July, 3918

T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y

jI1

ORIGINAL PAPERS
THE MANUFACTURE OF AMYL ACETATE AND SIMJLAR
SOLVENTS FROM PETROLEUM PENTANE
By BENJAMINT. BROOKS,DILLON F. SMITH AND HARRYESSEX
Received March 12, 1918

I n a recent paper1 we noted t h e effect of very high

pressures on t h e conversion of chlorpentane t o alcohol.
I n t h e following paper we describe a method for t h e
conversion of chlorpentane t o t h e corresponding
acetates under conditions which we believe are capable
of realization on a large scale without great difficulty
a n d without very costly or complicated apparatus.
T h e present prices of amyl alcohol a n d acetate are,
of course, abnormal. Yet it is very doubtful if t h e
prices during several years before t h e war will be t h e
rule for some time after t h e war, unless there is a large
production from some source not now known or t h e
synthetic article is brought into t h e market in large
quantities. Before t h e war this c o u n t r y imported
annually approximately 6,000,000 lbs. of fusel oil from
Russia. T h e decrease i n t h e manufacture of distilled
liquors a n d t h e spread of prohibition generally will
cause a n increased shortage of amyl alcohol a n d
acetate.
As is well known t o all familiar with fusel oil a n d
amyl acetate a n d their uses, these terms are employed
t o describe t h e mixture of amyl alcohols, or their
zcetates, together with more or less butyl and hexyl
derivatives. T h e composition of t h e natural fusel oils
varies considerably with t h e material fermented a n d
t h e character of t h e fermentation. Fernbachs recently developed fermentation, yielding chiefly isobutyl alcohol, is a n extreme case, a n d isobutyl alcohol
alone is too volatile for most of t h e technical uses of
fusel oil or amyl acetate. T h e following analyses
from Wordens Nitrocellulose I n d u s t r y illustrate
what is commonly found in commercial fusel oils:
COMPOSITIONOF NATURALFUSEL
OILS

FROM
CORNSPIRIT

FROM
POTATO
SPIRIT
Per cent
by wt.
Normal butyl alcohol . .
6.8
Isobutyl alcohol. . . . . . . . 2 4 . 3
Amyl alcohol..

........

67.8

F a t t y acids, etc. . . . . . . . 0.04

Per cent
b y wt.
Normal propyl alcohol.
3.7
Isobutyl alcohol.. . . . . . 15.7
Amyl alcohol.. . . . . . . . . 75.8
Hexyl alcohol. . . . . . . . .
0.2
F a t t y acids, e t c . . . . . . . .
0.56

T h e ordinary amyl acetate of commerce contains

approximately 70 per cent by weight, distilling within
T h e above analyses make clear
t h e limits 135 t o 140.
t h e fact t h a t it is not necessary t o isolate either pure
pentane as a raw material for synthetic amyl acetate,
or a single monochlorpentane t o make a n artificial
amyl acetate fulfilling all t h e ordinary requirements of
industrial uses.
A fairly large number of patents have been issued
which have for their object t h e manufacture of amyl
acetate from light petroleum mixtures, chiefly pentane.
T h e difficulties of most of these processes, so far as
we are acquainted with t h e m , appear t o be, first, t h e
formation of large proportions of dichlor a n d trichlor
1

J . Am. Chem. Soc., 88 (1916), 1369.

derivatives when t h e original hydrocarbon mixture is

chlorinated, entailing considerable loss of chlorine,
decomposition during distillation with evolution of
hydrochloric acid, corrosion of t h e distilling apparatus,
etc. The presence of higher chlorinated pentanes also
has t h e very objectionable result t h a t on decomposition,
as during distillation, chloramylenes are formed which
are relatively stable and make their presence known
i n t h e final synthetic amyl acetate by materially decreasing t h e solubility of many substances in t h i s
solvent. One patentee claims t h a t glacial acetic acid
need not be used as a solvent in t h e chlorpentanesodium acetate reaction, b u t acetic acid containing a s
much as 30 per cent of water m a y successfully be employed. Our experience is t h a t amyl acetate made
with acetic acid containing I O per cent or more of
water, contains considerable unchanged chlorpentane,
t h e presence of which markedly decreases its solvent
value. T h e second serious difficulty, common t o all
t h e processes known t o us, consists i n t h e formation of
relatively large amounts of amylene.
T h e first of t h e difficulties above mentioned has
been overcome almost completely a n d in a very simple
manner.
CHLORINATIOS

