Kogyo Kagaku Zasshi

Kogyo Kagaku Zasshi

(Journal of the Chemical Society of Japan, Industrial Chemistry Section)

Vol.64, No.5, pp.747•`944 (1961)

Abstracts

These abstracts are prepared for the benefit of our readers abroad to assist them, to form a general idea

of the contents of the present issue, written in Japanese by the respective authors. Readers are recommended

to refer to the tables, the figures, the formulae etc. in the original papers. Editor

Kogyo Kagaku Zasshi, 64, 757^--759 (1961)

Theoretical Consideration on Programmed-Temperature 'Gas

Chromatography

by Hideo YAMAZAKI*

A theoretical consideration on gas chromatographic process

was given by use of the statistical quantities describing

charactor of the chromatogram peak. With the present

theory the author can explain the experimatal results that

in the case of constant-temperature operation a linear rela-

tionship was obtained between logarithm of retention time

or the width of peaks and the number of carbon atoms in

the homologous series of compounds, whereas in the case

of programmed temperature chromatography with constant

rate of increase of temperature, a linear relationship was

observed between these statistical quantities and the number

of carbon atoms. Some consideration was given for the differ-

ence between packed- and capillary-column chromatography.

Chemistry Division, National Institute of Radiological Sciences 250, Kurosuna-cho, Chiba-shi, Chiba-ken, Japan.

' Kogyo Kagaku Zasshi, 64, 759^--763,(1961)

Quantitative Gas Chromatographic Analysis by Ionization

Detector

by Mikiya YAMANE* .

An account is given of a quantitative method for gas

chromatographic analysis'` in which Lovelock's ionization

detector is used. The ionization current varies' linearly with

the concentration of the component gases, assuming that

ionization due to energy transfer will not take place.

This theoretically deduced relation is verified by , the experiment using hydrogen as carrier gas. Remarks on

calibration are discussed in some details.

* Central Research Laboratory , Hitachi, Ltd. ; Kokubunji, Tokyo.

Kogyo Kagaku Zasshi; 64, 763'-'769 (1961)

Determination of Traces of Benzene, Toluene and Xylene

Mixture in Air

by Tsugio TAKEUCHI* and Daido ISHII

Determination of traces of benzene, toluene and xylene

contained' in air has been made by gas chromatographic

methods and ultra-violet spectrophotometric method.

Five; procedures are adopted. (1) Direct determination with gas chromatography, using

n thermal conductivity detector. (2) Colorimetric determination with sulfuric acid - for-

malin after separation by gas chromatography. (3) Determination with gas chromatography after they

are concentrated in a small column, cooled by dry ice. (4) Ultra-violet spectrophotometric determination after

they are absorbed in methyl alcohol, cooled with ice. (5) Direct determination with gas chromatography, using

hydrogen flame ionization detector. Results are as follows.

(1) The minimum determinable value is about 75 p.p.m. for 100 mi. of . air, , and about up to 700 p. p. m. of each component are determined.

(2) 25 p.p.m. of benzene in 100 ml. of air are determined, but as for toluene and xylene large error result in.

(3) The minimum determinable value is about 7 p.p.m. for 1.1., o<air, and about 1080 p.p.m. of benzene, 101$0 p. p. m. of toluene and of xylene can be determined.

(4) The minimum determinable value is about 5 p.p.m. I of each component for 5 1. of air anSI 10 ml, of methyl alcohol. (5) The minimum determinable value is about 1 p.p.m.

of air, and 2-250 p.p.m. of each component can be deter-mined.

* Institute of Techno Analytical Chemistry, Faculty of Engineering, Nagoya University: Furo-cho, Chikusa-ku, Nagoya, Japan.

Kogyo Kagaku Zasshi, 64, 769-772 (1961)

Gas Chromatographic Analysis of Quinoline Fraction of

Coal Tar

by Wataru FUNASAKA* and Tsuguo KOJIMA

Gas-liquid chromatography in combination with U . V. absorptiometry was used to identify pyridine homologues in quinoline fraction of coal tar. Gas chromatograms were obtained by using silicone DC-550, polyethylene glycol 4000 or diglycerol as a stationary

phase,' The results indicated the presence of quinoline , isoquino-line, 2-methyl-, 8-methyl quinoline, 2,8-dimethyl quinoline , and 3-methyl isot uionline.

