.THS

A STUDY OF THE PROGRESSIVE
OXIDATION OF CELLULOSE BY
HYF‘OCHLORITE SOLUTIONS

Thesis for the Degree of M. 5.
”C. L. EIaine Alvord
I 9 Z 7

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A STUDY OF THE PROGRESSIVE OXIDATION OF CELLULOSE BY HYPOCHLORITE

SOLUTIONS.

Submitted to the Faculty of Michigan State College of Agriculture and
Applied Science in partial fulfillment of the requirements

for the degree of Master of Science.

C. L. Elaine Alvord

May 1927

I wish to thank:Professor Bruce E. Eartsuch for the
suggestions and help he gave so graciously during

the course of this study.

9376"?

-1-

Table of Contents.

Introduction
Preparation of materials
General methods
Experiments
1. Comparison of lime water bleach with distilled water bleach
2. Effect of temperature and concentration of bleach
3. Effect of previous modification of cellulose
u. Study of alkalinity of bleach liquors

Summary

The work that has been done on the oxidation of cellulose,
consists,for the most part, of studies on the prOperties of
oxycellllose and the final products of the oxidation reaction.

The work reported in this thesis shows a somewhat different mode
of attack, in that the progress of the oxidation reaction was
studied.

Preliminary experiments on this problem based on an article
by Forster and.Pearman?;were discussed in a senior report by the
author.

The oxidation of cellulose and the resulting products involve
so many complications that Emil Eiuser :‘has said, “The further we
penetrate into the field of cellulose chemistry, the less explored
it becomes, the less clarity prevails about the course of the
reactions and the nature of the derivatives. This is especially
true of the oxidation of cellulose and its important oxidation products,

the oxycelluloses, so named by their discoverer, Witt.”

 

‘ Forster and Pearman, "The Bleaching of Trade Sulfite Pulps and Cotton
with Calcium Hypochlorite Solutions", Jr. of Soc. of Chem. Ind., 1925,

V01. RH, No. 20.

** Text-book of Cellulose Chemistry, Emil Hauser. Translated by West

and Esselen. McCraw-Hill Bock Company, Inc., New York, 192”.

Field Flower brand.muelin, boiled and thoroughly washed several
times with distilled water to remove the sizing, was used in this
study.

The “lime water bleach" liquor was made by mixing 100 grams of
bleaching powder (an; chlorine) in a mortar with lime water. This
was poured into a liter graduate, made up to one liter with lime water,
allowed to settle, and the supernatant liquid was filtered through
filter paper. More lime water was added to the solid material and the
supernatant liquid filtered. The two filtrates were mixed and diluted
to one liter with lime water.

The “distilled water bleach" was made in the same way, except
that distilled water was used in place of lime water.

These bleach solutions contained from 12 to 15 grams of chlorine

per liter.

Conditioning of Samples
All the cellulose and modified cellulose samples and the
Coaches containing filter paper were conditioned and weighed. This
conditioning was accomplished by leaving them in a normal atmosphere
Jar until a constant weight was attained. The normal atmosphere Jar
was a dessicator in which a condition of 65% relative humidity was
maintained'by the 35.7% sulfuric acid which replaced the usual drying

agent. ‘

 

* Wilson, Journal of Industrial and Engineering Chemistry, Vol. 13,

p. 328.

Method for Bleaching

Ninety cubic centimeters of bleach liquor was poured over a
weighed sample of cellulose contained in a 125 cubic centimeter
glass bottle provided with a rubber stopper carrying an open tube to
allow the escape of gases formed during the oxidation process. The
bottle was placed in a water bath where a constant temperature was
maintained. After a time the bottle was removed from the water bath
and (l) e 5 cubic centimeter portion of the bleach liquor was removed
with a.pipette, and the chlorine‘determdned‘by adding KI and HCl and
titrating with standard Na28293 solution using starch solution as an
indicator; (2) the remaining bleach liquor was filtered through.e
conditioned and weighed Gooch crucible with quantitative filter paper
on the bottom, and the filtrate saved; (3) The cellulose was washed
with distilled water, reagent HCl, then washed.free of acid (litmus
paper indicator) with distilled water, dried in the air, conditioned
and weighed in the Gooch.

