 

:33: 3333333333333 33:: (3:3 3:33: .353
93 3: (34 .35 3. (23:32.33:
(32:33:: 3.43.3.3“: (1:33 3333 (333:9 93.3393:
(33 3333:3(3335 $33: 3.3.3:: :3: WASTE

Fiﬁ-(3.3L (43.33335

T310333: 3:2: fits: £333.33: (3% BA. 5.
MAM-{$11.3 SYA'TE QﬁLLﬁﬁi
3“ . E 33731 ’97 . Fl .- 3.;
:éugn 33.393. .93. (“msbmg

W43

 
 

 

 

 

 
 

1.1312431? -
Michigan Stat:
University

t

~
'9.

0‘ ‘I

 

 

 

 

 

 

[HIE IlngSIjIUlLI 10.! CHI: 11‘: VIP Q? :204 AS A CATJEJYST
OIFIGFII—CAI (RIFLE FOR LXI) LIZLII SKI OF

FLI itOUS “ M? I III WASTE PICI.LEL LICJIOIIS

HUGH CIII‘J‘LES FORSBLRG

A TI‘JSSIS

Submitted to the Graduate School of michigan
tats College of Agriculture and Applied
Science in partial fulfilment of the
requirements for the degree of

LMS’ILII 033‘ SC TIICE

Depar+ ment of Cl-emical and Metallurgical Engineering

19 48

'°' 33*“ ere-"ﬁrm“:
A 3430.9 - I...-.I.'Ib

The au’cl‘Ior is deeply indebted to Dr. C. C. DeE‘Zi‘bt and Professor

J. If. Donnell for

is also expressed

f")

Engineerix‘g Btei'

their gﬂdamce and valuable advice. Agapreciation
to the members of the CI‘Iemicel and metallurgical

for their assistance and es.Icom'a4-;e:;.ents, and to

Dr. E. Leininger for his assistemce on ﬁle (analysis procedures.

TABLE OF COKTENT

IIII..ODUCTION .............................. l
HISTORICAL ................................ 3

IFDI’EI’ICAL coco-00o.cocooooooooooo-OOOIOIO 5
PICTUPLS OF EQ PHEUT ..................... 8
III'II’EFII-ITIET AEID PRICLLUZ’L ................12
DATA ......................................15

DISCUSSION 00000000....0.00.0.000000000000036

ACCURACY OF III}: PROCEDURE .................58

1—:I-1 1~o--1-_.,.‘-.

DA‘U—JLUJ-‘JNS unconsooooooooooooooooono.oooooc’g
f~ ﬂnglm 1 quIW 10-0 (-1
SUGUAML-LO-L:S FCIsi lUlh I-Ju. ‘aLJu‘o .740 K g.............20

MPE-I‘4-‘IX O...0.00.0...OOOOOOOIOIOOOOOOCOIOIM

B: ELI“, \JPLAI): {Y OOOOCICOOOOOOCOOOOIOOIOOOO...045

INTRODUC T1013

Since the advent of the modern practice in our steel industry,
both the producers and fabricators of that industry l‘Iave had to con-
tend with a still wavered problem. ﬁrst problem is $18 diS‘posal
of the waste pickle liquors, the exhausted sulfuric acid solution used
for the removal of the oxide scale formed on steel during any of the
heat treating processes.

This pickle liquor contains varying amounts of free sulfuric
acid, and of iron in the form of ferrous sulfate. This material is
at the present time neutralized with lime and discarded. Although
there has been a great deal of labor and time expended on the prob-
lem of salvaging this waste, so far no other process has proved to
be economically feasible.

Within the pest few years another factor has come into the
picture which makes it imperative that a solution be found to this
problem. National and local government authorities, spurred on by
the efforts of conservation and natural wildlife orgmﬁmtions, have
passed many laws to prohibit the dumping of this waste into the
streams and waterways of our nation.

Because of this last event, the economic picture has changed
to the extent that any process for the disposition of these wastes,
in order to be economically sound, must produce saleable products

only to the extent of paying for the process itself.

2

As an approach to the solution of this problem, Dr. C. C. De‘i‘ﬁitt
and various of his co-workers at idic‘nigan State College have been
working on a process to convert the acid wastes into saleable iron-
oxide paint pigments. The overall process consists of the follozﬁng
steps:

1. Oxidation, by a continuous process, of the ferrous sulfates

into ferric sulfate.

2. Conversion and precipitation of the oxide pigxents from

the resulting ferric sulfate.

It is with the first step that the work represented by this
thesis is concerned. '

The oxidation of ferrous sulfate to ferric sulfate can be accom—
plished with nitric acid, but here again the process becomes econom—
ically unsound. To overcome tnis objection it was preposed to accom-
plish the oxidation in a countercurrent, pressure, column using
N204 as the oxidizing agent. The H204 would act by releasing two
atoms of om'gen to the ferrous sulfate, but then under the temperature
and pressure conditions within the 001mm would combine with the free
oxygen present and thus regenerate itself. me mixture of N204, 02,
and N2 introduced into the column would be produced as needed from
the catalytic oxidation of ammonia, and from the atmOSpheric air.

The present problem then evolved to the study of the oxidation
process with regeneration of the catalyst amazon-carrier using the

range of gaseous mixtures obtainable from the axmnonia oxidation process.

 

Ill'll. ‘1'! 1'. ll‘

IiIS'lURICAL

Hoak(5) of Mellon Institute in a recent article in Lndustrial
gag Engineering Chemistry gives a very good overall picture of the
work which has been done on the (imposition of waste pickle liquors.

Some of the potential products Upon which work has been done
are: (a) copperas or other hydrates of ferrous sulfate, (b) recovery
of sulfuric acid, (c) iron onide as a first step for production of
iron powder to be used in powder metallurgy, (d) almonimn sulfate,
(e) iron oxide for paint pigments, (f) a constructional material,
Ferron, made from the sludge when pickle liquor is neutralized with
lime, (g) many miscellaneous inorganic compounds such as sodium
natrojarosite, Na2F95(OH)12~(SO4)2, ferric phosphate. None of these
processes has been operated cormercially as yet.

All of the processes developed have commercial possibilities
but so far all have come up to the stone walls of too high cost and
too little demand. Any of the various processes proposed are, be-
cause of the economics involved, limited to only large scale Opera-
tions. This means that the smaller producers will always have to
neutralize their liquor if other means of diaposal are impractical.
Extensive work has been done in order to provide the greatest pos-
sible economy for this type of treatment.

