.
Their w eight i s su b tracter from the same number o f c o n tr o l s e e d lin g s and
the d iffe r e n c e In w eight i s computed to percent# e o f the weight o f the
c o n tr o ls aud c a lle d in ju r y .
(I ) K e lle y , v ic to r K ., E ffe c t o f C ertain Hydrocarbon o l l a on the Res­
p ir a tio n o f F o lia g e and Dormant Twigs o f the Apple. 111. Agr. Expt.
S ta . B ui. 348, 1930.
(%)Swingle, ii. s . , and Snapp, 0 . I . , Petroleum O ils and O il Emulsions
a s I n s e c t ic id e s , and T heir Use A gainst nan Jose u cale on - oach Trees o f
the so u th . U. S. Dept* o f Agr. Pul. 253, 1931.
(S)KnilTht, Hugh, Chamberlin, Joseph C ., and Samuels, C. D ., Some
L im iting F actors in the Use o f Saturated Petroleum O ils aa I n s e c tic id e s .
In n t uysIolo g y , 4 : 299-821, 1929.
(* )c r e e n , J e s s e , Cnemical and P h y sic a l P ro p erties o f
O ils . Accepted fo r p u b lic a tio n by J . o f Agr. Rea. 1932.
etroleum
pray
- 3—
C o n sid e ra tio n o f ijexox in Method
Ttoera Ie o b v io u s ly a la r g e e r r o r in th e b a rle y s e e d lin g method,
b u t i t h a s serv ed a u s e f u l purp o se in e s tim a tin g th e in ju r io u s q u a l i t i e s
o f th e o i l s to p l a n t s .
F ig u re s I and 2 show th e e f f e c t o f p ro cessed o i l s .
They re p re ­
s e n t t e s t s Noe. 7 3 , 7 4 , 75 and 76 c o n sid e re d in th e d is c u s s io n o f ta b le
T ill.
The f i r s t th r e e a re extrem e c a s e s in which th e re was com plete
k i l l i n g o f th e p l a n t s .
A more ty p ic a l example i s shown in f ig u r e 3 ,
w hich i s a c lo s e -u p view o f t e s t No. 76 and th e c o n tr o l p l a n t s .
The
mere r e t a r d a t i o n in th e grow th o f th e tr e a te d s e e d lin g s a s compared w ith
th e c o n tr o ls i s th e u s u a l e f f e c t .
F ig u re 4 snows th e sam ples re p o rte d in ta b le VI a f t e r they were
o u t and ready to w eigh.
F ig u re 5 shows a c lo s e -u p view o f t e s t Ho. 55
in which th e r e was se v e re in ju r y .
The l a r g e s t e r r o r i s , o f c o u rs e , the la c k o f u n ifo rm ity o f
sam p les.
I n o r d e r to show th e l i m i t s o f t h i s e r r o r th e w eig h ts o f 8
a v erag e sam ples o f 10 s e e d lin g s each a r e re p o rte d in ta b le I .
The v a r­
i a t i o n from th e mean I e g iv e n and in t h i s t r i a l th e maximum p o s itiv e
v a ria tio n
a s 1 2 .7 p e r c e n t and th e maximum n e g a tiv e v a r ia tio n was 8 .4
p e r c e n t.
The amount o f o i l a p p lie d to th e s e e d lin g s in f lu e n c e s th e
amount o f in ju r y .
a p p e a r to b e .
I t i s b e lie v e d to be o f l e s s Im portance th an i t m ight
The amount o f o i l rem ain in g on th e s e e d lin g s when tney a re
weighed i s o f g r e a t e r im p o rtan ce.
? lth a very v is c o u s o i l a g r e a t d e a l
i s re q u ire d to co m p letely c o v er th e s e e d lin g s and th e re i s p r a c t i c a l l y
no v o l i t i l i z a t i o n o r r u n - o f f d u rin g th e t e s t .
Tabla I .
Sboalag V a ria tio n o f C o n tro l S aap lea Uaed In B arley
S M d lln g T eat
C o n tro ls
I (no tre a tm e n t)
2 "
"
3 "
"
4
"
5 w
*
6
7
•
•
6 "
•
"
Average
w eight o f 10
s e e d lin g s
grams
0.760
0 .720
0 .7 6 0
0 .7 2 0
0 .890
0 .7 9 0
0 .780
0 .610
0 .7 6 6
V a ria tio n
from average
grama
+0.004
-0 .0 6 6
+0.004
-0 .0 6 6
+0.104
+0.004
—0 .0 0 6
+0.024
P e rc e n ta g e v a r ia ­
t i o n from a v e ra g e
+O.b
- 6 .4
+ 0 .5
- 8 .4
+ 1 2 .7
+ 0 .5
- 0.8
+ 3 .1
O rdinary a etb o d a o f o b s e r v a tio n a re p e rh a p s J u s t a e u s e f u l a s a
com parison o f th e w e ig h ts o f th e p l a n t s , and have been used In e s tim a tin g
th e in ju r y in every c a s e ,
! h e re i s , how ever, p r a c t i c a l l y no means o f
re c o rd in g and p re s e n tin g th e d a ta o f a n a ly s e s made by o b s e r v a tio n .
A study o f th e v a rio u s t a b l e s w i l l show t h a t th e r e I s a wide
v a r i a t i o n in th e d eg ree o f in ju r y r e p o r te d .
grow ing
T h is i s due l a r g e ly to th e
c o n d itio n s which p r e v a ile d d u rin g th e t e a t .
I f c o n d itio n s were
good th e c o n tr o l p la n ts made ra p id p ro g re s s and l e f t th e in ju r e d cn ee
f a r b eh in d , th u s showing a la r g e amount o f in ju r y .
If
rowing c o n d itio n s
were p o o r e s m a lle r amount o f in ju r y would be causeu by th e same o i l .
F o r th e s e re a so n s i t i s n e c e s sa ry to examine th e d a ta in e a c h ta b le a s a
u n it.
A ll tb s t e s t s made in any s in g le ta b le were made a t the same tim e
and a r e com parable w ith each o th e r .
'
O U e Used
A s e r i e s o f 13 o i l s were used in a fo rm er in v e s t i g a t i o n , and
from t b i e group th e o i l s f o r t h i s work were s e l e c t e d .
C o n sid e ra b le d a ta
■ere o b ta in e d in th e e a r l i e r stu d y and a r e a tta c h e d to t h i s r e p o r t a s an
a p p e n d ix .
The r e l a t i v e In ju ry a s d eterm in ed In th e fo rm er work i s a ls o
g iv e n in th e ap p en d ix .
rIhe la b o ra to ry numbers o f th e o r i g i n a l o i l s a re
«5* 4* b* 8» 12* 15* lb* 16» 20» 21» 3 2 , 24* and 38.
These numbers should
n o t be confused w ith th e b a rle y s e e l i n g t e s t num bers, o r th e p ro cessed
o i l s which b e a r th e same number a s th e t e s t In which th ey were u sed .
The
o r i g i n a l o r n o n -tr e a te d o i l i s d e s ig n a te d a s "norm al o i l " .
D i s t i l l a t i o n o f O ils
The f i r s t a tte m p t to s e p a r a te th e I n ju r io u s p o r tio n from th e
o i l was by d i s t i l l a t i o n .
A bead to w er was used and was wrapped w ith an
e l e c t r i c a l h e a tin g elem en t and a s b e s to s in s u l a t i o n .
t u s i s shown in f ig u r e 6.
The com plete ap p ara­
A c e r t a i n amount o f f r a c t i o n a t i o n was accom­
p lis h e d i n th e bead tower* and a l l th e d i s t i l l a t i o n s were made a t an
a b s o lu te p re s s u re o f a p p ro x im a te ly 10 cm. o f m ercury.
The d i f f e r e n t o i l s were d i s t i l l e d in to 3 f r a c t i o n s each .
A
g iv e n amount o f o i l was p la c e d in th e s t i l l and the f i r s t f r a c t i o n con­
s i s t e d o f o n e - th ir d o f th e t o t a l , th e second f r a c t i o n o n e - t h i r d , and
th e r e s id u e rem aining in th e s t i l l o f o n e - t h i r d .
These sam ples were
a p p lie d to b a rle y e e e d li:« s and th e r e s u l t s re p o rte d in ta b le I I .
There was more o r l e s s c ra c k in g o r b re a k in g down o f th e o i l s
d u rin g d i s t i l l a t i o n .
D arkening o f th e r e s id u e , sudden changes i n tem­
p e r a tu r e -.nd in c r e a s e s i n s u lfo n a ta b le p o r tio n a re th e e v id e n c e s su p p o rt­
in g t h i s s ta te m e n t.
The v a r ia tio n s in te m p e ratu re from one f r a c t i o n to
a n o th e r were caused by th e r e le a s in g o f th e vacuum and c o o lin g down o f
th e s t i l l to change th e r e c e iv e r between f r a c t i o n s .
A ll the fr a c tio n s were analyzed fo r the s u lfo n a te ble p ortion
by the method used by f u r s b a l l ^ ) .
General trends can hardly be c ite d from a itu dy o f the d i s t i l ­
la t io n and e u lfo n a tio n valu es found.
There i s a s l i g h t tendency fo r the
f i r s t fr a c tio n s to cause the g r ea test in ju r y .
tio n data are presented g r a p h ic a lly .
In fig u r e 7 the d i s t i l l a ­
The su lfo n a ta b le p o rtio n o f the
fr a c tio n s has l i t t l e , i f any, r e la t io n to in ju ry .
In the ease o f o i l
/ o . 3 the su lfo n a ta b le value o f the resid u e i s Vury low and the Injury
caused by t h is fr a c tio n i s a ls o very low .
w ith o i l Ho. 3 4 , the su lfo n ­
a ta b le p o rtio n o f the resid u e i s h ig h , but s t i l l the injury produced i s
low .
These two resid u es were both very v isc o u s and i t has o fte n been
observed th a t very v isc o u s o i l s f a l l to cause the injury th a t would be
exp ected .
They do not appear to p en etra te th e p la n t a s do the o i l s o f
low er v is c o s it y .
From the graphs in fig u r e 6 i t i s q u ite ev id en t th a t d i s t i l e
la t lo n i s a very poor moans o f sep a ra tin g the su lfo n a ta b le m a teria ls
from the remainder o f the o i l .
The su lfo n a ta b le p o rtio n o f a l l the
fr a c tio n s o f any g iv en o i l runs f a ir ly c lo s e to g e th e r .
I t Is a ls o e v i­
dent th a t d i s t i l l a t i o n causes the form ation o f su lfo n a ta b le
in the o i l .
Itost o f the fr a c tio n s are high er in su lfo n a ta b le m aterial
than th e normal o i l .
fo n a ta b le
a t e r Ia le
O ils Hoe. 22 and 4 show a g rea t in crea se in s u l­
a t e r la l during d i s t i l l a t i o n .