In the two series run in 1926, the tube in the stepper carried
a pinch clamp and the pressure was released every 15 or 30 minutes.
The bottles were shaken about every half hour.

In the remainder of the work the tubes were left open and the
bottles were shaken every 10 minutes.

Bleach solution kept at 90°C for four hours showed no decrease
in oxygen content. Therefore, it can be assumed that the oxygen

disappearing from the bleach has reacted with cellulose.

Determination of Solubility in 37% NaOH
A sample of cellulose was boiled in a reflux condenser for

1 hour with 100 parts by weight of 3% NaOH. The solution was filtered

through filter paper in a conditioned and weighed Gooch, the filtrate
saved, and the residue washed with reagent EDI, then with distilled
water until free of acid (litmus paper indicator), dried in the air,
conditioned and weighed. The loss of weight of the sample was
calculated. The original commercially bleached Field Flower muslin

was 3.9% soluble in 3% neon.

Comparison of Lime Water and Distilled Water'Bleaches
TIME - From a study of Tables I, II, III, and IV, and Figure I

it is obvious that less time is required to use all of the oxygen from
the distilled water bleach than from the lime water bleach, and.that
the critical period when oxyhen is consumed at a greatly increased

rate appears sooner in the distilled water bleach than in the lime
water bleach. It has been mentioned before that the two series done

in 1926 were under slightly different conditions than the later series.

Therefore, the work shown in Table I can not be expected to check with

that shown in Table III, or the work in Table II with that in Table IV.

Rate of Oxygen Consumption

It is also shown in the tables and in Figure I that the amount
of oxygen used.per gram.of cellulose increases gradually for a time,
then there is a sudden marked increase, followed by a gradual decrease
in the rate of oxygen consumption.

In every case this critical period appeared later in the lime
water bleach than in the distilled water bleach. The study of the
alkalinity of the bleach liquors which is discussed later shows that
the critical pertod'begins Just as the reaction of the bleach.passes

from alkaline to acid. The approach of the critical period is retarded

by the higher alkalinity of the lime water bleach.

Table I
Series 1 - (1926) Distilled water bleach on hold Flower muslin at 50°C.

5 c.c. original bleach used 15.9 c.c. Of 0.10751! Ha28203

 

ifeight of:Hours in :C.c. of :Grams :Per cent :Grams 0 :Grams 02 :Per ceni
:samples :bleach Nazséoz. :loss in :loss of :used : used :soluble
:per

 

 

No. :in grams : c: weight :weight in:per gram :per gram :in

: ::b1each : : bleach :sample :loss in :neos
55 : : : 4: : : :weight 1 g
1 : 2.5380 : l : 14.87 : .0143 : .5634 : .00621 : 1.1020 : 3.524
2 : 2.5369 : 2 x 14.12 : .0403 : 1.6950 : .01074 : .6758 :
3 : 2.5055 : 3 : 13.07 : .0820 : 3.2740 : .01728 : .5281 :
4 : 2.4972 : : 12.14 : .1120 : 4.4810 : .02357 : .5257 ::
5 : 2.5850 : : 10.54 : .1420 : 5.4920 : .03173 : .5776 : 14.27
6 : 2.4906 : : 7.01 : .2146 : 8.6770 : .05462 : .6339 : 25.45
7 : 2.5492 : : 3.41 : .2901 : 11.3800 : .07498 : .6588: 30. 62
8 : 2.5539 : 5 : 1.29 : .3526 .13 8000: .08753 : .6357: 38. 98
9 : 2.5951 : ,55, .50 .:, .3986 W15.91 :.0950 3 5 .5912 g 41. 66

 

Table II
Series 10 - (1926) Lime water bleach in Iield flower muslin at 50°C.
5 c.c. original bleach used 15.9 c.c. of 0.1075! 8.23203

 