The present approach to the problem is not altogether new.
Back in 1894, iicCulloch (English patent 17112) described a process

for the oxidation of ferrous sulfate to ferric sulfate with air

using nitric oxide as the oxygen carrier. In 1906, Lienc‘not and
Zechentmayer (8) published data on the equilibrium between nitric

(10) and Frie11d(2)also

oxide and ferrous salts. Thomas and Williams,
publismed data on work done along this same line in 1921.

They showed, among other ﬁlings, that the reaction rate was not
slowed by time presence of the ferric products, the rate was somewhat

proportional to the concentration of the nitric oxide catalyst, and

that bigger temperatures increased the reaction rate.

W1? 71"":"1’
lulu 4.4.4“; AL

In order to explore the process from a theoretical standpoint,
a study of the AF, AH, and equilibrium constant (Kc) was aside. In
its most simplified form the reaction studied is as follows:

39304 + {302 + 112304 —— Fe2(804)5 + {120

Tue reactions involving the N204 are not considered since it is
regenerated and therefore acts only as a catalyst.

From the fact that all the reactants and products are present
in dilute solutions, it is possible to figure theAF for the reaction
directly from published data. From free energy of formation data
given in the Handbook 3: Chemistry and Physics,(4) theAFo at 25°C
for the reaction was calculated.

2Fe804 + 2:02 + H2804 —v F92(SO4)5 + 1120

-[2(-196,740) +. (-1?e,5oo)] +[(-555,740) + (-56,530)]
A?" a 42,520 cal.

From this the equilibrium constant (Ks) at 25 deg. C. can be

oalcxﬂnted.
AF° == .- RT ln (Ks) (3-1)
-22,320 = ~(1.9e7)(298) ln (Ks)
ln(Ka) = 57.65

(Ks) = 4.46 x 3.007
The (Ks) is independent of pressure but varies with temperature

according to the relation:

d [ingxaﬂ _ M"

d .. ..
(«35) R

 

Integration gives:

0
in (Kn) == - MAE ( 9-7- +
n T ) C

In order to apply this relation to investigate the (Ea) at
higher temperatures, it is first necessary to calculate theAH° for
the reaction.

From Hougen and E’e'etson( 5) and Letimer(7) theAH of formation was
taken and to it added the heat of dilution. It was also noted from
graphs given in the same sources that the heat of dilution did not
vary to a significant degree with increasing dilution after reading
a degree of dilution approzwcimeting that used in this work. ri'herefore,
the data given in the tables, even mough at very high or infinite
dilution, approscinmtes "the conditions used in this work very closely.
In the case of 112304, an estimate was made in order to bring the re-

sults as close as possible.

V 23.33044 + 302 + 112304 —"'" F62(304)5 '0' H20
Heat of
dilution «14, 700 ~18 , 750 (a)
in cue/molt
AH of formation «217,000 439,750 650,000 .. 68,587

AH°== -[2(-253.,7oo) .- (208,500)} + [-708,587 - 68,587]
AI1° == ~56,487 cal.

From the values of (Re) and (53° calculated above for '1‘ == 298%

 

4* AB given for dilute solution

the inLebration factor (C) is 13311316.

(W

a 52,487 [1
1.987 298

()3
\1
0

Ch
(:2

C ~23.60

Assuming H0 :3 H at 150017, th e (Ka) at 150°? is calculated!

a = §3,137 ; 1 7 ,
1:1(Ku) 1.967 [538 "’ out} . JO
1n(Ka) = 50.8
(Ka) at 150° F = 5.3 x 1050

As a final conclusion from these calculations, it can be so on
that, under the experimental c02'1di‘tions, the eQLﬂlibrimn should not
be a controlling £30 tor. The l 53 negativeAFo and large (Kc)
values indicu‘se a very strong driving, force for the reaction to go
to cazpletion. It is 11.1011 “to be a matter of resistance, or in other
words, the re action rates Kiel: Will control. The reaction rat as
are in turn controlled by the conditions under mulch the reaction
takes place and the effectiveness of the catalyst used. These '-‘"1en

are the variables to be inve tigated

 

PICTIIRE OF mmmmr

 

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l2

EXPEPlNJITAL 11:1) 13300111313193

The first step in this study was the design and construction of
19 necessary erriuipnent. T1113 equipnent censisted 01 a cylindrical

1

reactor (see accornxmying era's-wings and picture) approximtely 5:; inches
in character and 2 ft. long. Toe reactor was heated by controlled temp-
ernture water pmped through a jacket built around tie reactor itself.
Agitation and refer—liquid contact was accomplished by pumping the
reacting liquid from the bottom of the reactor through a Spraying; head
into the gas-vapor space. Toe temperature was measured by a merino-
couple inserted in a well widen extended into the liquid in the reactor.
Pressure was controlled manually by introducing an inert liquid, ker-
osene, from a blow case under nitrogen pressure. A laboratory standard
pressure gauge indicated the pressure to an accuracy of better than

one pound per square inch. The method of introducing tl.e inert sub-
stance also made it possible to remove a sample of gas or liquid with-

‘

out varying the total pressure inside toe reactor.

*- x

The reactor was constructed with all parts in coz'Ltact with no
reacting liquids and gases made of 18-8 stainless steel. Stainless
steel needle values were used thrmnghout.

The times gases, N2! 02, and 3:204 were introduced from tank
supplies, and weir vurious protortions censured by their respective
partial ;;re"sures. In order to increL-se the presmire of the 13204 ,
which has a vapor pressure of one ntnosohere at about (70°F), this

cylinder was placed in a drum and heated 1‘: th hot water.

15

To avert the dimer of toxic amoszmere of 11204, which is fatal
at a concentration of approximately 25 parts per million, a high-
Speed centrifugal blower was set up as an emausting; system, as can
be seen in the accompanying picture.

The procedure for seizing the experimental runs as given below
was followed with the exception of the run 1'1de at zero gauge pressure.
The variations in this run, and any other minor variations on the other
runs are noted along Hi th the data.

In order to exclude tne variation of composition which would be
present in coroner-Ciel pickle liquors, all tests were run using a
synthetic solution made up as follows:

650 grams of F8304 ' 7 H20 (Comerciel grade)
75 grams of 112304 (conc.)
23; liters of distilled water
ter preparation, this solution was allowed to age ove- '511t and
then filtered and analysed for ferrous and ferric iron. The perman-
ganate method!. of analysis was used.