O ils Nos. b and 21 do not show
an Increase o f su lfo n a ta b le m a te r ia ls, but an in crea se was th e trend In
most c a s e s .
(I )F a r s h a ll, arren G ., Ic o n o c le P o iso n s.
C a lif . D ept, o f Apr. 1929.
S p e c ia l Pub. 9 4 , S ta te o f
Table I I .
Test
number
O il
number
Injury to Barley
F raction
eed lin g * Caused ^
( s in g le determ inations)
Temperature
range
Injury
1
2
3
3
fir s t
second
resid u e*
1 8 0 -3 2 8
215 - 3bb
272 -
2 4 .9
86.8
2 7 .8
2 4 .0
2 4 .0
4 .0
6.0
4
4
fir s t
second
resid u e
147 - 210
200 - 26b
265 -
5 2 .3
5 1 .1
13 .9
2 8 .0
3 4 .0
3 2 .0
12.0
b
fir s t
second
resid u e
Ib b - 215
2 0 5 -2 3 0
230 -
5 1 .8
3 6 .5
21.6
4 2 .0
4 2 .0
4 6 .0
4 1 .6
12
fir s t
second
real due
UO - 320
ago - 250
250 -
3 7 .4
3 3 .4
1 7 .2
2 6 .0
3 2 .0
2 8 .0
27 .5
13
14
lb
lb
fir s t
second
resid u e
100 - 226
210 - 250
250 -
3 1 .2
3 0 .5
4 3 .2
20.0
26 .0
3 0 .0
26.4
16
17
18
lb
p a r a ffin
added
fir s t
second
th ird
140 - 200
200 - 225
220 - 240
6 5 .2
3 5 .2
23.6
12.0
1 8 .0
12 .0
19
20
21
20
fir s t
second
resid u e
155 - 192
IBb - 190
190 -
3 4 .5
2 5 .3
30 .0
86.0
38 .0
3 0 .0
1.0
KBB
per cen t
S u lfo c a ta b le P ortion
d i s t i l l e d normal
o ile
o ile * *
per cen t per c « it
21
fir s t
second
res Idue
14b - 180
125 - 196
196 -
4 5 .1
30 .5
30.6
1 4 .0
1 0 .0
2 6 .0
1 5.6
88
decrees
D is tilla te s
32
fir s t
second
resid u e
165 - 208
175 - 196
196 -
2 4 .1
2 4 .9
2 6 .1
8 8 .0
8 6 .0
3 0 .0
2 .0
28
89
30
84
fir s t
second
resid u e
200 - 257
230 - 270
270 -
3 1 .3
1 7 .6
13 .1
2.0
4 .0
3 8 .0
none
31
32
33
28
b
6
7
6
9
10
11
12
27
fir s t
190 - 828
4 4 .6
4 2 .0
3 5 .2
second
3 3 0 -8 5 0
4 8 .9
4 2 .0
r esid u e
850 2 8 .1
4 8 .0
*In t h is ease a th ird fr a c tio n eets taken, by d i s t i l l i n g o f f o n e -h a lf
o f the r e s id u e , tnus th ere i s a break in the temperatures between the
second fr a c tio n and the resid u e.
♦•These valu es were determined in a former in v e s tig a tio n .
The sample o f o i l Ho. l b , d e sig n a te d a s " p a r a f f in ad d ed ", was
made by d is s o lv in g 80 gram s o f p a r a f f in i n 400 cc o f o i l and d i s t i l l i n g
in to 3 f r a c t i o n s .
I t was th o u g h t t n a t p o s s ib ly p a r a f f i n m ight h o ld back
th e s u lf o n a ta b le p o r tio n d u rin g d i s t i l l a t i o n .
t u l a o b je c t was accom plished.
The in d ic a tio n s a re t h a t
A ll th e d i s t i l l a t e s had a s u lf o n a ta b le
v a lu e o f 13 p e r c e n t, w h ile th e norm al had 26 .4 p e r c e n t.
Of c o u rs e , a
g r e a t d e a l o f p a r a f f i n d i s t i l l e d o v e r, b u t th e amount was f a r g r e a t e r in
th e th i r d d i s t i l l a t e th a n i n the f i r s t , y e t th ey had th e sane s u lf o n a t­
a b le v a lu e .
I t i s very d i f f i c u l t to i n t e r p r e t some o f th e r e s u l t s , e s ­
p e c i a l l y th e f a c t th a t th e f i r s t , second and t h i r d d i s t i l l a t e s o f th e
p a r a f f in and o i l com bination gave in ju r y v a lu e s o f 5 5 .2 p e r c e n t, 3 2 .6
p e r c e n t and 2 3 .6 p e r c e n t, r e s p e c t i v e l y .
Three d i s t i l l a t e s $ ere made
from t h i s o i l and Vue re s id u e was d is c a rd e d on a cco u n t o f i t s h ig h p a ra ­
f f i n c o n te n t.
F iltr a tio n o f P ile
The f i l t e r i n g o f th e o i l s was accom plished w ith the a p p a ra tu s
shown in f ig u r e 6.
a
steam Jac k e ted tu b e a b o u t Z cm i n d ia m e te r c o n ta in ­
ed th e f i l t e r i n g m a te r ia l.
The le n g th o f th e f i l t e r column v a r ie d , but
was u s u a lly a b o u t 30 era lo n g .
S u c tio n wae alw ays used and in .some c a se s
p re s s u re was a ls o n e c e s s a ry .
T able I I I shows th e r e s u l t s o f f i l t e r i n g th ro u g h a c la y l i k e
m a te r ia l o b ta in e d n e a r Anaconda, Montana and d e sig n a te d in t h i s r e p o r t
a s "O sborne*a mine r u n " .
Two o f the th r e e o i l s used showed much le s s
in ju r y a f t e r f i l t e r i n g and a t h i r d was n o t a f f e c t e d .
Th* s u lf o n a ta b le p o rtio n o f th e o i l s waa d eterm in ed b e fo re and
a fte r filtra tio n .
t ra tio # .
euce
u lfo n a ta b le m a te ria l was removed in ev ery ease by f i l —
I t l a , th u s , h ig h ly p ro b a o le t h a t th e d e c re a se in in ju r y pro—
by f i l t r a t i o n l a b ro u g h t about by th e rem oval o f th e s u lfo n a ta b le
compounds.
T able I I I .
In ju ry to B arley S e e d lin g s by F i l t e r e d and Normal O ils
( d u p lic a te d e te rm in a tio n s )
T e st number
O il number
34
35
36
37
38
39
40
41
15
15
5
5
12
12
28
28
T reatm ent
normal
filte re d
normal
filte re d
normal
filte re d
norm al
filte re d
I n ju r y
per cent
64.2
33 .3
60.9
3 5 .2
5 0 .7
3 6 .1
5 8 .8
5 8 .5
S u lfo n a ta b le
p o rtio n
per cent
25
15
44
38
34
32
52
46
The f i r s t a tte m p ts to f i l t e r o i l were made f o r th e purpoae o f
removing c o lo r .
From p re v io u s e x p e rie n c e c o lo r had been th o u g h t to be
r e l a t e d to i n j u r y .
In at n t o f th e f l l t r a t i o ns the f i r s t few c u b ic cen­
tim e t e r a o f o i l coming thro u g h would be c l e a r , b u t a a th e p ro c e ss con­
tin u e d th e o i l would r a p id ly become d a rk e r and d a r k e r , and in a very
s h o r t tim e th e a b i l i t y o f th e f i l t e r to remove c o lo r • a s e x h a u ste d .
If
c o lo r and in ju r y a r e p o s itiv e ly r e l a t e d th e f i r s t c l e a r f i l t r a t e auould
be th e l e a s t in ju r io u s and the l a t e r and d a rk e r p o r tio n s more i n ju r io u s .
O il No. I b was f i l t e r e d through 60 cm o f O sborne’ s mine ru n e a r th and
i> s u c c e s s iv e f i l t r a t e s c o lle c te d .
In ta b le IT a l l th e f i l t r a t e s show a
-
10-
dee Ided d e c re a se in in ju r y below th e no m ail o i l .
&a th e f i l t r a t i o n p ro -
tiresued th e sam ples became d a r k e r , bu t th e r e was no in c re a s e in In ju ry
w ith in c je a a e in c o lo r .
Ttible IV.
In ju r y to I B arley
c e d iIngs by S u c c essiv e P o r tio n s
o f an O il P a ssin g Through a f i l t e r
( s in g le d e te rm in a tio n s )
T e st number
43
44
43
46
47
48
O il number
16
lb
15
16
15
18
Treatm ent
f i r s t f i l t r a t e ( l e a s t c o lo r)
sedond f i l t r a t e
th ird f i l t r a t e
f o u r th f i l t r a t e
f i f t h f i l t r a t e (m ost c o lo r)
norm al o i l
S e v e ra l k in d s o f f i l t e r s were t r i e d .
a re g iv e n in ta b le V.
meeh s e lv e .
In ju ry
per cent
18.4
1 6 .4
2 6 .8
3 1 .9
16 .8
3 5 .9
Ih e r e s u l t s o f th e se t r i a l s
A ll th e m a te r is le used were ground to p a s s a 60
A g r e a t d e a l o f th e m a te r ia l wae f i n e r , b u t p e r t o f i t was
about th e s iz e o f a 60 neah and p re v e n ted to o c lo s e p ack in g o f th e f i l t e r .
I t was found im p o ssib le to fo r c e o i l th ro u g h f i l t e r i n g m a te r ia l ground to
100 mesh s iz e w ith th e p r e s s u r e s u te d .
In c a rry in g o u t tn e f i l t r a t i o n
t e s t s th e same amount o f o i l was p u t th ro u g h th e same le n g th o f f i l t e r
column, and th e te m p e ra tu re and p r e s s u r e were k e p t c o n s ta n t.
The f i r s t f i l t e r was O sborne’s mine ru n .
T h is same m a te ria l
was t r i e d in com bination w ith N o rlt ( a c tiv a te d c h a r c o a l) , a n o th e r sample
o f i t was ig n ite d and s t i l l a n o th e r t r e a t e d w ith a c id .
The a c id tre a tm e n t
consiz te d o f w e ttin g tn e e a r t h w ith s u l f u r i c a c id and h e a tin g u n t i l :X)g
fumes were r a p id ly g iv e n o f f .
The m ix tu re w ith R o r lt was made by combin­
ing S p a r t s o f e a r t h , by w e ig h t, and 3 p a r t s o f B o r i t , and th e ig n ite d
-
11-
p o r tio n wee p repared by bolt, log the e a r th a t a red b e a t f o r two o r th re e
h o u rs .
The com m ercial F u lle r * e e a r t h used in th e s e t e s t a was p u rchased
from
11. S a rg e n t and Company, a s was a ls o th e h y d ra te d s i l i c a (40 p e r
c e n t m o is tu re ).