O F PENTANE

I n t h e earlier period of our work we lost considerable

time by attempting t o devblop a satisfactory method of
chlorination based o n t h e idea t h a t t h e reaction should
t a k e place i n t h e gaseous phase. Accordingly, a large
number of chlorinations were made b y introducing
chlorine into t h e hydrocarbons a t temperatures just
sufficient for t h e complete vaporization of t h e hydrocarbon. I n these experiments we assumed t h a t t h e
chlorine a n d hydrocarbon gas mixture should be
thoroughly mixed before reacting, a n d this was a t tempted by introducing t h e chlorine into t h e hydrocarbon gases in t h e dark a n d t h e n passing this mixture
through large illuminated glass tubes.
I n these experiments i t was found t h a t once t h e chlorinating
action h a d started it would proceed very smoothly i n
diffused daylight a n d t h a t ultraviolet light as a
catalyzing agent was not necessary; indeed, t h e reaction often proceeded with considerable violence a n d
t h e separation of some free carbon. It was difficult
t o regulate accurately t h e ratio of hydrocarbon vapors
t o t h e chlorine introduced, a n d t h e formation of
dichlor a n d trichlor derivatives was unavoidable. T h e
highest yields of monochloride derivatives were obtained when t h e chlorine-hydrocarbon mixture contained a large excess of hydrocarbons, namely, 2 t o 4
times t h e ratio necessary t o form t h e monochloride
derivatives. By employing mixtures containing 3
mols. of hydrocarbon t o one of chlorine, a yield of
monochloride of 88 per cent of t h e theoretical was obtained, t h a t is, 88 per cent of t h e chlorinated material
was monochloride. T h e large volume of hydrogen
chloride formed i n this reaction carries off large amounts
of pentane vapor, this fact necessitating t h e ab-

T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING C H E M I S T R Y

Vol.