The equipment was adjusted to the temperature desired. Next
one liter of the pickle liquor was introduced and allowed to come to
temperature. Placing the vessel under nitrogen pressure tested it
for leakage.

Each of the three gases were introduced to the partial pressure
required for the test and the recirculation pump turned on. Time was

measured from the instant this pump was started. Little or no reaction

 

3175130 Appendix

14
went on before recirculation was started as evi’enced by the fact that
there was no pressure drop until that time.

As the reaction proceeded the total pressure fell proportionally
as the oxygen supply was used. However, by introducing the inert kero~
sene, the total pressure of the test was held constant. Samples of
the liquid were taken as a time function and analyzed for their ferrous
iron content.

At the end of each run, which lasted usually from 30 minutes to

"i .L“

one hour, a sample or tee as was drawn off into a modified Greet

ﬂ
0
equigment. Any acid gases were removed here b7 washing tith KOH, and
then the percent of remaining rygen was found by absorption with

potassium pyrogellete solution.

During the run, the pressure and temperature were recorded.

’12 OF DATA

7’ l
the."

sex

 

-te

6'
\

Pressure
Psi. Gage

Appro‘

Run 110 o

 

If) H) {n 01 m m «I
up a) c) or a: (*0
+’ +3 +3 +3 +J '01
Cd Ed R u; so v.1 *1"
(acute c:cuu”‘

rain!

Y91EKRLE‘6-L‘e “ e‘l‘ox 1191?:‘1‘5'3 ‘6) V5" "-571 “:91 U3.
OOCDOOOO0.0 01060 7CD
OOCDOOCDOOEOOK‘OSCJOE

#51 1:1 ‘01 ‘31 '13-“ I931 115; ”:19. 1;" T& 3:“.
<3 1010 t~C3o~b-
O O O
C>eiq>r>c3L¢C3rz
q>€3rie*d>r4a)LJb-
H H

mmwmmmmoo ’30“?
<1‘t~)‘1“§‘ <1“ \‘Kl‘ 'd'ﬁ-ztDCD‘J‘
r

8 8".) 1:0 5.)")

tﬁtﬁ‘ﬁﬁithD -1; 111t1e111 e1r11111
«awncauuwom a: bOCDHQNDGDQQGDGDCD
H to H E?) H m H :6) 1.3 m to m

00 00mmmo.. {Ln
Doggoommmaggqﬁwg
HHHHHHHHHHHHO H
8901- 0000000 F‘)
oooagonommongﬁ
Hr-lr-lr-l r4 HHHHHr-lr—h—la

lnA
lpB
190
l—A
er
lyC
29A
8—D
2~C
5eA
5-H
SnC
4-0
6-0
8-0
9.0

Rates
Bo

5.1 %

15 %

100

‘
J.

8

£204

‘

ates

D.—
“.0

32.1 %

(I
I“)

7.4

r1

CO
is”)

100 l?O

Sp.l-C

E0 K204

l6

17
Run Number l-A

Condiuons: Ten 1e1ature 1000?. Pressure 100 pa

Ho
0
C1
{:3
(3

Bee; '3 “its:
Pickle Liquor:
Volume 1 liter ‘f'er'g,

811211919 130. Q ‘ t 1155 grams

 

Anal? sis: Ferrous 42. n , E11104 soln./5 ml. sample
Ferric negligible
Oxygen Partial p1 essure . . . . . . . . . . . . . . . . . . . . 3.2 1183'... abs.

 

Nitrogen partial pressure .................. 105,; 25;, abs.
6,5 9 si.,ebs o,

Normality Of {£11104 used 0090oo00.0.0000...-oooooooooocoooo 0.119

 

H204 partial pressure ......................

Gouge
Pressure Temperature Sarnle Anal sis '2‘? Conversionl‘
Time Psi. 0F. ml. $21104 soln. nemarks

per 5 11].. eagle

10:25 100 99

10: 23 102 100 Pump on
:39 " 105

10:43 " 132.5

10:58 " 102.5

llzﬂﬁ ' 101.0

11221 ' 100.5 25.1 17.5 Egd of Run

0:12;“ (.1

11 in gas at end of Rum

0.0%

 

 

* Per

pi c}:l

cent

e liquor.

convel oion 1'0
solution used to

'1d by: 100
"titrate 5 ml. Sample of
1111. of 112331104 solution used to t."1.tr:1te a 5

.1. ° .1... .
vltub 1-)

ml .

ti. e ratio
sen: le lI‘O 1 run civi ded by the

53.2.1013 or 141.9 OI‘l-U‘ 'inﬂul

or

the 1:11.

Kﬁn04

n_ q . 1
111m 1311111001? l-B
C..,_...,;,- J_.2 5“”. r03..,‘....,,,..1. .1... '1; 3071
”-231.5th “£1.89. .L‘J-«L‘JU4 CI. Ulla]. 9 .LJ ‘ 0
Reagents:
0 ~ 0 .
Pl‘Kle Liquor:
0,- .31 7-. ‘77 '1 . ..- .1 .1. ,. ‘7
1.2... 1.1.3 1.11.1 . 2 1101.11.48 2: 1.1.31}?
.. .. " -'| - .. . 1‘_ .._
Anal¢5183 ferrous ﬁg.” .1,
1 I t a
Ferric negli;iolev

3

Press"

E

18

e 130 131. "auge

1'.)

’91“... ‘; _- .6 q ‘ I 7 . r- \ Lu-
“#61311 pill 1.15.3.1 51.188.512.730 ..ooaoooooooooooooooooo 10.847391! ELLJZLL

 

HitrOSQH partial preﬁaure cocooocooo-oooooocooo 94g}

H204 partial ﬁreﬂaure 0c- oooooooooooooocooooot

Eormality of’KﬁnO4 used

0.00000oncoloqoooocoooocooo0.00000

6.4.psi.

“<22.
1-H..—

. aha.

 

 

Gauge

Pressure Temggrature Sample Analysis % Conversion*
Time Pei. F. ml. Kln04 soln. Remarks

nor 5 ml. samole
1850 100 100.5 Pump on
1:40 101 101.5 PTCS.
1‘1 011711.115?