:Weight of:Eours in :C. c. of :Grams :Per cent :Grens 02 :Grans 02 :Ter ceni
“maples :bleach 8.28 02 :loss in :loss of :used : used ::s01ub1e
N0. :in grams : :per ‘2; .c:weight :weiglt imper gram :per gram :in

 

 

 

:bleach : :bleach :sample :loss in :naOH

: : : : : weight : 5
10 : 2.4855 : l : 14.83 : 01.50 .6034 : .006587: 1.0915 : 6.38
11 : 2.5288 : 2 : 13.90 : .. .0520 2.0560 : .01213 : .5399 : 6.29
12 : 2.4808 : 3 : 12.90 : 0912. 3. 5920. .018504: .5034 : 7.061
13 : 2.5135 : 3; : 12.60 : .1078 : 4. 2900 : .02006 : .4678 :
14 : 2.4907 : a4 : 12.07 : .1113,» 4. 4680 : .0235 . 2655 : 8.245
15 x 2. 5265 : 4} : 9.02 : .1696 : 7.1990 : .02956 : . 3025 : 17.70(
16 :2 5552 : 5 : 3.00 : .2840 : 11.1100 : .07725 :: .695 : 34.55(
17 , 2. 5357 : 5} : 1.54 : .3245 : 12. 7800 : .08665. : .6929 : 38. oo<
18 ° .4 : 6 : .80 : .3531 : 14.1% .1027 .544 38 .1

Table 111
Series 50 - Distilled water bleach on Field.F10wer muslin at 50°C.
5 c.c. of original bleach used 18.28 c.c. of 0.0954111 Na28203

 

 

 

:Weight of:Hours in :C.c. of :Grams :Per cent :Grams :Grams 02
"triples :bleach :Naes 03 :loss in :loss of :used :used
No. :in grams : :per c.c:weight :weight in:per gram :per gram
: x jhleggh : :bleeach :sample gloss in weight
50 : 2.5039 : l : 17.1 : .0309 1.235 : .00647 : .659
51 : 2.5082 : 1' 30" : 16.48 : .0515 2.053 .009781: .4806
52 : 2.5089 : 2 : 15.94 : .0784 3.125 .01281 : .4451
53 : 2.4997 : 2' 30' : 13.1 .1430 5.72 .01748 : .3055
54 : 2.5103 : 2' 45" : 9.14 .2415 . 9.62 : .05002 : .
55 : 2.5030 : 3' 20" : 2.7 .3677 : 14.68 .08553 : .5821
56 : 2.5040 : 3' 34'I : 1. .4225 : 16.87 .0941 . .5619
: 2.4998 ° 4 : 0.;__ .4421 :17_.72 39991;; .5639
Table IV

Series 60 - Lime water bleach on Field Flower muslin at 50° 0.

5 c.c. of ortginal bleach used 17.95 c.c. of 0.0954111 Ha28‘203

 

 

:Weight of:Hours in :C.c. of :Grams :Per cent :Grams :Grams 02
:samples :bleach :Nazsg :loss in :loss of :used :used
. :in grams : :per 5 c.c:weight :weight in:per gram :per gram

: : :bleach : :bleach :sample :loss in weight

: 2.5027 1 A : 16.2 . .0335 1.338 : .009607: .7177
61 : 2.5050 2 : 15.18 : .0786 3.130 : .01519 : .4842
62 : 2.5015 3 : 14.46 : .0984 3.934 : .01918 : .4873
63 : 2.5065 g; : 13.52 : .1125 4.489 : .02428 : .5410
64 : 2.5093 : 10.5 : .1680 : 6.695 : .04079 a .6093
65 : 2.5040 : 4} . 4.16 : .2862 : 11.430 : .07566 : .6620
66 : 2.5033 : 5 : 1.96 : .3363 - 13.430 : .08776 : .6532
67 : 2.5029 : 5} : .7 : .3939 15.740 : .09469 : .6017
68 :355092 : 6 1 .04 : .4253 16.950 : .09806 : .5786

 

Series 20 - Distilled water bleach on Field Flower mmslin.at 40° C.