The v o lc a n ic ash was a good q u a lity o f t h i s m a te ria l
o b ta in e d from a l o c a l n a tu r a l so u rc e n e a r f f h ile h a ll, Montana.
A lthough th e d e U r a in a tio n e o f th e In ju r y caused by th e o i l s a f t e r
p a s s in g th ro u g h th e se v a rio u s f i l t e r s were m d e i n d u p lic a te , th e d i f f e r ­
e n ce s shown in ta b le V a re n o t s i g n i f i c a n t .
th e value o f f i l t r a t i o n .
They d o , how ever, a g a in show
The h ig h in ju r y v a lu e shown by th e o i l f i l t e r e d
through v o lc a n ic ash can be accounted f o r by th e f a c t t h a t f i l t r a t i o n
thro u g h t h i s m a te r ia l was v e ry ra p id and th u s th e f o r c e s o f a d s o rp tio n had
l i t t l e cnance to s e l e c t a p o rtio n o f th e o i l .
The c o rre sp o n d in g ly nigh
in ju r y v a lu e o f th e o i l f i l t e r e d th ro u g h h y d ra te d s i l i c a can n o t be
accounted f o r by any known re a s o n .
T h is m a te ria l appeared to have a l l th e
q u a l i t i e s o f a good f i l t e r and i t l a e x te n s iv e ly used in th e o i l I n d u s try .
Table V.
In ju r y to B arley S e e d lin g s by an
11 A fte r Being F il te r e d
Through V arious M a te ria ls
( d u p lic a te D e te rm in a tio n s)
T est
number
O il
MBfeMHT
42
43
44
lb
16
16
4b
16
46
16
47
4ti
49
16
16
16
Treatzvent
norm al
f i l t e r e d tnro u g h O sborne’ s mine run e a r th
f i l t e r e d tn ro u g h HgSO* tr e a te d O sborne’ s
mine ru n <a r t h
f i l t e r e d thro u g h O sborne’ s mine run e a r th
and N o rit
f i l t e r e d th ro u g h ig n its u O sborne’ s mine
run e a r th
f i l t e r e d tn ro u g h com m ercial F u l l e r ’ s e a r t h
f i l t e r e d th ro ^ h h y d ra te d s i l i c a
f i l t e r e d th ro u g h v o lc a n ic aah
In ju ry
p er cent
54.7
18 .6
26.0
1 7 .1
2 6 .8
26 .8
33*3
3 6 .4
•
12-
In ta b le VI the r e s u lt s o f o th e r f iltr a t io n ® are g iv e n .
The o i l
fo r t e s t Koe, bO and 51 was prepared from a standard m la elb le spray o i l ,
con tain in g 9 part® o f o i l No. Ib and I part o f c re so a p l1 ) .
T est No. 50
enow® an in ju ry o f 4 8 .6 per cen t from the f il t e r e d m isc ib le o i l and 6 0 .5
per cen t from the normal o i l .
The o i l used in t e s t No. BI was prepared
by washing tne m isc ib le o i l w ith water u n t il about o n e -h a lf o f i t s v o l­
ume had been c a r r ie r away as s o lu b le o r e m u lsifie d m a te r ia l.
The p o rtio n
re -aln in g caused an Injury o f 7 3 .B per c e n t.
The washing o f the o i l used fo r t e s t No. BI and a ls o sev era l
o th e r o i l s was done in th e washer shown in fig u r e 10.
A la y e r o f o i l la
flo a te d on water and a em ail stream o f water i s allow ed to f a l l on the
o i l and pass ou t below through an inverted syphon.
I f f i l t r a t i o n removes the In ju riou s p o rtio n o f an o i l i t should
be p o s s ib le to e x tr a c t the f i l t e r w ith c e r ta in s o lv e n ts and recover a
m a ter ia l th a t would be very harmful to p la n ts ,
with t h is idea in mind,
a la r g e p o rtio n o f O il N o.IB was f i l t e r e d through a long f i l t e r column
and tue f i l t e r washed with se v e r a l p o r tio n s o f g a so lin e in to another con­
ta in e r .
The g a s o lin e was d i s t i l l e d from th e cash in gs u n til tne product
appeared to have approxim ately the same c h a r a c t e r is tic s o f th e normal
o il.
This was ap p lied to barley s e e d lin g s in t e s t No. 53 and caused an
injury o f 5 9 .5 per c e n t, as compared w ith an in ju ry o f 4 7 .3 per cen t fo r
the o i l th a t had passed through the f i l t e r ( t e s t No. 5 2 ).
^1 H1B laneer, A. L ., S p uler, Anthony, and Green, E. L ., O il Sprays,
Their P reparation and Use fb r In se c t C ontrol. Wash, tixpt. S ta . Bui. 184,
1924.
Tbe e f f e c t o f f i l t e r i n g «uI form ted o i l No* 5 i s reported in
t e s t s Noe. 55 to
o f f and f i l t e r e d .
was washed.
5 9.
A fter s u lfo n a tlo n the o i l was c e n tr ifu g e d , decanted
The f i r s t f i l t r a t e had a s l i g h t a c id it y and a p o rtio n
For oowa reason t h is washed p o rtio n o f the o i l
high injury o f 7 9 .9 per c e n t.
ave a very
Hte remainder o f the f i r s t f i l t r a t e was
f i l t e r e d three tim es more and ap p lied in t e s t a Noae 5 6 , 57 and 5 6 , res­
p e c t iv e ly , and each time a p o rtio n was caved.
filte r e d o il#
The Injury v a lu es o f th ese
are not c o n s in ta n t, but the products o f the I a e t two n i ­
tr a tio n s caused Wery low in ju r y .
F ilte r e d and n o n -fllte r e d o i l No. 21 was used in t e s t a
and 61.
cess.
o s. 60
This o i l was r efin e d by the manufacturer by the M eleanu SOg pro­
The sm all amount o f d iffe r e n c e between the Injury o f the f i l t e r e d
and n o n -fllt e r e d o i l i s
ome evidence th a t SO2 removes the sume m a ter ia ls
th a t are removed by f i l t r a t i o n .
The tueory d f c o lo r removal from o i l by f i l t r a t i o n i s somewhat
I d e fin ite .
Ua e m a n concludes th a t the c o lo rin g m atter In o i l la c o l­
lo id a l and th a t i t Is o f th e nature o f the humic a c id s .
He s t a t e s fur­
th er th at a part o f the colored compounds in o i l i s p r e c ip ita te d by the
d l - a i l i c l o acicts In the f i l t e r i n g ea rth and that the remainder are f i l ­
tered ou t m ech an ically.
The theory o f adsorption i s summarized by T orm ey^ by the a t a t s sent th at the co n cen tra tio n o f any eist-o lv ed substance i s increased hear
( I ) Haaeman, J. D ., The Alleged C a ta ly tic A ction o f F u lle r 's la r th
on the Coloring Matter In O il. J . o f uya. Chem. Vo. 3 3 , 1514-1527, 1929.
( 2 Ilb r a e y , Harold, N otes on A dsorption.
1931.
The R e fin e r , F e b ., 78,
-
14-
th e I n te r f a c e o f th e s o lid and the l i q u i d .
T his m y be accom plished e l t h e
by th e fo rm a tio n o f chem ical coepli jiee o r by th e a c tio n o f p h y s ic a l a t ­
t r a c t i v e f o r c e s b e tse e n th e s o lid and the d is s o lv e d s u b s ta n c e .
A lthough
th e s e th e o r ie s a r e n o t s p e c i f i c th e y a re p erh ap s th e most a c c u ra te gener­
a l Iz a tlo n o t h a t can now be drawn.
O ilp ln and C r a t t ^ have found t h a t th e more dense p o r tio n s and
th e s u lf o n a ta b le m a te r ia ls a r e h eld back in th e p a ssa g e o f o i l s through
F u l l e r t B e a r t h , which would in d ic a te t h a t the most in ju r io u s p o rtio n o f
p etro leu m i s o f h ig h e r m o le c u la r w eight th a n th e r e s t o f th e o i l .
Table VI.
In ju r y to B arley S e e d lin g s by V a rio u sly F i l t e r e d P i l e
_____________________________ ( s in g le d e te rm in a tio n s )_________________________
T e st
O il
number number____________ m a t # n t__________________________________In ju ry
p er cent
9 p a r te o i l and I p a r t e re a o a p , f i l t e r e d
15
4 6 .6
60
61
15
9 p a r t s o i l and I p a r t e re s o a p , washed w ith
w ater
7 3 .5
16
53
la r g e p o rtio n o i l f i l t e r e d , t h r o u g h I f i l t e r
4 7 .3
63
16
Adsorbed m a te r ia l washed from above f i l t e r
w ith g a s o lin e
5 9 .5
Normal
16
54
60.5
66
66
67
56
6»
5
6
6
b
5
60
61
21
21
S u lf o n a te d ,
S u lfb n a te d ,
S u lfo n u te d ,
S u lfo n a te d ,
Nonaal
filte re d
filte re d
filte re d
filte re d
o n c e , and washed
tw ice
th r e e tim es
fo u r tim es
B deleanu JOg p ro c e ssed o i l , f i l t e r e d
Kdeleanu SOg p ro c e ase o i l , normal
79.5
4 6 .6
none
16.3
6 1 .0
66 .5
66.6
( I ) G ilp i n , J . E l l i o t t , and Cram, M arsh a ll P ., The F r a c tio n a tio n o f
Crude P etroleum by C a p illa r y D iff u s io n . U. 3 . G eol. su rv ey B ui. 36b.
Soiae Che d e a l Treat a n te
S ev era l chem ical p ro cesses <vere tr ie d on the o i l s .
was tr e a ted w ith c h lo r in e .
th e gen erator was used.
in temperature and the
o il.
O il ho. 15
In the f i r s t attem pt wet c h lo r in e r ig h t from
A vigorous r e a c tio n took p la c e , causing a r is e
>rouuct was much sore v isco u s than the o r ig in a l
In a second attem pt dry c h lo r in e was passed through the o i l .
The
r e a c tio n was much slow er but the product was much the same a s with th e
wet c h lo r in e .
The ch lo rin a ted o i l wus washed fr e e o f any d isso lv e d
c h lo r in e o r a c id it y and was then d r ie d .
The drying o f i l l o i l s was
accom plished by bubbling a i r thro ugh the o i l w hile i t was held in a con­
ta in e r in a b o ilin g water bath.
T est No. 62 o f ta b le VIX shows the in­
jury o f dry ch lorin ated o i l :>u. Ib to be 5 3 .6 per cen t a s compared with
6 4 .2 per cen t fo r the normal o i l .
O il No. Ib was a ls o tr e a ted w ith kodium h y p o c h lo r ite , according
to a method describ ed by l o s t and BeeemannU').