IO,

No. 7

sorption of the hydrogen chloride in cold water in dissolving in a heavier gasoline, this raw material
order t o recover this pentane. It was easily apparent should prove t h e most economical.
t h a t t h e manufacture on a large scale of crude chlorT h e fractional distillation of t h e monochlorides
pentane by this method would entail great practical furnishes another opportunity t o reject material of undifficulties, and would certainly add a great deal t o t h e suitable boiling point. A distillation analysis of t h e
cost of this comparatively simple operation.
monochlorides employed i n most of t h e work here deAfter a number of preliminary experiments, which scribed, t h e chlorides having been made from a crude
need not be recorded here, a method was developed pentane fraction boiling point z j t o 4 5 O , is given
which has proved t o be quite satisfactory and which below:
Boiling Point
has served for t h e preparation of large quantities of
Per cent by
. Weight
.
90-100;
3.8
these chlorinated hydrocarbons. The simplicity of t h e
100-110
46.6
110-1200
27.4
method makes it entirely adaptable t o large scale
120-130O
14.4
130-140O
5.3
operations, and a fairly large experience with it over
Above 140'
2.4
more t h a n one year's time shows t h a t t h e chlorinated
product consists of t h e monochlorides t o t h e extent of
Several results which are typical of those obtained
90 t o 94 per cent.
b y chlorinating t h e cold pentane are given below.
T h e principle of t h e method simply consists in main- T h e per cent yield is calculated on t h e per cent of
taining always a very large excess of hydrocarbon as monochlorides in t h e total chlorinated hydrocarbon,
compared with chlorine and also, which is very im- not on t h e amount of pentane originally taken. T h u s
portant, a very large ratio of hydrocarbon t o if t h e yield is go per cent, t h e balance of I O per cent is
chlorinated products. I n brief, t h e method consists a higher chlorinated product.
in passing chlorine through a large number of small
TABLE
I-CHLORIE\'ATION O F CRUDE PENTANE, BOILINGP O I N T 25-45
Lost
Monoorifices into a large quantity of cold crude pentane, and
Wt.
with
Wt.
Unchlorides
Pentane
Time
HC1
Product changed 95-140'
Dichlorides
stopping t h e chlorination before t h e concentration of
Grams Hours Per cent
Grams
Grams
Grams
Grams
t h e chlorine derivatives becomes greater t h a n about
5500
4.5
13.4
5233
3908
1155
170
5500
5.5
35.0
4108
2555
1371
182
2 0 per cent of t h e mixture.
I n practice, escaping
5500
4.0
29.0
4206
3312
884
10
2500
4.0
25.0
2698
1775
61 1
47
hydrogen chloride is absorbed in cold water and t h e
2070
5.5
28.0
1492
407
110
975
3700
6.0
25.0
2781
2309
444
28
pentane thus recovered is returned t o t h e reaction
vessel. T h e presence of moisture is not objectionable,
Concentration of chlorides
Per cent monochlorides in
when chlorination was stopped
chlorinated part
in fact it seems t o be desirable. Illumination of t h e
21
87
24
89
,.
reaction mixture is not absolutely necessary, although
16
99
we have employed a high-power tungsten light bulb
24
93
34
78
i n t h e upper part of t h e reaction vessel, t h e light
17
95.5
catalyzing t h e reaction a t t h e s t a r t . This reaction
If desired, a pentane fraction of much smaller
exhibits a peculiar phenomenon. At first t h e pentane
boiling
point range can be employed as t h e initial raw
appears t o dissolve t h e chlorine unchanged, b u t after
material,
a n d this will result naturally in a final acetate
a n interval of about t e n minutes t h e color of free
chlorine quickly fades and disappears and then chlorine of smaller .range of boiling points. The fractional
may be passed in very rapidly, reacting as fast as distillation t o obtain most of t h e crude pentane used
dissolved. The liquid should be kept chilled t o a t in our work was carried out in a small jo-gallon exleast 10' t o prevent too great vaporization of pentane perimental apparatus. More homogeneous fractions
would be obtainable from larger stills provided with
with the hydrochloric acid formed.'
suitable columns, such as those employed for t h e
The control of t h e process can readily be accomrectifying of crude benzols.
plished b y observing t h e specific gravity of t h e mixture,
A small amount of hydrochloric acid is formed
since a specific gravity of 0 . 8 2 0 corresponds t o about
during t h e distillation of t h e crude chlorpentane, due
20 per cent of monochlorides, when a crude pentane
t o slight decomposition of the chlorides. T h e amount
fraction boiling a t 2 5 t o 45" is taken for chlorination.
of decomposition resulting from this cause is so small,
I n order t o illustrate t h e per cent of suitable crude however, t h a t no appreciable diminution of t h e yield
pentane contained in a high grade of gasoline, 76 O BC., of crude chlorpentane results. This fact has t o be
t h e following table of fractions obtained b y slow taken account of, however, in t h e choice of apparatus
distillation through suitable column is given:
for distillation, as will be brought out later.
Boiling Point

Per cent by Volume

CONVERSION O F

60-70

Casing head or natural gas gasoline naturally contains the largest per cent of pentane and when suitable
provision is made t o avoid losing t h e butane, as b y
1

Brooks, Essex and Smith, United States Patent No. 1,191,196.

CHLORPEKTANE

INTO

AMYL

ACETATE

Although t h e conversion of chlorpentane into amyl

acetate b y heating with anhydrous sodium acetate is,
a t first sight, merely a direct application of a standard
method of organic synthesis, we found i t necessary
t o carry out a large number of experiments in order t o
determine t h e optimum conditions, particularly as
regards temperature and pressure, nature of solvent,
effect of agitating t h e reaction mixture, yield from

T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY

July, 1918

various gasoline fractions, material of construction

for apparatus, effect of catalysts, a n d possible utilization of t h e by-product amylene.
Early i n t h e course of t h e work we determined t h a t
somewhat better yields of acetate are obtainable with
t h e lower boiling fractions t h a n from hydrocarbons
of higher boiling point. Kerosene chlorides are highly
unstable, decomposing slowly a t room temperature
t o such a degree t h a t i n several cases t h e pressure
of t h e HC1 developed was sufficient t o expel t h e cork
from well stoppered containers. T h e tendency of t h e
alkyl chlorides t o decompose with t h e formation of
olefines increases with those of higher molecular
weight, as is shown b y t h e following results.
TABLE11-YIELD