5 c.c. of original bleach used 18.51 c.c. N710 N828203

 

 

:weight of:Eours in :C.c. of :Grams :Per cent :Grams 02 :Grams Q2 :Per cent

:samples :bleach :N8252 :loss in :loss of :used :used :soluble
N0. :in grams : :per 5 .c:weight :weight in:per gram :per gram :in

g : _:b1each : :bleach :sample :loss in :NaOH

: : : : : : :weight : g
20 : 2.4985 : 2 : 17.59 : .0242 : .968 : .005302 : .5475 4.66
21 : 2.5299 : 3' 50' : 16.40 : .0626 : 2.475 : .01201 : .4855 9.58
21 : 2.5069 : 4' 30'I : 16.70 : .0762 : 3.040 : .0104 : .3421 6.46
21 : 2.5319 : 5 : 15.59 : .0702 : 2.773 : .01456 : .5251 9.37
21 : 2.5195 : 5' 30- : 15.46 : .0888 : 3.524 : .01744 : .4958 : 12.25
22. : 2.5282 : 6 : 11.30 : .1528 : 6.043 : .04107 : .6797 : 21.66
23 : 2.5109 : 6' 25'I : 8.94 : .2379 : 9.475 : .05488 : .5793 : 30.22
23; : 2.4938 : 6' 50- : 6.66 : .2849 : 11.420 : .06843 : .5991 : 32.44
2 : 2.5162 : 7' 16' : 5.00 : .4783 : : .e7731 : .4067 : 40.91
25 : 2.5092 : 7'36“ : 3.58 : .3686 : 14.790 : .08572 : .5834 : 37.51
26 : 2.5182 : 7' 57' : 2.42 : .3609 : 14.33 : .092 : .642 : 39.25
27 : 2.5086 : 8' 17' : 2.33 : .3660 : 14.59 : .09289 - .6364 : 41.23
28 : 2.4979 : 8' 50” : 1.62 : .3704 : 14.83 : .09813 .6567 : 41.73
29 : 2.5275 : 9' 18” : 1.1 .3362, : 13.3 : .09964 .7455 : 36.16

 

-9-

MICHIGAN STATE COLLEGE

 

DEPARTMENT OF MATH EMATIC

-10-

SOLUBILITY - The first part of the curve in Figure 2 shows that the
cellulose is gradually being modified in such a way that it is soluble
in the bleach liquor, and Figure 2 also shows that during the critical
period an increased amount of oxygen is required to oxidize a unit weight

of cellulose to soluble material.

 

 

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The acidity of the bleach liquor may account for the critical
period. It is delayed by alkalinity. This was indicated by the
following experiment. Three 2.5 gram.samples of cellulose were placed
in distilled water bleach at ”0° C. After 3 hours 10 cubic centimeters
of 10% 103 were added to Bottle, No. l, 5 cubic centimeters of 10%

KOH were added to Bottle, No.2, but nothing was added to Bottle, No.3.

Table 71
At 3 hours approximately 16.8 c.c.Na28203 would.be used for 5 c.c.

of bleach from Series 20 - 29.

NO. 1 H00 2 N003

 

Hours in:C.c. of

bleach :Na25203

Hours in:C.c. of

bleach :Na28203

Hours in :C.c. of
bleach ::Na28 03
Eco.

.0 O. .0 O. .0

 

C. O. I. O. O. O. O. .0

:per :per 5 c.c :per 5 c.c.
:bleach bleach : :bleach

b' 20” : 14.10 6' 5! : lh.9 : b' 25" : b.”

1' 15' : 13.8 1; i' 5“ :;9.Hh : 1' g9" : .3.3

 

The sodium.thiosu1fate umed.in these titrations was 0.0988N

-13-

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1

   

DFF’AQTMENT OF MATHLMATT

-lu-

That some of the oxygen disappearing from the bleach was used
to further oxidize products soluble in the bleach was shown by the
following experiment.

the 2.5 gram sample of cellulose was bleached with distilled
water bleach at 50°C for li-hours and another sample for 2; hours.