2:00 101 l00.5
2:20 101 101.5 23.2 48.2 End of Run
Oxygen in gas at end of run: 0.0%
* Pressure was held constant by adcition of kerosene until this tioe.
At this time the orescure started to hold constant witﬁout further ed-

A

1-H.” I _‘ O
1‘. k {'2
11.1.: 1..

dition of kerosene.
tion is couglete.

'1'. "I
‘- 01.1.

an indication that a major portion of

.‘.‘
l

0.19

19

Run Eumber l-C

Conditions: Temperature 1000?. Presaure 100 psi. gauge
1.6.3.5311 w:
Pickle Liquor
Sample Ho. Q Volume lit-o *ie’oiglrt 11555 grmizs

Analys1s: Ferrous 4i.8 ml. Kmn04 soln./5 ml. Sample
Ferric nogligible

A.

 

Dig/gen partial pressure cocoon-cocoooooooooo. 40.4- !7Si1 3‘0"”;
Nitrogen partial presuure ................... 67,9 931. abg¥

 

C9
0

231,204 Péu‘tiallz‘11‘ei23we .0...‘.0.0l............ 6.4 psi; ab

E

Normality Of Ehﬁ4 used coo-uncoooooooocoooooocoto

Gauge
Pressure Temperature Sample Analysis % Conversion
Time P81. 0F. ml. Kin04 soln. Remarks
.pcr 5 ml. samole

.4:15 100 99.5 Pump on

4:25 100 98. Pres.
holding

4:35 100 98.

4:45 100 101.5 0.1 100% End of Run

Oxygen in gas at end of run: 6.8%

Hun umber l—A

Comli'ﬁons: Temperature 100%. Pressure 100 psi. gauge
Reagents:

Pi aisle Liquor:

 

 

Sample Ho. 2. Volumell liter Foight llﬁﬁ‘grams
Analysis: Ferrous éﬁ.2 ml, T2304 soln./5 ml. sample

Ferric norliﬁibls

1

$04 partial g‘ressm‘e ........................ 6.41381. ansL

L.

HOI’IIM‘Llity Of E3104 USCd 00090000000.oooooooo-ooo-ooooooooo O 1.195

Gauge
Pressure Temnerature Se"ple Analysis % Conversionv

Time PSi. . ml. Kﬁn04 Boln. Remarks
per 5 ml. sample _

 

1:45 100 927.5 Pomp on
1:46 100 97.5 Pres.

holding

1850 100 98. 38.6 8 4

2800 100 98. 38.1 9.8

O 5

23 20 100 98.5 5708 1 0 End Of Run

0—,

Oxygen in gas at end of run: 0. p

21

iizxrl IlliLllJEB]? ].-13

Conditions: Tempera'twe 100%. Pressure 100 psi. gauge

Reagents:

Pickle Liquor:

 

 

S““ole No. ;_ Volume .1 liter 'Reight 1155‘grams
Analysis: Ferrous 9.2 m1, "'n04 soln./5 ml. sample

Ferric nogllgiole
Oxygen partial pressure .................... 1;.3 Esi. abs.
Nitrogen partial pressure .................. gét. si._abg;

5
H.204 partial pres Jure ouooooooocoooooootocio 6 L4. p319 abs;

 

Homnality 0f 3;:th used cocoon.coco-cocoooooooooo O 1.95
Gal-LESS

Pressure Tosgerature Sungle Analysis $Conversion

Time Psi. or. 1:11. 2:304 soln. Remarks
per 5 ml. sample
4:00 100 100 Pump on
4:05 100 100 26.5 57.7 Pros.
holding

4815 100 100 23.8 43.6
4:26 100 104 25.1 45.2
4:40 100 97 23.0 45.5 End of Run

0m

e21 in gas at end of run: 0.0%

33
F3

Run 251mber l-C

Coz’nlitions: ’i‘empora ouie 1300?. Pressure 1730 psi. gauge
Reagents:
Pickle Liquor
Se;- ole 140. 1—; Volume _3_._ liter E'Eeight 11.55 grog}:

 

Analysi s: Ferrous 42 . G :11 . 101110 4 solu./5 1-11 . sample

 

 

 

Ferric toggligi’ le
03.32.3011 lmtiﬂ LI'eSE‘Jm‘S coo-000.000.000.00... 4304;113:510 abiﬁ“
Nitrogen partial pressure ................... {37.0 psi. abs.

 

1£204 partial pressure ....................... 8.4.4.15 . abs.L

{Iorlmlity 0.15: 531104 used COOOOOIOOOOCOO0.000000000UOICCCOCQO 0.113.

Gauge
Pressure Tall-jg: erature Sam; is AJLS';¢"’S/E;COI‘1*'ISion
lime Psi. 0". :11. . .1 soln . Remmks
per 5 1:11. 89:13-19

11: 00 100 93 Pump on

 

11:05 100 93.5 11.5 78.2%
11515 100 9805 0.10 100 % Pres.

110105.114;

11: 50 .10~ 93.5 103 5%

C.)
O

C)
(.21

Oxygen in ”as at and of mm: 8.023

25

 

Run Kumher 2—A
‘Couditionsx Ten;me 3‘8 1000 . Pressx L.re 155 psi. gauge
EugeWm
Pickle Liquor:
Sample ﬂo.‘§, Vol’ue ; liter weight 1150 rrnns
Analysis: Ferrous s4.7r .an04 soln./5 ml. sample

Ferric 11g;li.;ib.‘.e
03:33‘311 :m weir-Ll lJrQSS‘Ee ooooIoDOOOOOOOOIOCIIO 4.5 “81L8.b5._:
liitrosen Partial pressure .................. 35.71231. 3333.

N

1204 pa; 0.1.11 '31‘933111’6 OOOOOQIOIOOOOOOOOOOIOCQ 8.? 130... .:--S.

Lora... 'nty 0191:3104 used coo-occooooooocaoocoooooouoooooooco 301.1,:

Genny-e
Pressure Seuwerature Szmgle Analysis 2 Convers is on Remarks
Tim Psi. OF. ml. K::: '14 80111.
per 5 ml. sample

___._.A ___.__.

2:15 153 101 Pump on

2:25 155 101 Pres.
1101515.: 15;

2:35 155 101

2:45 135 101

2:55 155 101

5:00 155 101 39.0 15% End of Run

Oxygen in gas at end of run: 0.0%

Run Number 2-13

.1.?! -1. ‘ ..
Co. .112. 0115:

319112581320:

in}.

‘1"! !
P 011.22 Li

(1'.