ACETATEFROM CHLORINATED GASOLINEF R 4 C T I O N S l

OF

Boiling Point Yield Acetate Olefines

Original
Per cent
Per cent
Hydrocarbon of Theory
of Theory
Calculated for pentane
28-30'
50
35
30-350
49
34
Calculated for pentane
49
34
Calculated for pentane
35-40
46
42
Calculated for 50 per cent
45-50
46
42
Calculated for 50 per cent
50-550
43
43
Calculated for 50 per cent
55-60''
Calculated for 50 per cent
60-65
42
43
38
47
Calculated for 50 per cent
65-70
1 Heated 11 hours a t 190-195' in autoclave, not stirred.

pentane
hexane
hexane
hexane
hexane

Owing t o t h e large a m o u n t of solid material in t h e

reaction mixture, anhydrous sodium acetate a t t h e
beginning a n d sodium chloride toward t h e end of t h e
operation, we carried out several comparative experiments t o determine t h e effect of continual agitation
of t h e contents of t h e autoclave. When t h e reaction
mixture is not agitated, a hard, nearly solid salt cake
forms, which prevents further reaction.

Autoclave
rotated
Autoclave
stationary
Autoclave
rotated
Autoclave
stationary

580 g.
750 g.
375 g.
375 g.
580 g.
750 g.
375 g.
375 g.
730 g.
800 g.
472 g .
650 g.
650 g.
750 g.

Chlorides
Sodium acetate
Acetic acid
Amyl acetate
Chlorides
Sodium acetate
Acetic acid
Amyl acetate
Chlorides
Sodium acetate
Acetic acid
Chlorides
Sodium acetate
Acetic acid

230

394

1.2

51 6

250

273

7 1

22.1

513

this way containing relatively large amounts of unchanged chlorides, as illustrated by t h e following
experiments.
TABLE IV-INFLUENCE

OF THE

WATER

Time
SOLVENT
Hours
Acetic acid, 99 per c e n t . . , . . . 15
Acetic acid, 90 per c e n t . . . ,
15

.. .

REACTION
MIXTURE
Yield
Acetate
Chlorine
Per cent in Product
Temp. of Theory Per cent
2200
42.3
2.0
2200
38.0
5,s
IN

T h e presence of a solvent is necessary if a product

free f r o m chlorides is desired. T h e result obtained
without a solvent is shown i n Experiments I I a n d 19,
Table V , in which it will be noted t h a t t h e per cent of
unchanged chlorides in t h e product is very high.
-4 few substances, BaC12, FeC13, a n d CuC1, were
tried for their possible catalytic effect, b u t no benefit
could be noticed in t h e results.
It is possible t h a t t h e smylenes resulting in t h e
t r e a t m e n t of t h e chlorpentane mixture, as herein
noted, are derived largely from secondary or even
tertiary chlorides or acetates. We tested t h e stability
of commercial amyl acetate, consisting almost entirely
of acetates of primary alcohols a n d found t h a t during
8 hours a t 205' a n d about 300 lbs. pressure i n a copper
lined autoclave, only 6.5 per cent of amylenes were
formed. After cooling, t h e autoclave showed a pressure of 60 lbs., due t b gaseous products of t h e decomposition, probably COz a n d ethylene.
We have n o t h a d t h e opportunity t o examine t h e
constitution of t h e amyl acetates made from t h e
petroleum fractions, as t h e primary object in view
was t h e commercial utility a n d value of t h e product.
We find t h a t t h e solvent power of synthetic amyl
acetate for cellulose esters and gums is such t h a t by
these tests alone t h e natural and synthetic acetates
cannot be differentiated from each other. If, however, t h e acetate contains two or more per cent of
chlorine in t h e form of unchanged chlorides, its solvent
power for gums and resins is markedly diminished.
X number of typical results are included i n Table V.
UTILIZATIOP; O F A M Y L E N E S

12

240

458

0.9

50.1

12

240

300 1 6 . 5

26.0

T h e presence of water i n t h e glacial acetic acid

r e t a r d s t h e reaction very markedly, acetates made i n

U7e believe i t is very doubtful if t h e amylenes,

obtained as a by-product i n t h e conversion of t h e
chlorpentanes t o acetates, can profitably be converted
into alcohols or acetates. So-called hydration of
amylenes a n d other olefines t o t h e corresponding
alcohols has been investigated b y us a n d t h e results

TABI
+E 1
'
Sodium
EXPT.Chlorides Acetate
No.
Grams Grams
94
50
50
89
400
400
31
730
900
18
730
945
750
I7
580

Solvent
Time
Grams
Hours
100 g. Acetone
8
500 g. Absolute alcohol
9
470 g. Acetic acid
2
470 g. Acetic acid
5
375 g. Acetic acid
5
375 g . Amyl acetate
None
12
None
6
750 g. Acetic acid
4

195-200
205-210
195-200

Temp. Pressure
' C. Pounds
180-190
190
220
195-200
180
195-200
230

...
...
...