A sample o f the o i l was
shaken s e v e r a l tim es w ith p o r tio n s o f sodium h y p o ch lo rite in the presence
o f copper s u lf a t e .
The
rooesa was designed to remove c o lo r , but in th is
case very l i t t l e c o lo r was removed.
The barley s e e d lin g t e s t No. 63
shows very l i t t l e d iffe r e n c e from the normal o i l .
O il No. 28 was ch lo rin a ted by a s im ila r p rocess a s th at used on
o i l No. l b .
when the c h lo r in a tio n was com plete the product was so v is ­
cous th a t i t was thought b e s t to d i s t i l l i t before applying i t to barley
s e e d lin g s .
The f i r s t d i s t i l l a t e was l i g h t colored and had a very low
v is c o s ity .
I t was used in t e s t No. 65.
A second fr a c tio n waa very dark
U )post,
llhe-lm, and Beeemann, Franz, B leaching Mineral O il. U. S.
a te n t to. 1 ,7 8 6 ,2 0 4 , Jan. 1831.
and was ap p lied in t e s t No. 6 6.
The resid u e was too v isc o u s to be used.
%e ch lo rin a ted o i l , w ithout being d i s t i l l e d , was a p p lied in t e s t ho. 68.
Although some o f the ch lo rin a ted o i l s caused
l e s s injury than the normal
o i l the p o s s i b i l i t i e s o f improving spray o i l s by c h lo r in a tio n seem to be
very poor from th ese show ings.
fa b le /1 1 .
Injury to Barley S e e * lin g s by C hlorinatea U ils
(d u p lic a te d eterm in ation s)
T est
number
O il
number
Treatment
Injury
per cen t
58.6
60 .1
6 4 .2
62
63
64
lb
lb
lb
Treated w ith c h lo r in e , washed and dried
Treated w ith sodium h y p o ch lo rite
Hcrmal
6b
28
66
28
67
28
68
28
Treated w ith c h lo rin e and d i s t i l l e d - f i r s t
fr a c tio n
Treated with c h lo r in e and d i s t i l l e d - second
fr a c tio n
T rea tei w ith c h lo r in e , n o t d i s t i l l e d , but
washed and dried
Normal
6 4 .0
64.0
4 5 .0
68 .8
N itr a tio n produced r e s u lt s very s im ila r to c h lo r in a tio n , o n ly they
were more se v e r e .
The r ea c tio n was accom plished by tr e a tin g 100 cc o f o i l
w ith 40 cc o f commercial n i t r i c acid and m aintaining the temperature a t
100° C fo r two to th ree hours, with freq u en t shaking.
The products are
s i H a r in appearance to tn ose o f s u lf o n a tio n , end the r e a c tio n proceeds
a t about the same r a te .
A r es inoua p r e c ip ita te i s formed in the sludge
which d i f f e r s from the product o f e u lfo n a tio n .
I t i s brown and Ie p la s ­
t i c a t ordinary tem peratures.
E e se t measurements were h o t made during tne n it r a t io n p ro cess,
but 30 per cen t o f o i l ' o . Io and 6b per cen t o f o i l
by the n itr a tio n p rocess as i t was carried o u t .
o . 5 were removed .
According to th ese f i g -
-
17-
urea n i t r i c a c id a tta c k s a l i t t l e io r e o f an o i l than does s u lfu r ic a cid
under the seme c o n d itio n s .
T ests No. 69 and 70 o f ta b le VIII show the
injury caused by n itr a te d o i l s Noe. 15 and 5 .
In both c a se s the injury
was about o n e -th ir d g r e a te r than th a t o f th e normal o i l .
Table V III.
Injmzy to E arley : e e d lin s Iqr N itra ted O ils
(sin , I e d e te r !n a tio n s)
T est
number
O il
number
69
70
15
15
N itrated
Normal
Injury
per cen t
3 0 .1
1 9 .2
71
72
5
5
N itrated
Normal
2 6.3
1 9 .8
Treatment
Three sam l e e o f o i l No. l b , th a t had been su lfo n a te d and
trea ted under s l i g h t l y d if f e r e n t c o n d itio n s a s d escribed in t e s t s Nos.
91* lsO and 79* were n itr a te d .
They were ap p lied in t e s t s Nos. 73» 74
and 7 5, with No. 76 fo r the su lfo n a ted o i l (s e e ta b le IX).
in ju ry waa caused by th e su lfon ated and n itr a te d o i l s .
Very high
F igure I shows
tn e seed !in , a b efore treat,ren t and fig u r e 3 a f t e r tr e a t a n t .
ai.owa the e f f e c t o f the s u lfo n a te d ,b*t not n itr a te d , o i l .
Figure 3
I t is te s t
o . 7o b esid e th e c o n tr o l sam ples.
fab le IX.
Injury to Barley S eed lin g s by N ltr a te d -S u lfonatsd O ils
(d u p lic a te determ inations)
T est
number
73
74
Tb
76
O il
number
15
15
15
15
Treatment
N itr a ted -au lfon a ted
Nit r u t e d - s u lf oneted
N itr a te d -e u lfo n a te o
S u lfon ated , but n o t
o i l from t e s t
o i l from t e s t
o i l from t e s t
n it r a t e d , o i l
t e s t No.
No. 91
No. 60
No. 79
from
91 a s check
Injury
per cent
66.7
6 2.3
7 1 .1
1 4 .6
Sulfonated and Other Chemically Treated O ils
tioma com binations o f s u lfo n a tlo n end f i l t r a t i o n were tr ie d and
reported In ta b le X.
normal o i l .
A ll th e su lfon ated o i l s show an Inpxovenent o v er the
The a lig h t v a r ia tio n s in treatm ent are probably o f l i t t l e
s ig n if ic a n c e .
Two p o r tio n s o f o i l lio. Ib were reflu xeu v io le n t ly fo r 4b min­
u tes w ith an e x c e ss o f PbO (lith a r g e ) and CuO.
The o i l s were decanted
o f f , f i l t e r e d and used in t e s t s fios. 81 and 6 2 .
I t was thought that
th ere was a p o s s i b i l i t y o f removing s u lfu r compounds by treatm ent w ith
th ese o x l ee as i s done in the Prasch
ro cess^ .
The r e s u lt s in d ic a te
th at in any even t there was d e te r io r a tio n o f the o i l as regards i t s value
as a spray o i l .
The high temperature and v io le n t r e flu x in g may have
promoted o x id a tio n , or the form ation o f in ju r io u s compoundo , in the o i l .
Table X.
Injury to Barley Seed lin g* by su lfo n a ted O ils and P ile
Heated tilth Copper and Lead Oxides
( s in g le d eterm in ation s)
T est
number
O il
number
77
16
78
lb
7»
15
80
Treatment
Injury
per cent
lb
Sulfonated and f i l t e r e d , f i r s t f i l t r a t e , no
fu rth e r treatment
Sulfonated and f i l t e r e d , f i r s t f i l t r a t e , t r e e ted w ith NaOH, washed and d r ie d .
Sulfonated and f i l t e r e d , second f i l t r a t e .
trea ted w ith HaUM, washed, dried and f il t e r e d
S u lfon ated , trea ted with NaOH, washed and dried
15.5
14.7
81
82
lb
lb
Refluxed with CuO and f i l t e r e d
Refluxed with PbO and f i l t e r e d
3 4 .0
31.4
63
15
Normal
26.3
( ^ G ru ee, i l l Iao A ., fetroleum and I t s
Gd. , New York, 14#28.
roducts.
2 1 .6
20.1
McGwaw h i l l (Book
One hundred ec o f o i l No. Ib were tr e a te d w ith 20 grains o f co p p er
tiu lf a te and an e q u a l amount was tr e a te d
a n a te .
i t h £0 grams o f p o tassiu m p e r .an-
he two sam ples were h e ld a t 100° C on a steam p la te f o r 36 h o u rs
w ith o c c a s io n a l sh a k in g , a f t e r which th e o i l s were d e ca n te d o f f and f i l ­
te re d .
The f i l t r a t e s were d iv id e d in to th re e p o r tio n s by d i s t i l l a t i o n ,
t h a t I s , a f i r s t ami second d i s t i l l a t e and a r e s id u e .
produced on b a rle y s e e d lin g s i s re p o rte d in t e s t s
T able X I.
The In ju ry they
64 to 69 in ta b le X I.
In ju ry to B arley S e e d lin g s by o i l s T reated a i th
Copper S u lf a te and V otasslum Vermant a n a te
ls in g lo d e te r m in a tio n s )
T eat
number
O il
number
64
15
Bb
15
86
15
67
15
88
15
89
90
T reatm ent
In ju v
per cent
CusO* tr e a te d and d i s t i l l e d , f i r s t f r a c t i o n
(140° - 19dP)
CUSO4 t r e a t e d and d i s t i l l e d , second f r a c t i o n
(166° - 174°)
CUSO4 t r e a t e d and d i s t i l l e d , re s id u e (174®)
5 3 .8
4 5 .1
4 4 .6
15
KtSnO4 tr e a t e d and d i s t i l l e d , f i r s t f r a c t i o n
(138<» - 170°)
K%®*)4 tr e a t e d and d i s t i l l e d , second f r a c t i o n
(1600 - 1770)
IOtaO4 tr e a te d and d i s t i l l e d , re s id u e ( 1770)
5 3 .5
3 7 .0
15
Normal
5 0 .0
Some f u r t h e r work was done on a u lf o n a tio n .
5 3 .0
O il No. 15 warn
t r e a t e d a c c o rd in g to th e method o f S te lk and C a s s a r ( D .
one hundred oc
o f th e o i l were tr e a te d w ith 25 cc o f fuming s u l f u r i c a c id and allow ed to
s ta n d ti t room te m p e ra tu re f o r 3 h o u rs w ith fre q u e n t s h a k in g .
The slu d g e
( D a t e I k , K a rl, T ., and C aesar, H arold A ., C o lo rle s s o r A hlte M in eral
O il. U. S . P a te n t 1 ,8 0 3 ,1 4 0 , A p r il, 1931.
-
20-
wae c e n tr if u g e d o f f and th e o i l tr e a te d a ^ a ln w ith 66 p e r c e n t a c id a t a
te m p e ra tu re o f 75° f o r a few h o u rs .
I t was c e n trifu g e d a g a in , f i l t e r e d
tw ic e , and used In t e s t So. 81 o f t a b l e I I I .
A low in ju r y was o b ta in e d
from t h i s o i l , b u t i t i s p robab ly n o t s u p e r io r to th e earns o i l a u lfo n a te d
by th e o rd in a ry method
O x id a tio n K ffe c ta o n o i l s
In o r d e r to show th e e f f e c t o f h e a tin g and o x id a tio n , o i l s Ho.
16 and 5 were h e a te d in a r e f lu x in g s t i l l f o r 8 h o u rs , and a t th e
tim e a i r was drawn th ro u g h th e o i l .