Oxygen partial pre

HitrO‘zen partial pressure 0.0.0.0...OOQOOOOIOLéﬁol—‘c

I 0
I2 4

T
me&imrm.m'

11
5.153.331: 31‘} 1:00

’\
r" a. .L1‘1r'1 . \. .
reagerauure 13¢ t. Preagur

TY- . '1 .' J. .. T"...' -..‘
‘ 7 L138 2.; .1...‘ 2/31? 11'1'.1.;‘,.12.'ta

t
i

 

Ferrous ‘§§.7 m1:. KXnO 801n4/5 m1.

Ferric nn111u-n‘e

 

7‘0
3:}

"5 115'? 51-13} (7":
4 .LI .. . Inc— 11-)“,

"' "(WIS
«m

sample

m1 qt-

SSIH‘B IOOOIIOIOIOI....C.... 131.53" ’35... 1.133;

 

partial pressure .......................

éused 0.0.0.000...00......00...

1'11"?" 0 PM."
\

'-.')-'—L..‘_ '--v-‘l. i

'1"
8,7;931. abg;

 

Gauge
Pressure "amperature Samgl Analysis % Conve‘sion
T1339 81. 01". ml, 1:11104 593111, 1381.13.31:
per 5 :11. 3111.. ‘18

5:45 13‘ 1 P“"p 11

5:53 185 101 Pres.
holding

4:05 135 131

4:15 134 102.5

4:30 134 ;5 15.1 65.3ﬂ End of Run

Oxygen in gaa at end of an: 0.0%

N
0'!

Run Number 2—C

Conditions: Temperature 100°F. Presgure 155 351. gauge
Reagents:

Pickle Liquor:

559-1111315110. E Volume _1_ liter 53013111,

 

Analysis: Ferrous 4.5.1 1'- 7 {0.2110 soln./5 ml. sample
Ferric negligible

Oxygen partial pressure coccQOQOoooo-ooc.000005498 231. abs,
Nitroaen partial Pressure o-ooooocoocccoooodi‘§§94#p51. abs;

H&04 partial pressureoooooooocoon-coonc-oooco. glprSiQ_absl
‘v

 

Normality of’Kﬁn04 “38d oo0.000000000000000.000I¢OOOOOOQQ§C 4
Gauge
Pressure Temperature Sample Analysis % Conversion
Time 1’ Si . 0F . ml . $11104 soln. Remarks
A_per 5 m1. sagple
9:45 155 102 Pump on
9:55 134 98 Pros.
10:05 134 98 holding
10:15 154 98.5
10:25 154 99
10:50 154 99 0.1 103% End of Run

Oxygen left in gas at and of run: 15%

Run Number 5A

. . .. o , .
Comhtions: Taz‘iperatuce 130 F. Pressure 100 1153.. gauge
Reagants:

Pi 03:18 Li ziuor:

8211:3118 Ho. 2 Volume 1 1153' Weight 1130 1371128

 

12111131313: Ferrous 4.5.1 £3104 soln./5 211. sample
")

Ferric n12

 

Omfgen partial pragbmeoanoooooooooooo000000.. 5.2 p31. .5le.

 

T

nitrogen partial prosaure....................105.1‘psi. abs.

 

£1204 partial pref-53130 IOOOOOOOOOOOCOOIOOOOOOO. 614. D310 at;

 

Ilorﬂality 011.151.1104 used 0.0.0.0...oooocooocaoolooooooooooo- 0.114

Gauge
Pressure Taiﬁ;'\g:atlu‘e Sample Analysis 7., Conversion
Time P81. 1". ml. 12.11104 £30111. Remarks

per 5 1111. 83.1.1319

2:00 .100 128.5
2:10 101 152
:20 101 152
2:50 101 150.5
2:45 101.5 151.0 - 58.5 14.5% End of 1)un

1|.

Pump on

01:33:31} in gas at and of run: 0.03%

27
Run Number 5-B

‘ ' f" O H . 0
Conditions: Temperature 100 F. treasure 100 p51. ﬁgure

Pickle Liquor:

Sample Ho. 3; Volume .l_liter E-ight 1152 rrlgs

W m

 

Analysis: er“oua $2.8 m1. Kﬂn04 soln./5 ml. sample
Y!

.L
O ”"1 .8 1““: 1
ric noullmlble

 

0:3an partial pressure “nun".............L’5.8 1331. abs.

 

Hitrogen partial pressure.....................94.5 psi. abs.

 

 

H.104 pm‘tit'll i:-re:-3E3ur3.......................o- 6.4 3'35 . 3135*;

Iiomlity Cf £31104 u.sed...C...OOOOOOOOOOOIOOOOOOOCICOOOIIIO. 11-19

Gauge
Pressure Tangerature Bangle Analysis % Conversion
Time Psi. 0F ml. Kﬁn04 soln. Remarks

per 5 ml. Bagglg

10:00 100 152 Pump on
10:00 101 125 Pres.

holding
10:20 105 124
10:50 10 126
10:40 104 128
10:45 104 129 22.8 46.5% End of Eun

xygen in gas at and of run: 0.0%

28'

Run Number 5-0

Conditions: Temperature 15OOF. Pressure 100 951. gauge
Reagents:

Pi ’13 Liquor:

Sample No. 9". Volume 1......— liter Weight 1150 131151315

 

Analysis: Ferrous 4.2.5 ml. 1:11:04 soln./5 ml. 833.1916

Ferric 113;:‘11‘1'lible
(Dr-$569171 lmuile}. BSSWO ooooooooooooooo-oo-oo £30.; twig £3135

Nitrogen Partial lTiI‘essuI‘e can-000.000.000.000 63.9 "S 1;". E...

 

“. L: -. ._ ‘-‘ o . n.- :‘A
“Li-)4 pﬁil'uléxl preobm‘e coco-cocoooooo-ooooooOO 0151' ESL. €13,131

 

IJOl‘dality Of KIM-O4 used-0.0000.o.000.00.00.00.000IOQOOOOOOO 001195

Gauge

Pressure Temperature Sample Analysis ﬁConv ersion
Time P 81 . 0F . m1 . Lino 4 soln . Remark 8

per 5 Ella eagle
2:45 100 152 Pump on
2:55 100 124
5:05 100 127
5:15 100 129.5
:25 100 150
5:50 100 129 0."