19
11
5

1100
950
580

1422
1215
750

580

750

750 g . Acetic acid

1.5

195-200

580

750

375 g. Acetic acid

375 g. Amyl acetate

195-200

170
300
400
430
200
260

...

Yield
Crude Acetate
Per cent of
Theoretical
60
63.3
51.5
55.0
55.4

Chlorine Yield Acetate

in
Corrected
Product
Per cent of
Per cent
Theoretical

....

3.14
0.9
7.0

.,..

REMARKS

1.2

53.2
49.7
43.4
53.4

Product contained free amyl alcohol

47.0
45,3
43.0

11.0
6.4
1.0

31.4
36.6
41.2

30 g . BaClz in reaction mixture

45.0

3.5

31.9

30 g. FeC13 added

50.0

0.9

48.8

T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERIlYG C H E M I S T R Y

514

FLOW

AMYLA C ~ T A T E
SHEET-QUANTITfES FOR ONE D A Y
CHLORINATIO~~

No. 7

FLOW
SHEET-ACSTWATXON
Cryst. Sodium Acetate

tank

Monochlorpentane

3.
Melting pans, fused Acetate

Glacial Acetic
Acid, storage tank

Rec. Fenfane, 3225 gal.

5.000 gal. storage tank

Condensing Water

IO,

AMYLACETATE
.

Pentane, 1075 gal.

18,000 gal.

Chlorine, 5620 lbs.

or 1 10 cells

1701.

Autoclaves, copper lined

3 Chlorinating Units

Wash water

Washing tanks

Salt and Sodium Acetate

Salt

Pentane and Monochlorpentane

18,000gal. storage tank

+J

Pump

d*+

16%

Pentane Loss

Dichlospentane Loss

Recovered Pentane, 3225 gal.

Monochlorpentane, 6750 lbs.

8,000gal. storage tank

Acetic Acid, glacial

Amyl Acetate, storage

embodied in a separate paper.1

With sulfuric
acid the principal results are polymerization t o
heavier, more viscous oils (not tars), the formation of alcohols a n d of acid and neutral esters of
sulfuric acid. We have not been able t o obtain
yields of alcohol as high as noted by Wischnegradsky2
in the case of amylene made from natural fusel oil.
T h e yields obtained b y us are given in t h e following
fable, and it will be noted t h a t with 50 per cent acid
very little change was effected a n d with 9 5 per cent^
acid a t j.0 mostly polymers were formed.
TABLE
VI-ADDITION OF WATER TO AMYLENS-HEXENE
MIXTURE
BY
PURIC ACIDOF VARYING
CONCENTRATIONS
h

ii

2
Frl

0
50
75
75
75

2
3

4
5

7
8
9

8 1.%

*6
._g o
%E
$3
p

95

- 5

-5

g0

05
BE

3E

0s

18

$ ?rJ.0
%

$&
G

@
D

34;
d

90.0

1.0

50

E
G

0
0

2
2.5

2
2.5
2.5
2

.Y ;s
p-

gd
M C

2
3

-10

7 5 ( 2 vols,)
-15
75
85
-15
-10
lvol.

+
acetic acid
85

1.0

:E::
10.0.
22.0
13.0
4.0

22::
2;7;:0 . 0

SUI,-

:
E*
ig

3.2

l
i
8.0

i:

32.0
56.0

12.0
14.0
18.0

8.0
32.0
13.0

5.0

11.0

75.0

I n view of the readiness with which olefines react

many mineral acids, such as H2SO4, HCl, H B r ,
HOC1, a n d in some cases even H C N a n d H,S, we
thought it possible t h a t under certain conditions
acetic acid might react with t h e amylenes direct.
Accordingly t h e conditions of t h e usual acetylation
1

J . A m . Chem. Soc., 42 (1918), 822.