Quantitative analysis of quinoline, isoquinoline , 2-methyl quinoline in quinoline fraction was carried out by using silicone DC-550 as stationary phase and satisfactory results were obtained.

* Institute of Industrial Chemistry , Facudt% of Engincering, Kyoto University, Yashida, Sakyo-ku, Kyoto, Japan.

A 46 Kogyo Kagaku Zasshi Vol. 64 No. 5 (1961)

Kogyo Kagaku Zasshi, 64, 772'-780 (1961)

Gas Chromatography Using Mixed Carrier Gas

by Nobuyoshi HARA,* Hiroshi SH,IMADA, and Minoru OE

Gas chromatographic analysis of mixture of 112 and gaseous hydrocabons by the conventional method is not so accurate, in consequence of an abnormal peak of H2 on chromatogram with carrier gas of He or extremely low relative response for hydrocarbons with N2 or Ar carrier. Studies have been made for a method using mixed carrier gas of He-Ar or He-N2, which is capable of effecting accurate analysis ` of f orementioned gas mixture by gas-liquid chromatography. By the use of mixed carrier gas, a normal peak of H2 in

proportion to its concentration and moderate response for hydrocarbons as well as for H2 have been attained. In gas-solid chromatography, on the other hand, a peculiar

phenomenon has been found, in which a sample of single component gives two peaks on chromatogram. In general, a sample composed of n components gives (n+1) peaks with these mixed carrier gases. It has been shown that adsorbent

packed in column adsorbs mixed carrier gas in a different composition from the feeded one at an equilibrium state and desorbs this adsorbed carrier gas by displaced adsorption of injected sample, giving an extra peak on chromatogram.

* Tokyo Institute of Technology: Ookayama, Meguro-ku, Tokyo, Japan.

Kogyo Kagaku Zasshi, 64, 777^780 (1961)

Gas Chromatographic Analysis of Methyl Esters of Long-

Chain Patty Acid by Using Polyvinyl Acetates as Partition

Media

by Masao MARUYAMA* and Setsuya SEND

Polyvinyl acetate and copolymer of vinyl acetate and

crotonic acid were proposed as the stationary partition media

for the gas chromatographic separation of methyl esters

of long-chain fatty acids.

Polyvinyl acetates serve not only as stationary liquids but

also as binders for Celite 545 powder, and the partition media

are prepared by mixing and kneeding Celite 545 powder

with acetone solution of polyvinyl acetates and granulating

into 30 to 40 mesh.

Methyl esters of stearic, oleic, linoleic, and linolenic acid

can be separated by these partition media. Relative reten-

tion volumes were 1.00, 1.13, 1.36 and 1,69, respectively.

The efficiency of this medium is as well as that of polyester

plasticizes Reoplex 400. It can be widely applicable to the studies of fatty acids, because of commercial availability

and simple preparation.

Gas chromatographic results for several vegetable oils and

animal tissues were shown in this paper.

* Shinagawa Plant, Sankyo Co.,Ltd. : 1-888, Nishi-shinagawa, Shina-

gawa-ku, Tokyo, Japan.


Gas Chromatographic Analysis of Mixtures of Chlorinated

ropanes and Propylenes

by Sachio NISHIMURA* and Isamu ICHIZUKA

Gas chromatographic methods were developed for the

analysis of mixtures of chlorinated propanes and propylenes.

Polyether-urethanes, especially made by reaction of 2 moles of pluronic polyether L-35 and 1 mole of toluene diisocyanate, have proved very useful as the stationary liquid in gas chromatography for the separation of unsaturated chlbrides. Pluronic polyether L-35 is the block polyether glycol having molecular weight 2000, which consists of 50$ ethylene oxide and 50 $ propylene oxide. A further application of gas chromatography by the use of polyether-urethanes as the stationary liquid has been developed and the data of relative retention volumes of aliphatic hydrocarbons, aromatic hydro-carbons and alcohols are presented.