The p ro d u c ts were very d o rk .
A
p o r tio n o f each was f i l t e r e d and te s t e d i n com parison w ith th e n o » - f t i ­
te r e d o i l in t e s t s Nos. 9 2 , 8 3 , 95 and 9 6 .
O il No. 15 d id no t show any
marked change due to o x id a tio n , b u t O il No. 5 showed in c re a s e d in ju r y
because o f t h i a tre a tm e n t.
Both t r e a t e d o i l s gave much lo w er in ju r y
a f t e r being f i l t e r e d .
T able X II.
In ju r y to B arley See l i n e s by & Double S u lfo mated o i l
and OH s s u b je c te d to Severe O x id atio n
__
T eat
number
91
92
93
64
(Blnt-Ie d e te rm in a tio n s )________________________
O il
number_________ Treatm ent____________
In ju ry
per cent
15
Double s u lf o n a tio n and d ouble f i l t r a t i o n
23.0
lb
R efluxed and a i r bubbled through f o r 6 h o u rs
45 .6
lb
R efluxed and a i r bubbled th ro u g h f o r 8 h o u rs ,
and f i l t e r e d
33.2
15
Normal
4 5 .3
95
96
5
5
97
5
R efluxed and a i r bubbled th ro u g h f o r 6 h o u rs
R efluxed and a i r bubbled th ro u g h f o r 8 h o u rs ,
and f i l t e r e d
Normal
4 4 .6
3 0 .3
3 6.5
—21 —
Tbo r e s u l t s o f m ild e r o x id a tio n tre a tm e n ts a r e re p o rte d In t e s t s
fcc to 109 o f ta b le X I I I .
Three p o r tio n s o f each o f o i l s No*. 1 5 , 5 and
04 were p la ce d In 4 ounce b o t t l e s and each s e t o f b o t t l e s was connected
In s e r i e s so t h a t a c u r r e n t o f a i r could be drawn th ro u g h th e o i l .
The
f i r s t b o t t l e o f each s e t c o n ta in e d th e norm al d ry o i l , th e second o i l
and w a te r, and th e t h i r d o i l and w a te r a c i d i f i e d w ith s u l f u r i c a c id .
A ll th e b o t t l e s were p la c e In a b o ilin g w ater b a th and a i r was a s p i r ­
a te d th ro u g h th e o i l f o r 8 h o u rs .
The r e s u l t s show no s i g n i f i c a n t d if f e r e n c e s in th e in ju r y caused
by th e d i f f e r e n t sam I e s o f th e tame o i l .
may be o n ly e x p e rim e n ta l e r r o r .
The low v a lu e In t e s t No. 108
The In J u rlo u e p r o p e r tie s o f th e th re e
o r i g i n a l o i l s a r e w e ll shown by th e a v erag e v a lu e s o f 55.8 p e r c e n t,
4 4 .5 p e r c e n t and 1 4 .3 p e r c e n t f o r o i l s Hoe. l b , 6 and 2 4 , r e s p e c tiv e ly .
O il Ho. 24 i s c o n sid e re d th e l e a s t I n ju r io u s o i l used and o i l No. 15 th e
most I n ju r io u s in t h i s and th e fo rm er in v e s t i g a t i o n .
T reatm ent o f O ils by E l s c tr o ly a la
G everal u n s u c c e ss fu l a tte m p ts were made to d e c re a se th e In ju ry
o f sp ra y o i l s by e l e c t r o l y s i s .
A f te r f in d in g t h a t f i l t r a t i o n decreased
th e in ju r y caused by th e o i l s i t was th o u g h t p o s s ib le to acco m p lish th e
same r e s u l t in a more e f f i c i e n t way by e l e c t r o l y s i s .
The movement o f
m a te r ia ls c o l l o i d a l l y d is p e r s e d in l i q u i d s u n d er th e In flu e n c e o f an
e l e c t r i c a l p o t e n t i a l h a s been o b serv ed to be a n alo g o u s to th e movement
o f d u e t p a r t i c l e s in a C o t t r e l l p r e c i p i t a t o r .
There was a ls o th e p o s s i­
b i l i t y o f s e p a r a tin g o u t any e l e c t r o l y t e s t h a t m ight be p r e s e n t in p e tr o -
leuia.
The h ig h r e s i s t a n c e o f o i l w ould, o f c o u rs e . I n d ic a te t h a t th e
q u a n tity o f e l e c t r o l y t e s , o r charged p a r t i c l e * suspended. In th e o i l
was v ery s m a ll.
T able X III ,
In ju r y to B arley S e e d lin g s by o i l s S u b je c te d to
Mild O x id a tio n T reatm ente
I s in g le d e te m i; a tio n a )
eat
number
O il
number
Treatm ent
96
99
100
101
16
16
lb
16
A ir bubbled th ro u g h d ry o i l
A ir bubbled th ro u g h o i l and w a ter
A ir bubbled thro u g h o i l , w a ter and BgSO*
Normal
Average
In ju ry
per cent
66.8
5 1 .3
5 5 .1
60.3
5 6.8
102
103
104
105
5
6
5
5
A ir b u b b le , th ro u g h d ry o i l
A lr bubbled th ro u g h o i l and w ater
A ir bubbled th ro u g h o i l , w a ter and ligSQ*
Normal
Average
4 9 .6
4 9 .1
3 6 .9
4 0 .2
4 4 .5
106
107
106
109
24
24
24
24
A ir bubbled th ro v ^ h dry o i l
A ir bubbled thro u g h o i l and w ater
A lr bubbled th ro u g h o i l , w a te r and H2SO4
Normal
Average
1 9 .2
1 3 .2
5 .6
1 9 .2
14.3
C e ll He, I in f ig u r e U was f i r s t t r i e d in th e e l e c t r o l y s i s
tr e a tm e n ts .
O il was p la ce d in a c e llo p h a n e s a c k , which wae lmueraed in
a b e ak e r o f w a te r.
The n e g a tiv e carbon e le c tr o d e wae p la c e d i n th e o i l
and th e p o s i t i v e co p p er e le c tr o d e in th e w a te r, and d i r e c t c u r r e n t o f
140 v o lte wae a p p lie d , b u t no a c tio n to o k p la c e u n t i l th e p o le s were
roved c lo s e to g e th e r .
The a c tio n th e n became n o tic e a b le and a t a r - l i k e
m a te r ia l c o lle c te d on th e c e llo p h a n e s a c k .
Copper was d is s o lv e d from
23-
tb e p o a itiH e e le c tr o d e and a
w a te r com partm ent.
re e n s a l t e e t t l e a to th e bottom o f th e
The o i l from t h i s ex p erim en t waa t r i e d in t e s t No.
101 o f ta b le XIV and shows no d if f e r e n c e i n In ju ry from th e norm al o i l .
The t a r - l i k e m a te r ia l was p e rh a p s somewhat an alo g o u s to th e p r e c i p i t a t e
found on o i l soaked i n s u la tio n o f e l e c t r i c c a b le s s tu d ie d by
and F e llo w s ^
.
c h o e p fle
These a u th o rs a t t r i b u t e d th e d e p o s itio n o f a w a x -lik e
m a te r ia l In th e in s u l a t i o n o f e l e c t r i c c a b le s to th e a c ti o n o f cathode
ra y # , and have found t h a t s e v e r a l p u re h y d ro carb o n s b reak down under
e l e c t r i c a l In f lu e n c e s , y ie ld in g u n s a tu r a te d h y d ro carb o n s and g a s e s
c o n ta in in g hydrogen and m ethane.
C e ll No. 4 in f ig u r e 12 was c o n s tru c te d by p u ttin g two carbon
e le c tr o d e s in a (U) tu b e f i l l e d w ith o i l .
observe)
and 113.
No a p p a re n t a c tio n could be
but o i l from th e two com partm ents was t r i e d in t e s t s Nos. 112
A lthough th e r e was no v i s i b l e e l e c t r o l y s i s i t was th o u g h t t h a t
p o s s ib ly th e r e m ight have been a movement o f p a r t i c l e s which was n o t
e a s i l y d e te c te d , how ever, th e r e s u l t s a r e n o t c o n sid e re d s i g n i f i c a n t .
A n e g a tiv e carb o n e le c tr o d e and a p o s i t i v e co p p er e le c tr o d e
were p la c e d in o i l in c e l l No. 2 o f f i g u r e 11, but no a p p a re n t e l e c t r o ­
l y s i s co u ld be made to ta k e p la c e on acco u n t o f th e h ig h r e s is ta n c e o f
th e o i l .
Then c e l l No. 3 was c o n s tr u c te d .
A la y e r o f o i l was placed
dn w a te r in a b e a k e r and a n e g a tiv e co p p er e le c tr o d e was p la ce d in th e
o i l and a s i m i l a r p o s itiv e copper e le c tr o d e in the w a te r.
They were
brought very c lo s e to g e th e r on each s id e o f th e o il- w a te r in te r f a c e .
A c o n s id e ra b le a c ti o n took p la c e w ith th e e v o lu tio n o f g a se s and th e
^ S c h o e p f l e , G. S . , and F e llo w s , C. H ., Gaseous P ro d u c ts From th e
A ctio n o f Cathode Rays on H ydrocarbons. In d . and Eng. Chem. Vol. 23,
p . 1396, 1931.
-
24-
p r e e l p i t a t l o n o f a t a r - 1Ike m a te ria l and some copper s a l t in th e w a te r.
A fte r t h i s tre a tm e n t th e o i l was d i s t i l l e d .
The re s id u e from th e f i r s t
d i s t i l l a t i o n was used in t e s t No. 11 6 , th e d i s t i l l a t e o f th e f i r s t d i s ­
t i l l a t i o n was r e d i s t i l l e d in to a d i s t i l l a t e and a r e s id u e , which were
used in t e s t s Nos. 11? and 116, r e s p e c tiv e ly .
The r e s u l t s a r e n o t con­
s id e r e d s i g n i f i c a n t .
The e l e c t r o l y s i s o f a 4 p e r c e n t e re so a p f i e l d em u lsio n o f o i l
No. 1 6, p re p a re d from th e m is c ib le o i l used In t e s t e Noe. 60 and 81,
was t r i e u in c e l l No. 4 (O -shaped ty p e ) and a d. ig h t movement o f th e
suspended o i l d r o p le ts from th e p o s i t i v e to th e n e g a tiv e p o le was o b ­
s e rv e d , in d ic a tin g t h a t th e d r o p le ts were p o s itiv e ly c h a rg e d .
An emul­
s io n o f o i l No. 34 was a ls o t r i e d i n t h i s way and th e same r e s u l t was
o b se rv e d .
Carbon b la c k was suspended in o i l No. 15 and t h e com bination
p la c e d in c e l l No. 4 .