 

100p End of Run

C;
(A

PC
. ‘3/7

()1

Oxygen in gas at enﬁ of run:

29
Run ﬁumber 4—0
Conditions: 'anaerature 10J% 1. Pressure Atmosgheric
Reagents:

Pi clvzle Li quor:

 

 

 

Sample 50. §_ Volume _1 liter Weight 11501graus
1111;115:315: 1'81'30118 42.5 :11. 10.11104 80111./5 21:1. sample
Ferric no li"ible

 

[4*

Ozxjceil coco-0.00.0000.ooooooo-o-ooooooooooo 40.4 4-9;

0 _~ 59- —f
1“}. 01.00 CH goooooooOOo cocoooiooooonoooooooo. 33?;

“no ",ﬂ-g'
1“ A coo-oooooOQOOOoooooo-ococoa-occuoooooc 0 '1: ’

ti

Iior'na' tyOf I‘U‘h104 used OOOOOOIOQOOOOOIOOOOOOQCO 0:135

Gauge
Pressure T-m Jrluuie Sumyle Analysis % Conrersion
Time Psi. 0F. ml. ﬁnn04lsoln. P0"r 8

er 5 m .szmple

A

10:25 035 in
10:40 P.L. in
10:55 95 Pump on
11:00 101.5

11:10 99

 

OOOOCO
I.
00000

11:25 . 100 . _
11:50 . 99 55.5 16. 5;
12:55 .0 98 34.8 18..;

1:00 End of Run

Oxygen in gas 5.0 92-0 of run: 5.0;

 

* Se

(D

next page

 

30
30181 Koﬁe on "on 4-0
Since 11 total P gouro in one reactor for iris r n was onl]
one atao )“Lre, a u_1-eront method was needed for ~-aour11' in *H3 3 “s.
This :33 do; by 111111; 31a reactor 71th water and Cd 5.1acir‘ defiuite
propor one of Lie waoe with iho rosoecbive and s.
roual volume of reactor = 5.5 liiors
Voluns o: r“:cr diaglacod by each gas:
N204 6.4f of 5.5 1 = 224 ml.
02 40.4,“: Of 505 l = l"II ’I._1_ Cal.
:2 5002:: O.- 3.5 1 z 186 I; g
A. or o e r1533 were introduced, the liter of 1onla liquor was
ihtroducod from a 31a33 blow case ur.,r Litre

gon pressure.

Run Number 3-0
Conditionu:
Reagents:

' 7.31 ‘2‘ ‘ ..-.
P1011: “1.1.1013:

A
0-4 a. ’0
l. .-. ."~’ A v
U.-1.z_*.-,1.:.¢J 1.0 g A.
& *
71

”T'- --0 .- ....—'-.~T H
0.13," .3011 pa; w...»

I}? «I. .. 1‘ ~ In ‘1 9 .
‘ I '_ "f. "
Lt U; 1 '5..-

Fl

Tangerabure 1009?.

Volum

11' 01"? 0113

Ferric

1‘ h-«v '- 0) ","1F ("7“"5 2 r.‘ ' .
;)G.L 0.1.9.1. 1.1.5.3...416 .0.ooooooaooooooooo-t'éos 13:31. ‘3»

o:
H

r.’ . ' - '9
oJ p51. gangs

. I
1 lwmnn

”m

 

 

ﬂ 5‘
n. 'h; Al; ‘ LA ail 5?:
V‘ ~ -"“‘-F, . h .
‘.v1‘e&u.u‘e...................... 23.33181; abs.

 

 

: _ 1-... M. 1...... . 9
1163304 iDaroJ—d 333.40.136 gonoooooooooouoooooooooo 4.1 "3531. 3-35-
” h

’" 77's"

5' I ’. t“ '.
. p. W" (I. -~- O f' ‘ 3 . - r3
11U1mull VJ 0;. “an“

augo
Pressure
Psi.

T an; era tur 6

Time 05'.

5mm

4 1;:qu Cocooooo-o-eccocooocoooooooo5.00.9002...“1.0

Sauple tnulysis % Conversion

Ill. E17104 S "1111.
per 5 m1. sample

Remarks

 

97
97.5

a; :3:
”$88

97.5
v 97
K! 97

96
98

(ﬁt
0

”00.... I. 0‘ 0.

53> 51> lb #3 (:3 C11 (:1
sf»- Ol H O (:1

tn 0 U1 0‘: (n

0x=gen in gas at end of run:

Pump on

25.5 45.8%
15.5 61.25
8.2 80.5%
6.5 85.0%
6.5 85.0%

End of Run

0.0%

Run HL’ber 8-0

Comt'. “13'. ans:

Reagents
Pickle Liquor:

Time

a 1 u . f Q
unu.ys-.: Ferrous
1 ~ .7
Eerr.c
O‘:-rnpﬁ
‘V uJV‘

7" . _ , r. " r0 - '5 n 3 my.
L‘Vlbl‘o‘3‘3n chI‘TJLr'll F’I'OQSUIS 00000000000000.0000 1.1.1.1 :_J3_.,_. c':.'

«g,»

H ..,. - arr-u,
L'ICI'IJCL....Luy 0.1. 15.1.10! used-00000000000000...-000009000000...-
.1:

Gauge
Pressure Temperature
Psi. 9F,

m . . - J. ,’\ ’. .
.emgerauure lua°-.

*1
'|

Volume

47.0 ml. K3h04 so

‘ . .~ .r .,1‘. 1.
1; LL.- ,1.;.. 3L0

 

Sample Analysis
ml. K1: soln.
per 5 ml. sample

1 liter

 

.A..&-0

Presaure 25 p31.

partial Tressure...................... 1601 WCL.

_'.2 .~ .~. . l‘, n.’ ,.‘,._
E)8.Tu4.&l LJI‘QSul-Lra 00.000000000000000-00000 (v.5 17.3}. (LLS

% Conversion

/5 1113.0

03
TO

n”: r:-
U9.1.1963

2"" 3"
SK... '4.

’ abs.