, Asahi Electro-Chemical Co., Ltd.: 2850, 9-cho~ne, Ogu-machi, Arakawa-ku, Tokyo, Japan.

Kogyo Kagaku Zasshi, 64, 784-'787 (1961)

Analysis of Methylchlorosilanes by Gas Chromatography

by Kazuhisa KAWAZUMI,* Setsuo KATAOKA, and Kazuo MARUYAMA

A gas chromatography of methyichlorosilanes was studied for analyzing mixtures of methyl-chlorosilanes containing

close-boiling homologs, faster, more convenient, and more precise than other usual methods.

Six kinds of stationary liquid phases on 30 to 60 mesh Fire Brick C-22 were examined, of which a liquid paraffin or an insulating oil phase gave good selectivity. However, the use of the above two stationary liquid phases in series gave excellent selectivity for analyzing mixtures of five methyl-chlorosllanes-(CH3)2SiCl2, CH3SiCls, (CH3)3SiCl, CH3SiHC12, SiC14. ° The quantitative results obtained chromatographically were accurate within 1 mole % error, if correction factors were applied to the observed peak areas.

* Tsurumi Research Laboratory, Tokyo Shibaura Electric Co., Ltd. 4, 2-chome, Suehiro-cho, Tsurumi-ku, Yokohama, Japan.


Direct Gas Chromatographic Analysis of Organic Compo-nents in Aqueous Solution

by Yoko MURATA* and Tadao TAKENISHI

Recently, gas chromatography has become one of . the most elegant methods of analysis of volatile organic compounds ever devised. But it seems to be valuable to extend its boundaries of application to the analysis of ;dilute aqueous solution of organic compounds. The difficulty of the gas chromatographic analysis of aqueous solution is due pri-marily to the long retention time of water and the distur-bance by tailing of water. This paper is concerned with the direct gas chromoto-

graphic analysis of a small amount of alcohols, nitriles and aldehydes in water without extracting the components from the aqueous solution. It was found that polyethylene glycol or glycerol is ' a convenient stationary liquid for these pur-

poses, and mixed stationary liquid (glycerol and silicon grease( is effective for the separation of some aldehydes. The results obtained in routine analysis indicate that this method can be used to determine alcohols with a probable error of ±5'$.

A further application utilizing glycerol and silicon grease as the stationary liquid has been developed for the deter-

Kogyo Kagaku Zasshi Vol. 64 No. 5 (1961) A 47

mination of amino acid (i. e. alanine, valine, norvaline, leucine and norleucine) in aqueous solution , with the combination of an oxidizing reactor column.

* Central Research Laboratory, Ajinomoto Co. , Inc.: 2964, Suzuki-cho, Kawasaki-shi, Kanagawa-ken, Japan.

Kogyo Kagaku Zasshi, 64, 791-'795 ((961)

Analysis of Terpene Hydrocarbons by Gas Chromatography

(Part 2)

by Tamon MATSUURA,* Hisashi KGMAE, Takaaki ARATANI,

and Shuichi HAYASHI

A basic investigation on gas-liquid partition chromato-

graphy of terpene hydrocarbons was carried out on packed columns containing various stationary phases (polyethylene

glycol 6000, tricresyl phosphate; squalene, and squalane). Helium was employed as a mobile phase. Retention times for several sample sizes of each of the

purified authentic twenty-two terpene hydrocarbons were obtained, and on the basis of these data the absolute relative retention values, that is, the ratios of the retention times which were extrapolated to zero size of each sample to that of internal standard substance (1, 8-cineole or cyclohexanol), were determined.

It should be noted that the terpenes are eluted from the column in the order of increasing boiling points. The retention time eras prolonged with increasing sample size, and in general, the longer the original retention time, the larger the prglongation becomes. Also, the resolution with each stationary phase was esti-mated for a synthetic mixture of seven authentic _ terpene hydrocarbons and 1, 8-cineole. From the estimation, it was observed that polyethylene glycol 6000 provided optimum separation of the terpenes. By using tricresyl phosphate stereoisomers of p-menthane

could be separated.