I t was th o u g h t t h a t , a s carbon b la c k was an
a d so rb in g m a t e r i a l . I t m ight be made to move u n d er an e l e c t r i c a l poten­
t i a l and c a rry w ith I t a p o r tio n o f th e o i l , b u t t h i s was n o t th e c a s e .
A fte r s e v e r a l h o u rs a t a p o t e n t i a l o f 140 v o lte th e s l i g h t e s t movement
o f carbon b la ck could n o t be d e te c te d .
C e ll No. 5 in f ig u r e 18 was d e sig n e d to red u ce r e s is ta n c e to
a minimum.
A t h i n l a y e r o f o i l was s e p a ra te d from w a te r o n each s id e
by L heete o f c e llo p h a n e .
Carbon e le c tr o d e s were p la c e u in th e w a ter on
each s id e o f th e o i l w ith the id e a t h a t some m a te r ia l m ig h t be d ia ly z e d
w ith th e a id o f th e e l e c t r i c a l p o t e n t i a l from th e o i l and I n to th e w a te r.
No a c ti o n co u ld be made to ta k e p la c e even th ro u g h a l a y e r o f o i l 0 .6
c e n tim e te r th ic k .
Another t r i a l was made w ith the above c e l l by p la cin g a th in
s h e e t o f aluminum In the o i l la y e r .
I h le wee connected to the ne, a tiv e
term inal and the carbon e le c tr o d e # in the water compartments on each
a id e were both made p o s it iv e .
An a c tio n s im ila r to th a t obtained in
C e ll No. I , in which th e cellop h an e sack o f o i l warn Immersed in water*
•as o b ta in e d .
Gasee were g iv en o f f from the o i l near the n eg a tiv e a lu ­
minum e le c tr o d e , a black p r e c ip ita te c o lle c te d on the cello p h a n e, and
a w hite p r e c ip it a t e , presumably some aluminum s a l t , s e t t le d to the bot­
tom o f the o i l compartment.
The o i l from t h is e l e c t r o l y s i s was a p p lied
in t e s t No. 118, and, although the Injury Walue obtained was somewhat
low er than th at produced by the normal o i l , th e e l e c t r o l y s i s method o f
sep aratin g th e to x ic p o r tio n o f spray o i l s was abandoned.
Table
XIV.
Injury to Barley S eed lin g s by O ils Treated
by E le c t r o ly s is
T est
number
HO
U iln gle d e te r m in a tio n s)_____________
O il
number___________Treatment
5
U l
S
112
113
114
16
15
15
Treated in c e l l No. I - p o s itiv e carbon
e le c tr o d e in o i l in cello p h a n e sack and
n e g a tiv e copper e le c tr o d e in surrounding water
Normal
Injury
per cen t
26.4
27 .1
Treated in c e l l No. 6 - o i l from p o s it iv e p o le 2 5 .7
Treated in c e l l No. 5 - o i l from n eg a tiv e pole 3 1 .8
Normal
3 5 .9
-
Table_XV.
26-
I n ju r y to B arley S e e d lin g s by O ils T re a te d by
E l e c t r o l y s i s and D i s t i l l a t i o n
( a ln p le d e te rm in a tio n s )
T est
number
O il
number
115
5
116
5
117
5
lie
5
119
In ju ry
p er cent
Treatm ent
5
T rea te d by e l e c t r o l y s i s in c e l l No. 3 and
d i s t i l l e d - re s id u e from f i r s t d i s t i l l a t i o n
R esidue from r e d i s t i l l a t i o n o f f i r s t d i s t i l l a t e
o f above
D i s t i l l a t e from above r e d 1 s t i l l a t i o n
3 9 .5
4 0 .0
T rea te d by e l e c t r o l y s i s in c e l l No. 6 w ith
n e g a tiv e aluminum p o le i n o i l
3 0 .5
Normal
4 0 .4
28 .9
E x tra c tio n o f O ils A ith V o la tile S o lv e n ts
The e x t r a c t i o n o f o i l s w ith v o l a t i l e s o lv e n ts was su g g ested by
F e r r l s ( I ) and S te ln b r e e h e r t2 ) .
Soate p re lim in a ry work was done to d e te r ­
mine what s o lv e n ts c o u ld be used .
O il No. Ib was found to be co m p letely
m is c ib le w ith e t h e r , c h lo ro fo rm , carb o n d i s u l f i d e , carbon t e t r a c h l o r i d e
and to lu e n e .
I t was o n ly p a r t l y m is c ib le w ith a c e to n e , 95 p e r c e n t a lc o ­
h o l and 40 p e r c e n t form aldehyde, t» u s th e se s o lv e n ts were used to ex­
t r a c t th e o i l e . ,
A p p a ren tly th o se s o lv e n ts which a re m is c ib le w ith w ater
a re n o t c o m p letely a i s e l b l e w ith o i l and thorn which a r e n o t m is c ib le w ith
w a te r a re m is c ib le w ith o i l .
(1 ) F e r r i s , 3 . . , B irk h i e r , 8. R ., and H enderson, L. I I ., S o lv en t
E x tr a c tio n o f l u b r i c a t i n g O ils . In d . and Eng. C h ea ., V bl. 2 3 , 753-761,
1931.
(2)
S te in b r e c h e r , H ., R e fin in g O ils by Gold F r a c tio n a tio n .
le n a r c h iv , No. 3 0 , 1 -1 0 , 1930.
Braunkoh-
-Z l-
One hundred cc o f o i l No. 15 was shaken w ith 10 s u c c e s s iv e p o r­
ti o n s o f 95 p e r c e n t a lc o h o l in a s e p a ra to ry fu n n e l.
th e o i l was re c o v e re d .
About o n e -h a lf o f
T hie amount was d iv id e d in to th re e e q u al p a rts *
one was n o t tr e a t e d f u r t h e r , a n o th e r was d i s t i l l e d w ith steam , and s t i l l
a n o th e r was d i s t i l l e d w ith d ry h e a t to d r iv e o f f th e a lc o h o l rem aining in
th e o i l .
The d i s t i l l a t i o n w ith steam was c a r r ie d o u t in th e a p p a ra tu s
siiown in f ig u r e 1 3.
The th r e e p ro d u c ts o f a lc o h o lic e x t r a c t i o n were
a p p lie d in t e s t s Noe. 120, 121 and 122 o f ta b le XVI.
.h iIe th e av erag e
in ju r y o f th e se o i l s was o nly a few p o in ts below t h a t o f th e norm al o i l ,
th e s e e d lin g s a p p ea re d to s ta n d th e e f f e c t s o f th e o i l very w e ll.
The same p ro c e d u re was fo llo w ed w ith form aldehyde a s w ith a lc o ­
h o l.
There was p r a c t i c a l l y no lo s s o f o i l due to e x t r a c t i o n w ith fo rm al­
dehyde.
The r e s u l t s a r e g iv e n in t e s t s Nos. 123, 124 and 12b o f ta b le
XVI.
The e x t r a c t i o n w ith a c e to n e had to be v a rie d somewhat from th e
p ro c e d u re follow ed w ith a lc o h o l.
e x tr a c te d too g r e a t a p o r ti o n .
I t was so m is c ib le w ith o i l t h a t i t
The m i s c i b i l i t y was d e c re a se d by adding
20 cc o f w a te r each tim e a f t e r au ak in g w ith a c e to n e .
Ih e m i s c i b i l i t y
o f a c e to n e and w a te r i a g r e a t e r th an the m i s c i b i l i t y o f a c e to n e and o i l ,
hence more o f th e a c e to n e would le a v e th e o i l f o r th e w a te r and th e
lo s s e s o f o i l were n o t to o g r e a t .
The in ju r y o f o i l s e x tr a c te d w ith
a c e to n e i s re p o rte d in t e s t s Nos. 126, 12? and 128.
A a l i g h t d e c re a se
in in ju r y i s shown.
h aving o b serv ed some bad e f f e c t s from steam d i s t i l l a t i o n e a r ­
l i e r in th e stu d y o f spray o i l s , a sample o f o i l No. Ib was d i s t i l l e d
-
28-
" i t h steam f o r 8 hour# and a p p lie d In t e a t No.128.
2».& p e r c e n t w h ile t h a t o f th e norm al o i l wae 1 8 .2 .
The in ju r y eaueeu was
Two o u t o f th re e
StL-iI1le a o f th e steam d i s t i l l e d and e x tr a c te d o i l s showed g r e a t e r in ju ry
th a n the o th e r e x tr a c te d o i l s .
a t atm o sp h eric p r e s s u r e .
A ll steam d i s t i l l a t i o n # were c a r r ie d o u t
In every e ase th e r e s id u e , o r p o r tio n n o t v o l­
a t i l e w ith e te e a a t a t m s p h e ric p r e s s u r e , was re c o v ere d and u sed ,
a
v ery sm all p o r tio n d i s t i l l i n g o f f w ith th e steam was not recovers-, and
th u s th e term "steam d 1 s tI U e u ” i s in ten d ed to a p p ly , in t h i s work, to
th e re s id u e and n o t th e d i s t i l l a t e .
T able X7I.
I n ju r y to B arley S e e d lin g s by O ils E x tra c te d a I t h V o la tile
S o lv e n ts and by Steam D i s t i l l a t i o n
( s in g le d e te rm in a tio n s )
T e st
number
120
121
122
O il
number
16
lb
lb
123
124
lb
15
12b
lb
126
127
128
15
lb
lb
T reatm ent
E x tra c te d w ith &5$S a lc o h o l i n s e p a ra to ry fu n n e l
E x tra c te d w ith 65% a lc o h o l and steam d i s t i l l e d
E x tra c te d w ith 85% a lc o h o l and d i s t i l l e d w ith
d ry h e a t
Average
E x tra c te d w ith 40% form aldehyde
E x tra c te d w ith 40% form aldehyde and steam
d is tille d
E x tra c te d w ith 40% form aldehyde and d i s t i l l e d
w ith d ry h e a t
A verage
E x tra c te d w ith a c e to n e
E x tra c te d w ith a c e to n e and steam d i s t i l l e d
E x tra c te d w ith ace to n e and d i s t i l l e d w ith d ry
heat
Average
In ju ry
p e r c en t
6 .3
1 8 .2
1 3 .8
13.4
27.4
3 1 .2
3 7 .7
32 .1
13.2
3 3 .8
2 4 .1
23 .7
128
15
D i s t i l l e d w ith steam f o r 8 hours
2 9 .5
130
15
Normal
1 8 .2
-
28-
An e x t r a c t o r baaed on the p r i n c i p l e t h a t u lc o n o l f l o a t s on o i l
• a s made f o r the purpose o f g e t t i n g b e t t e r e x tr a c ti o n (s e e f ig u r e 1 4 ).
The id e a o f e x tr a c ti n g n o a v le r l i q u i d s w ith l i g h t e r o n es was used by
F a y o lle and Lom and
^ and la d e sc rib e d by
o rro w ^ L
T e sta Nos. 131
to 136 o f ta b l e X Tll show some o f th e r e s u l t s o f e x tr a c ti n g o i l s w ith
S h la a p p a r a tu s .