(’1

*1

 

1 i 9;.131‘1: s

 

hahab‘hlklk‘
0000000000

.0
000101010

()2 H CH Hp. [:4 (N

Oz‘gen in gas at end of run:

94
100
93
99
100
100

NﬁJNﬁDY‘D?!)
010127131010"

a!
000/?-

26.2
41.7
47.6
50.2

50.7

Pump on

End of Run

*1. 1?. ”.1...
1.011 n uduui' 9‘0

 

01

 

 

 

 

 

C- ‘ -. m 00°? PW ~~ 100 m.
051...... 4.1;..01hJ0 .L 01...:H}... 8. 1'. HA. 8 l .L bus) L11. 0 p014... ﬁkLLUe
T‘.‘ _ "3 '1'“
£LU§.’..Q~‘)*-U§)I
.7 1,1 .. 7 y ,.,
P501148 .41. “UV. 8
" r“ . ‘ .n' . TY... T 1 ch ‘0‘ : 0L ’qﬂ ' ﬂ .; Kr .... F-..
UuAJ. 3.5.1.; 0“»). 3-) \rOLLLuL 1 z- -(TJ. ‘4 ‘31:”. 1.4.. -) fr“; .8
.— u— —— mm +
.- .1.--.' ,.. I .. a r‘ '1 ' -' ... . 0. c7 1 _.
.-0.J.15. P0. 00. al.! H-. KMnC4 50.n. u 3.. 5009.0
3"‘3'31'1'0': V‘. ‘ 1.5. I.‘.‘I 3“, 2"
9.5;... a: -‘A.L1 1'. L1 ‘1
.. . ...- 4.: a - ,.- A-n () _ ..: . -
an .7 ~. 1 .r‘. .1‘ . .‘Hn . « ..r . r x"
u-JQV. phi Luna.)— 1‘ J‘s-r I 00000000000000.000000 ‘.'.‘..oU u... ul'uo
'_.0 z - qr n. u -
-. '0 " -. r"'.- —--. r 5‘ ﬁ -'~1 fun 7, f‘ r, 13*.
0IlLlOUCI-L 209....hul I)... 5.4de8 000000000000000000. ‘Jo j..‘l0 L t’H0
‘l" A ‘01 \ I.!-“ t. .r. 11 >: r . r
L1;~.‘J4 uMb...L.l #005040 00000000000000.00000000 not) E'IJ-L-O UNI-0
iv ‘3.
I - ~~ ->;.'.":. 1'18
..u..-c..L...uf 0L and... 0000000000000.00000000000000900000 {30--

Gang; 7 e
rcssure
P 3.1 0

3

IE?"

08»- ;;\J “4

£1: .21 )13 til-6.1:] {:5 S
fill. {ﬁn-.1104 304.11.
per 5 ml. sample

Yemarka

 

4:00 100
4:05 101
é:15 100
4:25 103
4:.5 100
Oxygen in gas at 9

91.5
96.5
101.5
101.5
100.0

lid Of

rum

25.5
12.5
11.9
11.8

19.8%

Pump on
58.8
70.5
71.5

71.7 End of Run

54

Run Number Special l-B

Conditions: T9m133ra+ ure 101)9F.Pressure 100 381. gauge

Reagents:

833313 No. ‘Q Volume 1 liter Weight 1150_grans

Analysis: Ferrous 44 .7 ml. Kﬁn04 soln./5 ml. sample
Ferric no; gible

0.9’1’811 partial 1.3Tef33ure 00000000000000.0000000 151853351. '3. so.
UitrO5 en par+*al pressure ................... 100.9 081. abs.
N534 parti" pressure 0000000.000000000000000000 :30 03.4.1 E1133

Ilomlit 03' Of I’CI-Jlod used 00000000000000.00-c.0000.0000000000 00114

 

Gauge
Pressure Tem3era+ure Sam 19 Analyfsis % Conversion
Time Psi. OF. ml. 1011304 soln. Remarks
per 5 ml. sample
2x20 100 95 Pump on
2:50 100 100 45.1 3.5%
2:45 100 99 42.5 5.0%
2:55 100 100
5:05 100 100 42.4 5.1% End of Run

Oxygen in gas at end of Rum: 11.2%

Run Number Special l-C

Conditions: Temperature IOOOF. Pressure 100 psi. gauge
Reagents:

Pickle Liquor:

Sample Ho. .Q’ Volume .i liter Weight 1150 grams

m

AneLysis: Ferrous 44.7 ml. Kﬂn04 soln./5 ml. saMple
Ferric neglivible

Owgen partial preSSUI'B OQQIIo-Ioooaooocoooooo. 58 PS]... ab_f~3_3_
I‘EitrOEQD Wﬁﬂl pressure OCOIOOOOOOOOOOOOOOOOO 76.7 3510 abs!
11204 pal'tial preJS‘dre 00.0.0.0.000.000.00.60...130 335... :1th

'f'? r

13'01‘L1ality0fIL-ilﬂ4used .COIOIIOOOOOIQOOIOIOOOOOOOOOOIOOOOQ.w

Gauge
Pressure Tempgrature Sample Analysis % Conversion
Time Psi. F. ml. KHn04 soln. Remarks

W

per 0 ml. sample

 

10:50 100 95 Pump on

10355 100 101 42.2 5.7%
11:10 100 100 41.6 7.2%

11:20 100 100
11350 100 100 41.4 7.5%
11840 100 100 41.5 7.4% End of Run

01
N
0

{Ti

Oxygen in gas at and of run:

(R
L 3

’ DISCUSSION

As a starting place for the experimental work, the easily obtained
conditions of 100 deg. F. and 100 psi. gauge were used. Six runs were
made under these conditions, using various concentrations of nitrogen
and oxygen. A constant concentration of N204 was used in these runs.

From Curtis(l) it was determined that from the oxidation of
ammonia, concentration of N02 in the range around 12% could be obtained
and an equivalent of 6.4% N204was then used in most of the tests. Con~
centration of 5%, 15%, and 58% 02, with the remainder Hz were inves—
tigated.

It was found from runs 1A, 18, and 10 that in all cases the
reaction went to completion, using Up all of the oxygen present under
the conditions of the lower or gen concentrations, and giving complete
conversion of FeSO4 to F92(SO4)3 in the case of the highest oxygen
concentration. Two runs made at each of these conditions gave similar
results. Checking of the tine—rate function showed the reaction to go
to completion for the amounts of material present in from 50 to 45
minutes.

Runs 2A, 2B, and 20, made at lOOQF., 155 psi. showed that an
increase in pressure had no great effect. As the amount of free oxy»
gen present was larger, however, due to the highs pressure, the per-
centage conversion of the ferrous to ferric was correSpondingly greater.

Similar runs, 5A, 3B, and SC, made at 150 deg. F., 100 psi. showed
identical results with the other two sets.