The partially exhausted bleach was filtered, cooked, a sample titrated
with Na28203 solution, 50 c.c. added to #0 c.c. new bleach and this
mixture kept at 50° 0. i

The chlorine in the mixture was determined at certain intervals.
The amount of oxygen in the mixtures decreased which showed that
oxidation products of cellulose soluble in the bleach could.be further
oxidized. That there is an accumulation of these soluble products is
shown by the fact that the oxygen disappears more rapidly in the second

mixture than in the first.

Table 711

5 c.c. of original bleach used 17.82 c.c. of 0.0994131 $28203

 

.1} hour filtrate 3 lb.02 c.c. Na2$203 2} hour filtrate : ‘3 c.c. M28203

 

Mixture :: Mixture
Hours : c.c. N S :: Hours : c.c. Na 5 O
o : lb?§22°3 :: o : 10.862 2 3
l : 16.70 :: l 3 5.26
2 : lb.“ :: 1% x 3.66
: 16.12 :: :
1+ : ;6_J8 :: :

 

When the solid residues from the bleach were boiled for 1 hour
with 100 parts by weight of 3% NaOH, the solubility increased with the
degree of modification. During the critical period the per cent solubility

in NaOH increased mch more rapidly than the per cent solubility in the

bleach liquor, as shown in Figure 14.

0‘

0.0

t

It is stated by Hibbert and. Parsons" that oxycellulose is
not as resistant as cellulose to aqueous alkaline solutions. It
appears that during the critical period oxycellulose is being formed

very rapidly. (Figure ll»)

 

"' Eibbert and Parsons, Journal of the Society of Chemical Industry,

Vol. xuv, No. In, Oct. 9, 1925.

 

DEPARTMENT OF MATH EMAT

Effect of Temperature and Concentration of Bleach.

In this series the 90 cubic centimeters of bleach were placed
on cellulose samples weighing 5 grams, 2.) grams, 1.25 grams, and 0.62
gram. The temperatures used were “0°C, 50°C, and 60°C. At suitable
intervals, a 3 cubic centimeter sample of the bleach was removed and
its chlorine content determined. The time when cloudiness and.gassing
occurred was observed. These results are shown in Tables VIII to
XIII and Figures 5 to 9.

1. Keeping the temperature constant but doubling the weight
of the cellulose caused one half the total oxygen to be used in less
than one-half and more than one-third of the time required by the
smaller sample. (Figure 5)

2. Using the same weight of cellulose and increasing the
temperature 10°C caused one-half the total oxygen to be used in less
than one-half and more than one-third of the time required at the
lower temperature. (Figures 6 to 9)

Thus, every 10°C rise in temperature more than doubles but

does not triple the speed of reaction.

 

  

   

 

 

 

 
 

 

 

 

 

 

 

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MICHIGAN AGRICULTURAL COLLEGE

 

 

DEPARTMENT OF MAOHEMAt U. S

.27-

MICHIGAN AC-PJC‘ULTIJR 3L COLL

 

 

ULPAR TMENT OF

 

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MAIfiLMAIIK -

MlCHlGAN

AGRICULTURAL COLLEGE

 

.Jbr’AR I'MENT OF MAI Ham w

Effect of Previous Modification of Cellulose

The modified cellulose was prepared by oxidizing 2.5 gram samples
at 50°C. Distilled water bleach was used for series 50 - 57 and lime
water bleach for series 60 - 68. At suitable intervals the reaction was
stepped. In this way two series of modified cellulose were obtained
in which the degree of modification increased from member to member.

These modified celluloses were treated for one hour with fresh
bleach ( 90 c.c. on a sample) at 50° C. This is called the (a) series
or 50 a - 57 a and 60 a - 68 a.

The residues from 50 a - 57 a were treated with fresh.bleach.
for one more hour. This is called the 50 b - 57 b or the (b) series.