In t e s t s No. 134 and 13b th e o i l s were e x tr a c te d w ith
a b s o lu te a l c o h o l .. Anhydrous lim e was p la ce d In th e s t i l l to ta k e up any
w a ter e x tr a c te d from th e o 11 and e v ery p re c a u tio n was used to c a rry o u t
th e e x tr a c ti o n in such a say a s to remove a l l the w a te r from th e o i l .
Iiowevert th e r e s u l t s show t h a t th e o i l s p re p a red In t h i s way were more
I n ju r io u s th a n th e norm al o i l .
No re a so n f o r th e d i f f e r nce can be
advanced.
Table XVII.
I n ju r y to B arley S e e d lin g s by O ils E x tra c te d viith
A lcohol, in an E x tra c to r
(d u p llc a te tie t e rm in a lio n s )
T est
number
O il
number
T reatm ent
In ju ry
p e r c en t
9 .4
15.4
3 2 .6
131
132
133
15
15
15
E x tra c te d w ith 85% a lc o h o l - 50% reco v ery
E x tra c te d w ith 95% a lc o h o l - 70% reco v ery
E x tra c te d w ith 65% a lc o h o l - 86 % reco v ery
134
135
15
15
E x tra c te d w ith a b s o lu te a ICohoI - 50% re c o v ery
E x tra c te d w ith a b s o lu te a lc o h o l - 82, re c o v e ry
26.2
3 6.4
136
15
P o r tio n reco v ered from above a lc o h o l e x t r a c t s
52.4
137
15
Normal
24.4
H a y o lI e and Lormandt Ch. t A p p a re il tie P e r f o r m tlo n Pour E p u ise raent ties L iq u ld ee p e r Io e L iqueties. Llquddee non M lacl b l e , Chemie
and I n d u s t r i e , 8, 873-274, 1822.
l*)iSorrow , G. A ., B iochem ical L ab o rato ry ietkodo. John A lley and
Sons, New Y ork, 1927.
-
30-
Fort her te s ta were made with a lc o h o lic ex tra cted o i l s and
r e o r t e d in ta b le XVIII.
I t was thought th a t a lc o h o lic e x tr a c tio n in
the e x tr a c to r wae not producing th e d e sire d r e s u lt .
The in ju r io u s por­
tio n o f the o i l may be v o l a t i l e w ith a lc o h o l and thus go round and round
in the e x tr a c to r w ith out being e lim in a te d .
In fa c t a p o rtio n o f the o i l
i s v o l a t i l e w ith a lc o h o l a s shown by the f a c t th a t when the a lc o h o lic
vapors from the s t i l l f i r s t h it the condenser an o i l y substance accumu­
la te d .
a
study o f the d a ta , however, in d ic a te th at a t l e a s t some o f the
in ju r io u s p o r tio n o f the o i l la removed by e it h e r method o f e x tr a c tio n .
The decrease in injury caused by a lc o h o lic extra cted o i l s i s probably
due to the same reason th a t in ju ry la reduced by a u lfo n a tio n o r f i l t r a ­
t io n .
S u lfo n a tlo n v a lu es were determined on part o f the a lc o h o lic
ex tra cted o i l s o f ta b le XVIII.
In every ca se a lc o h o lic e x tr a c tio n
removes the same m a te r ia ls th a t a u lfo n a tio n d oes.
E xtraction o f P i le w ith Ammonia
A p ro cess d escribed by A lbright^1 ) fo r n e u tr a liz in g acid
tr e a ted o i l s w ith ammonia has suggested th a t i t might be p o s s ib le to
I prove spray o i l s by e x tr a c tio n w ith am o n ia .
The s u lfu r content o f
o i l s trea ted by t h is p rocess i s sa id to be decreased .
F ifty cc o f o i l No. Ib was e x tr a cte d in a separatory funnel
w ith b co n secu tiv e p o r tio n s, o f bO cc each , o f commercial ammonia and
steam d i s t i l l e d to d riv e o f f the d is s o lv e d ammonia.
About o n e -h a lf o f
th e o i l e x tra cted was recovered a f t e r e x tr a c tio n , and i t was applied
in t e s t a No. 149 o f ta b le XIX.
A sample o f o i l No. l b , th a t had been
su lfo n a te d , was a ls o ex tra cted with ammonia.
The in ju ry shown by t h is
(I )A lb r ig h t, J . C ., Ammonia fo r N e u tr a liz in g and T reatin g.
iie fin e r , September, 1 6 .il.
Tne
sample was l e s s th a n Utiat o f th e norm al o i l , p o s s ib ly because o f th e
e f f e c t o f s u lf o n a tlo n .
The sam ple t h a t wae n o t a u lfo n a te d , b u t was
e x tr a c te d w ith ammonia, showed p r a c t i c a l l y no d if f e r e n c e from th e norm al
o il.
Table X V III.
I n ju r y to B arley s e e d lin g s by O ils E x tra c te d w ith
A lcohol by Two D if f e r e n t
T eat
number
O il
number
136
15
139
16
140
16
141
5
148
6
143
5
144
28
146
26
146
28
147
8
146
6
ethooa
T reatm ent
T r i p l i c a t e D e te rm in a tio n s f o r In ju ry
E x tra c te d 10 tim es w ith 95# a lc o h o l In
a s e p a ra to ry fu n n e l - 60% reco v ery
E x tra c te u w ith 95# a lc o h o l in an
e x t r a c t o r - 40# re c o v ery
Normal
E x tra c te d 5 tim es w ith 95# a lc o h o l In
a s e p a ra to ry fu n n e l - 50# reco v ery
E x tra c te d w ith 95# a lc o h o l In an
e x t r a c t o r - 66# re c o v ery
Normal
In ju r y
p er cent
S u lfo n a ta b le
p o rtio n *
per cent
4 7 .6
8
6 3 .2
6 2 .6
Iti
4 6 .0
34
4 0 .3
4 9 .2
—
40
D u p lic a te D e te rm in a tio n s f o r In ju ry
E x tra c te d w ith 95^ a lc o h o l in an
e x t r a c t o r - 66# re c o v ery
E x tra c te d w ith 96# a lc o h o l in an
e x t r a c t o r - 40# reco v ery
Normal
4 1 .1
—
3 7 .7
4 9 .4
84
44
E x tra c te d w ith 96# a lc o h o l in am
e x t r a c t o r - 50# reco v ery
Normal
1 1 .3
2 3 .0
42
80
♦The s u lf o n a ta b le p o r tio n o f th e norm al o i l s In t h i s ta b le d i f f e r s
from t h a t found in th e appendix because th e same s tr e n g th o f a c id was
n o t a v a i l a b l e . However, a l l th e v a lu e s on t h i s ta b le were o b ta in e d w ith
th e same a c id and u n d er th e same c o n d itio n s .
- 32-
Table XIX.
In ju g y to B arley S eed lin g # by O il# rjctxacted
A lth Aaaonla
( d u p lic a te d e te a a ln a tio n e )
T est
number
149
O il
number
18
T reatm ent
In ju ry
p e r cen t
E x tra c te d B tim e s w ith ammonia in a s e p a ra ­
to ry fu n n e l - 80# re c o v ery
3 6 .0
180
18
S u lfo n a te d and th e n e x tr a c te d a s above
2 3 .5
181
18
Hormal
37.7
D iecu aalo n
A ll th e o i l s a p p lie d caused aome r e t a r d a t i o n in grow th o f b a r­
le y s e e d l i i ^ a , b u t i t waa very e v id e n t t h a t eo se a r e s o r e in ju r io u s than
o th e rs #
The u n tre a te d o i l s were fo u n d , in th e p re v io u s in v e s t ig a ti o n ,
to cau se a wide range o f i n j u r y .
T h is v a r i a t i o n may be due to th e f o r ­
m ation o f in ju r io u s compounds d u rin g th e r e f in in g p r o c e s s , o r to th e
o r i g i n a l p r o p e r t i e s o f th e o i l .
The d a ta p re s e n te d on the fo rm a tio n o f s u lfo n a t a b l e compounds
d u rin g d i s t i l l a t i o n and on th e in flu e n c e o f s e v e re o x id a tio n c o n d itio n s
show t h a t th e r e f in in g p ro c e s s may make an o i l more i n j u r i o u s , b u t th e
p r o p e r tie s o f th e o r i g i n a l o i l a re a ls o im p o rta n t.
S e v e ra l I n v e s tig a -
t o r s ^ * *'* tj 1 have p o in te d o u t th e e f f e c t o f th e movement o f th e o i l in
th e e a r t h , o r i t s f i l t r a t i o n w h ile in s to ra g e in the e a r t h .
They have
shown t h a t th e p a r a f f i n e , o r l i g h t e r f r a c t i o n s o f p e tro le u m , d if f u s e
W Bay, David T .,
r o c . Am.
U ilo s . S e e . , 1897.
(Z )G ilp ln , J . E . , and Cram, M. P . , The F r a c tio n a tio n o f Crude P e tro ­
leum by C a p illa r y D iff u s io n . If. S. Geo. u r . Bul. 3 68, 1908.
( Z )G llp in , J . S . , and Bi snak y , 0 . H ., The D iffu s io n o f Crude P e tro ­
leum Through F u l l e r ’ s E a rth . U. S . Geo. u r . Bui. 4 7 b , 1910.
-3 3 -
mure s lo w ly .
The n atural o i l s In sto ra g e In th e ea rth may have thus
been su b jected to more o r l e s s fr a c tio n a tio n during movements in geo­
lo g ic t i n s .
D iffe r e n c e s in the r a te o f d if f u s io n o f the various fr a c tio n s
rasy be poverned by the same fo r c e s th a t apply to g a ses o f d if fe r e n t
d e n s ity .
Graham's law s t a t e s that the r a te a t which a g a s d if f u s e s
through a sm all opening, or another space, i s In v ersely p rop ortion al
to th e siiuare root o f the d e n sity o f the g a s .
A c lo s e analogy seems to
p r e v a il between gaseou s d if fu s io n and the d if fu s io n o f o i l through a
filte r .
The above I n v e stlg a to r e have g iv e n e x te n s iv e data shoeing th at
the l ig h t e r fr a c tio n s o f petroleum d if f u s e more rap id ly through F u lle r 's
earth and hence conclude th at some o f the d iffe r e n c e s occurring in
natural o i l s have been caused by the f i l t r a t i o n o f the o i l w hile in th e
earth and o v er long p eriod s o f tim e.
Maberry(I) has c a lle d a tte n tio n to the remarkable s im ila r ity
o f petroleum o i l s in gem r a l , and s t a t e s th a t petroleum i e a mixture
o f a few homologous s e r i e s , v a r ia tio n s o f which cause th e d iffe r e n c e s
found.