Ann., 190 (1877). 328.

were tried on amylene itself. A q u a n t i t y of crude

amylene, 1 2 5 g., boiling point 30 t o 60, was heated
in a n autoclave a t zoo for j hrs. with a n equal weight
of glacial acetic acid. F r o m the reaction product we
isolated only 4.5 g. oil boiling a t I O O t o 135 a n d 4.0
g. residue above 13j O , these fractions consisting of
polymers of t h e original amylenes. I n another experiment 90 g. amylene were heated 20 hrs. a t 100
with 90 g . acetic acid a n d 30 g. zinc chloride a n d t h e
result was 14.j g . polymers boiling over 100. A
reaction mixture duplicating t h e last was let s t a n d 3 0
hrs. a t 2 0 t o 24, obtaining 8 g. polymers.
It is not t h e purpose of t h e present paper t o go i n t o
the details of producing a given o u t p u t of synthetic
amyl acetate. However, a brief discussion of t h e
character of the apparatus required and a conservative
estimate of costs should make clear t h a t the commercial
manufacture of synthetic amyl acetate is entirely
feasible. I n view of t h e amount of amyl acetate
annually consumed in t h e United States alone a n d t h e
amount of the synthetic acetate which might conservatively be expected t o find a ready place in t h e
market we have, for t h e sake of definiteness, based
estimates on a daily production of 600 gal. of s y n t h e t i c
amyl acetate. T h e figures used are based u p o n a
yield of monochlorides of go per cent, a low average
for t h e method described, and a yield on acetylating
of 5 5 per cent of t h e theory, a result actually a t tainable a n d probably exceeded. T h e minor b y products>amy1ene, common
and
acid,
have not been given a n y value i n t h e estimate. It
has been assumed t h a t the crude pentane would be

T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING C H E M I S T R Y

J u l y , 1918

furnished in t a n k s or steel drums, being most advantageously manufactured a t t h e source of production of casing head gasoline. T h e price of such a n
article i n fairly large quantities bears no relation
whatever t o t h e prescription doses of pentane sold or
photometric work. I t has also been assumed t h a t
t h e most advantageous location for such a plant would
be i n t h e neighborhood of a chlorine-caustic soda plant,
where t h e chlorine would be available for use without
liquefaction. T h e diagrams indicate roughly t h e flow
of material.
APPARATUS REQUIRED

I-STORAGE

ESTIXATED
COST

515

SYNTHETIC AMYLACETATEON THE BASIS OF 600

GALLONSDAILY PRODUCTION
DAILY COSTS
Gasoline, 990 gal. a t 40 c t s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
$ 396.00
130.00
Chlorine, 5200 Ibs. a t 2 . 5 cts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
732.00
Acetate of soda, 4880 lbs. cryst. acetate a t 15 cts.. . . . . . . . . . . . .
Soda ash, 1450 lbs. a t 3 c t s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
43.50
Interest on $35,000 a t 6 Der cent. and deDreciation a t 20 Der cent
per a n n u m . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
30.30
Labor one chemist a t $8,OO, 10 laborers a t $4.00.. . . . . . . ... . . . .
48.00
40.00
Fuel i n d Power. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
OF

TOTALDAILYCOSTS.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
VALUE OF PRODUCTS
Amyl acetate, 600 gal. a t $4.50 per g a l . . . . . . . . . . . . . . . . . . . . .
Total daily costs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

$1419.80

DAILYPROFIT. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

$1280.20

$2700.00
1419. 80

MELLONINSTITUTE OF INDUSTRIAL RESEARCH

PITTSBURGH

FOR

Crude pentane, 18,000 gal. steel tank.

Crude chlorinated product, pentane and chlorpentane,
18,000 gal. lead-lined steel tank.
Distilled chlorpentane, 8,000 gal. lead-lined tank.
Sodium acetate, crystalline, IOO ton covered wooden
bins.
Glacial acetic acid, 10,000 gal., j wooden tanks,
2,000 gal. each.
Amyl acetate, finished, I j , O O O gal., 3 steel tanks, j,OOo
gal. each.