In Table XIV a comparison is made between the grams of oxygen
used per gram of cellulose in the 50 -57 series and the 50a - 57a series.
Considering number 52 and 52a, it is seen that more oxygen was used.per
gram sample in the additional one hour than in the preceding two hours
of continuous bleaching. Since unmodified cellulose used a certain
amount of oxygen per gram in one hour, this figure (.0065) was regarded
as a blank and was subtracted from the figures obtained in the (a) series
to show the increase in the amount of oxygen consumed due to previoum
modification of the cellulose. The same calculations were made on the
(b) series with similar results. From these figures itfzoncluded that
the partially oxidized cellulose was more easily attacked by oxygen and
that this susceptibility to further oxidation increased with the degree
of previous oxidation. The table shows that this increased amount of
oxygen consumed caused a great increase in the per cent less in weight

of the sample.

-30-

Table XV shows a similar comparison of results obtained from
lime water bleach. The effect of previous oxidation of the cellulose
is the same in this series as in the 50 - 57 series. The most notable
difference is shown in the time factor. It has been mentioned before
that the action of lime water bleach is slower than the action of
distilled water bleach.

In Tables XVI and XVII the following data was calculated on the
basis of the weight of the original sample :

(1) total grams of oxygen used in all the bleaches,

(2) total loss in weight in all the bleaches,

(3) total grams of oxygen used.per gram loss in weight,
(4) total per cent loss in weight.

In Figure 10 it is shown that,more oxygen is required to cause
1.gxam loss in weight in 2 hours intermittent bleaching (50a) than is
required to produce this loss in weight in 2 hours continuous bleaching.
This is true also of (50) and (50b). The first part of these curves
is explained by two facts. (1) Bleach liquor that has been used one hour
is more alkaline than bleach that has been used 2 hours. It has been
shown that alkalinity inhibits the oxidation process. (2) The first
few minutes of the bleaching period are required for the temperature
of the liquor to change from room temperature to 50°C. It has been
shown that the rate of reaction is greatly influenced by changes
in temperature.

As the curve of 50 - 57 turns UpWQrd.at the critical pOriod,
oxygen is being used to further oxidize soluble products. When these
soluble products are removed, more of the oxygen from the bleach liquor
acts on the insoluble but modified cellulose. Since the amount of

soluble products that could accumulate in one hour would be comparatively

-31-

small, the decrease in the amount of oxygen required to produce a
definite loss of weight indicates that the modified cellulose is
more easily oxidized to soluble material, and that this effect
increases with the degree of modifications.

This conclusion is not in accordance with the results of

Clibbens and Ridge *. However, they used lower temperatures and a

weaker bleach.

The same reasoning applies to the curves shown in Figure 11.

 

* Clibbens and Ridge, Tournal of Textile Institute, Vol. XVIII, No.u,

April 1927.

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DFF’AQTMFNT OF MATHEWATICA

-33-

Study on Acidity of Bleach

Twenty cubic centimeters of the bleach filtrate was decomposed
by boiling with 10 cubic centimeters commercial hydrogen peroxide
solution. It was then cooled and titrated with sulfuric acid and
sodium hydroxide using methyl orange as an indicator. The normality
of the acidity or alkalinity of the bleach was calculated.

In every series studied the alkalinity of the bleach decreased
gradually for a time, but at the beginning of the critical period the
bleach liquor became acid and the acidity increased rapidly for a time.
Toward the end of the critical period the acidity decreased. These

results given in Tables XVIII to XXI are shown graphically in Figure 12.

Table XVIII
Series 50 - 59. 2.5 grams cellulose in distilled water

bleach at 50°C.

 

 

 

No. Hours in bleach Alkalinity Acidity
5o : 1 : .006815N :

51 : 1% : .OO6580N :

52 : 2 : . : .001789N
5 : 2% : : .01531 N
5 : 2% : : .02798 N
55 : 3 : : .01692 N
56 : 3' 3H" : : .OO9125N
57 : H : .OOSOMBN

TTable XIX
Series 50a —58a. Modified cellulose treated for 1 hour with
fresh distilled water bleach

No. Hours in bleach Alkalinity Acidity
50a : : .OOM86MH :

51¢. : : : .ooh81N
52a : : : .0173 N
53a : : : .021 1N
5ha : : :

55a : : : .01177N
56a : : : .0116?“

P‘- _ A‘I'Ififl"

-3 9..