F ilt r a t io n in nature has apparently been an important fa c to r in
the sep a ra tio n o f the in ju r io u s p o r tio n s o f so me spray o i l s .
B ra n a lQ r
G ilp in and
have shown th at s u lfu r compounds and m a te r ia ls th a t combine with
s u lfu r ic a c id and w ith bromine are retarded in the passage o f o i l through
earthen f i l t e r s .
The p resen t in v e s tig a tio n shows th a t eu lfo n a ta b le ma­
t e r i a l s are held back during f i l t r a t i o n (se e ta b le I I I ) .
I t has a lso
been A own th at a lc o h o lic e x tr a c tio n removes a u lfon ata b le m a te r ia ls.
( I ) Waberry, C. F ., Pro. Am. P h il# # . 3 o e ., 1903
- 34-
Thue ttie re Is e v id en c e t h a t th e th r e e p ro c e e e e sf f i l t r a t i o n , e u lfo n a tio n
and a lc o h o lic e x t r a c t i o n , remove some o f th e e ase m a te r ia ls and th a t
ta e s e m a te r ia ls a r e th e cause o f p la n t in j u r y .
D e n sity d e te rm in a tio n s were n o t made in t h i s in v e s t ig a ti o n on
tie
p ro d u c ts o f f i l t r a t i o n , s u lf o n a tio n and a lc o h o lic e x t r a c t i o n , but
th e work o f some o t h e r i n v e s t ig a to r s in d ic a te s th e d e n se r f r a c t i o n s a re
removed.
As p re v io u s ly s t a t e d , G ilp in and Bransky have i.hown t h a t the
f i r s t p o r tio n s o f a p etro leu m o i l d if f u s in g th ro u g h F u l l e r 's e a r th a re
o f low er d e n s ity th an su cceed in g p o r ti o n s .
Bacon and H a m o r^ and
O thera(B ) have s t a t e d t h a t s u lf o u a tlo n te n d s to d e c re a se d e n s it y , th u s
th e re a r e re a s o n s to b e lie v e t h a t Lhe d e n s e r compounds o f p etro leu m e ra
re s p o n s ib le f o r p la n t in ju r y .
I t was a ls o found in a fo rm er la v e a tig a -
t l o n O ) , ..here d e n s ity d e te rm in a tio n s were made, t h a t th e r e was a a l i g h t
tendency f o r th e d e n s e r o i l s to be more in j u r i o u s .
T h is bein g th e c a s e ,
th e re sh o u ld be a good p o s s i b i l i t y in f u tu r e I n v e s tig a t io n s to s e p a ra te
th e o b je c tio n a b le p o r tio n o f sp ra y o i l s by c e n tr if u g a l f o r c e .
The c e n tr if u g in g o f lu b r i c a t i n g o i l s has been p r a c tic e d in so #
r e f in in g m e tb o d sl* ).
I t I s claim ed t h a t by th e a id o f th e modern h ig h ly
developed c e n tr if u g a l machine t h a t the "p o u r p o in t" o f l u b r i c a t i n g o i l s
(I)B ac o n , It. F . and Hamor, W
. A ., American e tro le u m In d u s tr y , Vbl.
8, p . 681. MeGraw h i l l Book C o ., Hew Y ork, 1V16.
(B)Bedwood, B overton , P etro leu m and I t s P ro d u c ts ,
J , B. L l p p in c o tt, P h ila d e lp h ia , 1896.
tfo l. I , p. 398.
(3 )
o r e e n , l e a s e . Chem ical and P h y s ic a l P r o p e r tie s o f p etro leu m Spray
O i l s . A ccepted f o r p u b lic a tio n by J . o f A gr. Boa. 1932.
(4 )
Day, a v id T ., Hand Book o f th e P etroleum I n d u s tr y , Vol. 2 , p 369.
John A lley and Sons, Hew Y ork, 1922.
■36-
can be reduced lb to 20 d e c r e e s.
The sep a ra tio n o f suspended s o lid s and
c o llo id a l m a teria l i s undoubtedly r esp o n sib le fo r the low ering o f the
"pour p o in t" , o r the temperature a t which the o i l w ill flow under c e r ta in
s p e c if ie d c o n d itio n s .
Suwmary
1.
D i s t i l l a t i o n was found to be a very poor means o f sep aratin g
th e in ju r io u s p o rtio n o f spray o i l s .
2.
C h lo rin a tio n , n it r a t io n , h ea tin g under co n d itio n s th a t favor
o x id a tio n , and steam d i s t i l l a t i o n make spray o i l s more in ju r io u s to
p la n ts .
3.
f i l t r a t i o n , s u lfo n a tlo n , and e x tr a c tio n with a lc o h o l were
th e beat moans found to improve the q u a lity o f spray o i l s .
4.
A ll o f th e o i l s used caused some injury o r r eta rd a tio n in the
growth o f barley s e e d lin g s .
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Appendix
Table aborning 011» . rran g e d in C ru er o f In o re a s in c In jm y
a e D eterm ined in & Form er I n v e s tig a tio n
OU
number
24
22
3
20
16
4
8
21
12
5
26
13
15
In ju ry
per c e n t
7 .6
1 4 .4
1 4 .7
2 8 .8
3 1 .0
3 2 .1
3 8 .0
4 0 .4
4 5 .6
5 2 .5
5 8 .7
5 9 .6
6 0 .7
ii
Cheraleal and I h y s le a l A nalyeee o f Spray O il#
Kind o f an alyses
Laboratory numbers fo r spray o i l s used
13
21
18
16
16
20
22
24
28
4 0 .4
1 4 .4
7 .6
56J
4 0 .9
7 9 .6
3 8 .9
1 1 .0
70 JL
56
98
56
59
68
130
270
300
280
310
330
360
260
290
285
306
350
390
3%
375
3 .6 0
3 .5 0
0 .3 6
0 .1 3
0 .3 7
0 .2 5
no
c o lo r
8 .5 0
6
4
0 .5
good
0 .5
very
poor
3
good
7
very
good
good
poor
0 .6
very
poor
9
very
good
3 6 .0
3 6 .3
3 5 .5
3 4 .6
3 4 .8
3 5 .1
3 4 .9
3 4 .1
3 6 .1
4 2 .8
4 2 .2
5 8 .4
4 0 .4
3 7 .1
3 8 .1
3 7 .6
3 7 .4
3 6 .3
4 1 .9
4 1 .6
3 9 .2
4 1 .9
3 8 .6
3 9 .7
3 5 .3
3 6 .6
3 5 .3
3 4 .9
3 5 .1
3 9 .7
0 .6 6 1
0 .9 1 9
0 .9 3 0
0 .9 0 8
0 .9 0 6
0 .8 9 6
0 .8 7 4
0 .679
0 .8 8 4
0 .6 6 3
0 .6 3 7
0 .9 2 3
6 .0
1 2 .0
4 1 .6
5 3 .0
2 7 .5
3 1 .8
2 6 .4
1 0 .0
1 .0
1 5 .6
8 .0
none
3 5 .8
0 .0 2 0
0 .0 2 1
0 .3 9 0
0 .5 5 6
0 .3 5 0
0 .3 3 0
0 .2 1 3
0 .1 1 0
0 .0 4 1
0 .0 4 2
0 .0 4 6
0 .0 * 8
0 .5 7 0
B ltrq ge n , per cent
none
none
none
0 .0 2 5
0 .0 3 0
0 .0 1 2
0 .0 1 1
0 .0 0 3
0 .0 0 2
0 .0 0 3
none
none
Bromine ad sorp tion , per cen t
Bromine s u b s titu tio n , per cen t
Bromine a d d itio n , per cen t
0 .3 4
0 .0 1
0 .2 2
0 .8 9
0 .2 6
0 .3 7
5 .7 3
2 .7 6
0 .2 1
6 .9 4
8 .0 4
1 .0 6
5 .4 8
2 .2 8
0 .9 2
4 .9 3
1 .6 2
1 .6 9
4 .3 0
1 .9 8
0 .2 4
0 .6 8
0 .2 6
0 .4 6
0 .6 2
0 .0 8
0 .3 6
1 .4 3
0 .4 8
0 .5 9
0 .0 2 8 0 .0 2 6 0 .1 7 0 0 .1 7 0
i0.0 1 3 6 0 .0 3 0 6 0 .6 4 2 0 0.0320
5 .8 6 6 5.511 4 .1 9 3 5 .4 9 5
0 .0 8 5
0 .0 5 6
0 .0 6 5
0 .0 2 8
0 .0 2 8
0 .0 4 2
6
14.7
3 2 .1
5 2 .5
3 8 .0
4 6 .6
5 9 .6
6 0 .7
3 1 .0
2 8 .8
4 7 .8
5 6 .3
8 3 .8
6 9 .2
70 .9
7 6 .3
8 3 .9
8 3 .9
V isc o sity - Saybolt a t 100° F.
113
53
136
425
125
82
62
F la sh p o in t, d egrees F,
F ir e P o in t, d egrees F.
310
345
280
295
315
365
360
410
315
355
300
340
C olor, as compared w ith s o lu tio n (no
containing S mg Iodine per 100 c e (c o lo r 0 .2 0
6 .0 0
3 3 .3 3
1 2.60
Eem ilelfica tio n w ith water alone t
m inutes req uires fo r o i l to
sep arate
0*5
E m u lsifica tio n w ith w ater, c e - very
soap aa em u lsifyin g agent
poor
6
poor
36
very
poor
good
17
very
good
3 5 .4
3 4 .6
3 6 .6
3 7 .0
4 0 .5
3 6 .1
4 1 .7
3 6 .4
3 6 .1
0 .6 7 3
Free fa t t y a c id * , as p er cen t
o l e i c acid
Cti x 10-4
PB
4 .6 3 5
4 .6 6 3
4 .2 6 0
4 .3 4 5
6 .036
0 .2 4
0 .0 6
0 .1 2
0 .0 6
0 .0 2
0 .0 4
tra ce
6 .4 0
3 .1 4
0 .2 6
0 .0 4 2 0 .0 1 4 0 .1 2 0
0 .0100 0 .0 1 1 6 0.1920
5 .3 4 2 6 .0 0 2 5 .9 3 4 4 .7 1 7
O
S u lfu r , per cen t
0
S u lfon atab le p o r tio n , per cen t
$0
S p e c ific g r a v ity by teetphal
BalaM e
#0
Surface ten sion o f pure o i l .
Dynes per cm.
Surface ten sio n o f
eresoap
em ulsion, Cyaen per cm.
Surface te n sio n o f 6^ eresoap
em ulsion. Dynes per e-a.
5
O
Injury to b arley s e e d lin g s .
per cen t lo s s In weight
Injury to apple le a v e s , per
cen t lo s s In weight
1
S
1
1
1
'I
5
#0
4
3