THE EFFECT OF ANNEALING ON THE ELECTRICAL

RESISTANCE OF HARDENED CARBON STEELS
By I. P. PARKHURST
Received iVovember 24, 1917

T h e electrical resistance of steels as affected b y impurities or b y different heat t r e a t m e n t s applied over

wide ranges of temperature, has attracted t h e a t t e n tion of several investigators. A resume of previous
work is here given.

2-CHLORINATION

3 units complete, each consisting of one joo gal. earthen-

ware vessel fitted with lead coil for cold water or brine,
glass Hart condenser of the type used for nitric acid,
and earthenware receiver for separating recovered pentane
and aqueous HC1.
3-STI1,LS
2 Steam jacket Duriron stills, 1000 gal. charge capacity for
rectifying chlorpentane.
I Steam jacket copper still for rectifying amyl acetate,
acetic acid, and amylene mixture, capacity 900 gal.
4-ACETYLATION

Copper-lined steel autoclaves, jacketed, heated by hot

oil circulation, provided with agitators of copper or

Duriron, capacity 900 gal. each.

j-ACCESSORIES

Centrifugal extractor, 30 in. copper mesh basket, for

separating salt from reaction mixture.
I Agitator, copper, for washing amyl acetate with soda ash
solution, capacity 900 gal.
I Wooden tank with chain type agitator for washing excess sodium acetate from salt, capacity joo gal.
2 Crystallizing pans, iron, in brick setting, slow direct fire
for recovering sodium acetate, 300 gal. each.
3 Melting pans, steel in brick setting, slow direct fire for
fusing sodium acetate, capacity zoo lbs. sodium acetate
each.
I Motor for agitating autoclave, 8 h. p. steam, zoo boiler
h. p. for distillation, heating building, pumping, etc.
4 Dump cars and track for conveying salt, sodium acetate,
etc.
I Motor, 8 h. p., for operating pumps.
3 Low-pressure rotary pumps for pumping pentane, amyl
acetate, etc.
I

BUILDINGS
I
I
I
I

Shed for storing acetate of soda.

Building for chlorinating pentane and distillation of
chlorpentane, fireproof asbestos board.
Building for acetylating and distillation of amyl acetate.
Building for boilers and fusing sodium acetate.

Suitable vessels of this size are regularly manufactured,

RfiSUMf

O F PREVIOUS WORK

W. H. Johnson2 made a s t u d y of t h e electrical resistance of steels in order t o determine t h e effect of

impurities. T h e resistance of seven samples of differe n t analyses was measured. T h e impurities were
found t o increase t h e resistance, b u t t h e d a t a obtained were not sufficient t o allow of specific conclusions.
A. Campbell3 determined t h e effect of stress o n
t h e resistance of iron a n d iron-nickel wires. Practically no change was observed u p t o t h e breaking
point.
H. Le Chatelier4 investigated t h e effect of high temperatures on t h e resistance of iron, steel, hard steel,
iron-nickel, platinum, etc. His measurements were
made i n a n atmosphere of hydrogen. In a 0.6 per
cent carbon steel h e observed breaks i n t h e temperature-resistance curves a t 710 a n d 820 C.
H . Le Chatelier5 studied t h e effect of hardening
a n d tempering on t h e resistance of steels. His results showed t h a t t h e resistance was increased b y
hardening a n d decreased b y tempering.
L. Compredone made a s t u d y similar t o t h a t of W.
H . Johnson, referred t o above, a n d obtained similar
results.
J. D e War a n d J. A. Fleming determined t h e resistance of iron a n d nickel a t temperatures down t o
t h e boiling point of oxygen. T h e y found t h a t t h e
resistance decreased rapidly with t h e decrease i n t e m perature.
1 Read in abstract a t the Metallurgical Symposium, Boston Meeting.
American Chemical Society, September 1917.
Chemical Composition and Electrical Resistance of Steel Wire,
J. Iron and Steel Inst., 19 (1881), N o . 2, 605.
3 Electrical Properties, Engineering, 63 (1887), 468.
4 Electrical Resistance of Iron and Its Alloys a t High Temperatures,
Comfit. rend., 110 (1890), 283.
5 Effect of Tempering on the Electric Resistance of Steel,
Comfit.
rend., 112 (1891), 40.
6 Electro-conductivity of Steel, Le Genie Civil, 19 (1891), 309.
7 Electrical Resistance of Iron, Phil. Mag., 34 (1892), 326.