Table XX

Series 60 - 2.5 grams of cellulose in lime water bleach at 50°C.

 

 

 

 

No. Hours in bleach Alkalinity Acidity
60 ~ 1 : .01200 N z
61 : 2 : .009595N :
62 : 3 : .00661 N :
Ea - 3% : : .000609N
u z : .0165§ N
65 : he : : .02336 N
66 : 5 : : .01201 N
67 : 5% : : .00228 N
68 : 6 : : .0005 N
Table XXI
Time - Water bleach filtrates from 1926 series at 50°C
At time of bleaching Three days later
No . Time Alkalini ty Aci di ty : : Alkalini ty Aci di ty
liefu? ::
bleach ::
l : l : 6.02lEEN: :: .01768N :
2 : 2 : .0195hN: ': .01386N :
a : 3 : .01699N: :: : .01679N
: 3% : .0123MN: :: : .01601N
5 : h : .01009N: :: : .01312N
6 : hi : : .01562N :: : .0070 N
7 : 5 : : .02233N :: : .01038N
8 : 5} : : .0081 N a: : .0061 N
9 : 6 : : .0031 N :: : .0023 N

 

——-——— —— -

4+0-

MICHIGAN STATE COLLEGE

 

DEPARTMENT OF' MATHEMATICS

MlCHiGAN STATE COLLEGE

 

DEPARTMENT OF MATHEMATICS

4+2-

One series of bleach filtrates were kept for three days and

the alkalinity determined again. Every filtrate had become more acid.
The first members of the series had become cloudy on standing in the

air. The following reaction explains these facts.

Ca H2(C03)2 -+ ggé 3:2; CaC03 +- H2003

1512003 ~—> 3204-002

The soluble calcium bicarbonate gives and alkaline reaction. When the
calcium is precipitated by carbon dioxide in the air as calcium
carbonate, a small amount of carbonic acid is left in solution. These

two things work in the same direction to produce an increase in acidity.

Summary

Observations on the general progress of the bleaching reaction.

1. The first marked change was the appearance of cloudiness in
the bleach liquor. This cloudiness was due mainly to the formation of
calcium carbonate, indicating a reaction between the calcium hydroxide
in the bleach liquor and the carbon dioxide from the oxidized cellulose.

2. At the time when cloudiness appeared, the reaction of the
bleach liquor changed from alkaline to acid. The acidity increased
rapidly to a maximum point which was reached a short time before
gassing began.

3. During the gassing period, considerable amounts of carbon
dioxide were evolved. During this period there was a rapid decrease
in the acidity because the accumulated organic acids were oxidized

to carbon dioxide and water. The cloudiness of the bleach liquor

_ __ .'_ _. .42.;— azfi—aLLH‘h— .

4&3-

also decreases during this period, because the large amount of
carbon dioxide converts the calcium carbonate to the more soluble

bicarbonate.

The Critical period showszthe following characteristics:

1. A marked increase in the rate of oxygen consumption per
gram of cellulose in a unit time.

2. A marked increase in the amount of oxygen required to
cause a given loss of weight of the cellulose. This was because much of
the oxygen was being used in the further oxidation of soluble products.

3. A marked increase in the per cent solubility of the cellulose
in the bleach solutionl

M. A.greater increase in the per cent solubility of the residue
from the bleach in 3% NaOH solution, which indicates the rapid formation
of oxycellulose during this period.

5. The amount of oxygen disappearing from the bleach per hour

increased greatly, i.e., the rate of oxygen consumption increased.

The rate of the oxidation of cellulose is greatly influenced
by changes in temperature. A 10°C rise in temperature more than
doubles but does not triple the speed of the reactionl

Cellulose that has sugfered attack by uxidizing agents is
more susceptible to further attack, and this susceptibility increases

with the degree of previous oxidation.

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