Two other variables were investigated: very much lower pressures,

57
and lower concentrations of the catalyst.

Run 60 made at lOOoF., 50 psi., using the highest concentration
of 02 showed no significant change from the other runs. Lowering of
the pressure still further to 25 psi., run 80, showed definite slow—
ing of the reaction rate but nothing else. Run 40 made at atnOSpheric
pressure gave a rate decrease to the point there the reaction was
incomplete in 2; hours as compared to the previous average tine of
45 minutes.

Catalyst concentration was shown to be controlling in run 90
when it was dropped to one-half that used in the previous runs.

Here incomplete reaction was found with excess oxygen present. It
is believed that side reactions, such as the formation of nitrosyl-
sulfuric acid may account for the disappearance of sufficient £204
to act as the oxygen carrier. Complete elimination of the H204 in
runs Special 1B, 10 showed conclusively that, although some conver-
sion took place, the action of the H204 was necessary for successful

Operation.

ACCU‘L’LACY 0F Til}? ROCEDUITLE

The methods of analysis used were standard methods as found in
various books on quantitative analysis. The exact methods followed
are given in the Appendix of this thesis. ’I‘lie mute-tic pickle
liquor was analyzed for both ferric and ferrous iron before it was
used. However, the samples taken from each run were cl-aecked only for
ferrous. All reductions were made with 8. Jones Reductor since here
was no chloride ions present in the solution. The method of reducing

with etarnous chloride did not work on the sulfate solution.

On

COKCLUSIOES

the basis of the experimental and theoretical work done,

the author believes the following conclusions may be safely drawn:

1.

2.

5.

4.

6.

In the oxidation of ferrous to ferric sulfate in waste

pickle liquors the controlling factor is the rate of

reaction.

Commercially feasible rates are obtainable at temperatures

ranging from room temperature to 150 degrees F., at pres-

sures from 25 psi. to 150 psi. ga we, using N_O¢ as a

catalyst, oxygen carrier.

Concentration of oxygen in.the reaction mixture is not
tﬁnn

controlling as lose as morenstoichiometric amounts are

present.

Concentration of H204 is not controlling as long as suf-

ficient N204 is present so that side reactions do not

completely use it up.

Conditions of 100 degrees F., 100 psi. gauge pressure,

58% 02, 12; H02, 50% H2 are acceptable conditions for the

reaction.

Operation at the 02 concentration of natural air should be

only a matter of introducing sufficient 02 for the reaction,

as it is independent of concentration.

17$." ‘2‘qu| ‘T Ff—‘q‘. {17}. .,ff¥f1~~.,ﬁ 1"{Nltﬁ’r
SUdJuULLOl-S Kli“. I bs‘ulltau‘b Width-PA

much more work could be done on this process in order to give a

‘1

more complete background for commercial plant design. Some of tee

factors the author suggests would be:

1.

2.

5.

4.

Investigation of rates at higher temperatures and pressures.
Theoretical investigation of the kinetics involved in the
various reactions.

Corrosion studies on the reaction mixtures.

Determine ion of the absolute Optimum conditions and concen—
trations with enphasis on excess of materials over the
stoichionctric amounts.

Design and Oper tion of the process as a coztinuous process

instead of batchwise process.

41
APPEIIDIX

Analyti cal Procedure

Ferrous Iron:

A 5 ml. sample of the sulfate solution of the iron salt“ was
transferred to a 250 1:11. erlenneyer flask and diluted with about
K) ml. distilled water. 10-15 a" . of Zim:ern:1:n:—-Rci hardt solution
was added and than it was titrated to a faint permanent (for at

least 15 sec.) pint-r. witf'x 0.1 s $31104.

Ferrous j; Ferric Iron:

A 5 ml. sample of the sulfate solution was transferred to a
250 ml. erlemxeyer flask and ciluted with 50 ml. distilled water.
2 to 5 ml. of concentrated 112304 was added. The solution was then
run very slowly though a Jones Reductor upon which a blank had just
been run. Followir; the solution, tree or four 50 ml. portions of
distilled water were put throuﬁx the reductor and added to the ori-
ginal solution in a 750 ml. flask. The last few ml. of this wash
water was collected separately and titrated. If a single drop of
permanganate gave a peruament pink, wasting was discontinued and
the solution, after adding the Zinuernarur-Reizﬂxardt solution was

titrated with the permmmmte solution.

Molten; and Standardization of 0,121 3:75:104 Solution

~ t 'l a ﬁ 0 0
Light grams of pure IC.‘.nO4 were dissolved 1.11 2:;- litors of dis-
tilled water. The solution was heated to just below boiling for at

least two hours. The solution was then allowed to stand until cool

2‘)

h ‘-

and filtered wrought glass wool.

Standardization was accomplished by weighing; out 0.23-0.55 gram
of dried, pure sodimn oxalate, dissolvig it in 50 r" . of distilled
water and adding 25 ml. of 1:8 [12504. Ellis solution was heated just
to boiling and titrated with tl'ze permanganate while hot. Normality
of permangamate was calculated from the following reaction:

3§a20204+ 8HgSO4 + 3’31104‘51‘5a2304 + 10002 + K2 504 «0- Sin 5304 + 831

, .' I” .,‘ .,., ... 13,... 1- ....t. 0.1 .L.’ ,.
Prep ration of Quantum—rlineal u oolu»...len

 

Dissolve 70 g. of {521804 - 41120 in 500 m. I120. Add with stir-
ring; 125 ml. concentrated {12804 and 125 ml. 852;? phosphoric acid.

Dilute to approzinately one liter.

(1)

(2)

(4)

(5)

(6)

(7)

(8)

(9)

(10)

(11}

BI BLIOGPAPIE

v'r.

Curtis, H. A., Fix:- .L-Id it1o.;en, C enical Catalog Co., Inc., II.

(195 2).

Friend, .7. A. IL, A Colloid “Sheer: of tie Corrosion and Passivity
92 $3333}, 3;} 9}: the O;;;?_datioz;1 o___.i'._' i r;11“o11 .1 Cults, Journal of the
Chemical Society, Vol. lid, 9.3/-' 319 (11321.).

Honk, E. D., Waste Pickle Liguor, Industrial'and Engineering
Chemistry, Vol. 53, 614, (1947).

Hodoman, C. D., 1311., 2211-15 of C 191.15 ".011 and. Physics, Chemical
Rubter P1. bli sling 00., Cleveland (1944.-

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