* Department of Chemistry, Faculty of Science, Hiroshima University : Hiroshima-shi, Hiroshima-ken, Japan.


Catalytic Effect of Support for Gas-Liquid Chromatography on Samples to be Analyzed

by Tamon MATSUURA,* Takaaki ARATANI, Hisashi KGMAE, and Shuichi HAYASHI

The investigation aims to clarify the catalytic effects of supporting materials for gas-liquid chromatography on the compounds to be analyzed. Fourteen supporting materials (28•--48 mesh) such as crys-tallized quartz, Pyrex glass, supporting firebrick, Isolite N-4 firebrick (these materials were treated with several mineral acids), three commercial supports and others, were tried.

A coiled copper tube (3 m in length, 4 mm in internal diameter) was packed with the above supporting material, and was connected in a series with a column (20 00 P.E.G. 6000 on the commercial support for hydrocarbons, 20 4 Thermal-1 on the same support for oxygen-containing com-pounds) to separate the products which were produced from the original compound by the action of supporting materials . The temperature of the thermostat was maintained at 100°C in the case of hydrocarbons and at 140°C in that of oxygen-

containing compounds. Helium was employed as a mobile

phase. Purified authentic fifty compounds (hydrocarbons, carbonyl

compounds, alcohols, and esters of terpene compounds and

of perfumes) were used as samples for analysis. A great advantage of the use of the crushed crystallized

quartz which was beforehand treated with nitric acid its chemical inertness to the compounds. Substances such as commercial supports or other firebrick showed unsatis-factory results; it was observed that hydrocarbons were either isomerized or decomposed and that oxygen-containing compounds (mainly carbonyl compounds and alcohols) were either strongly adsorbed or decomposed.

* Department of Chemistry, Faculty of Science, Hiroshima University: Hiroshima-ski,: Hiroshima-ken, Japan.

Kogyo Kagaku Zasshi, 64, 799^-802 (1961)

Studies on Crushed Crystallized Quartz Support for Gas-

Liquid Chromatography

by Tamon MATSUURA,* Takaaki ARATANI, Hisashi KGMAE,

and Shuichi HAYASHI

The investigation was carried out to clarify the applic- ability of crushed crystallized quartz which was treated with nitric acid as a support in the analysis of the mixtures of terpene compounds and perfumes (carbonyl compounds, alcohols, and esters).

Thermol-1 was used as a stationery liquid phase. All the columns used were of copper 3 m long, 4 mm internal diameter.

The efficiency of four crushed crystallized quartz columns

(2848 mesh, liquid phase 4 l ; 80100 mesh, 100-x-180 mesh, above 200 mesh, liquid phase 10 %o, respectively) was compared with that of manufactured support column (28'-48

mesh, liquid phase 200). In the . analysis of two artificial mixtures [high-boiling

mixture (220290°C) and low-boiling mixture (130--220°C)] it was found that the crushed crystallized quartz (1001 .80

mesh) column gave a satisfactory seperation. The optimum conditions were the following: temperature: 180°C, carrier

gas: helium, 20 ml. /min, for high-boiling mixture; temperature: 140°C, carrier gas: 15 ml./ min. for low-boiling mixture .

The advantage of this support summarized is in the following. (1) This has not catalytic and adsorption effects on terpene compounds and pqrfumes. (2) This is mechani- cally very resistant and does not form fine dust, (3) The

pressure drop in the column is ' very small,

* Chemical Laboratory, Faculty of Science, Hiroshima University: Hiroshima-ski, Hiroshima-ken, Japan.

Kogyo Kagaku Zasshi, 64, 803806 (1961)

Study on the Tailingless Solid Support for Gas Chromatogaphy

by Yuzi TAKAYAMA*

As reduction of stationary liquid phase against the solid support is desirable for reducing the retention time and the ionization detector dark current and far speeding up the chromatography, retention time and peak tailing shape were determined by means of argon gas chromatograph using dioctyl sebacate (DOS) 1-'25 ©o on the acid treated C-22 and Celite columns, The results are as follows; When the DOS


content gets lower, water insoluble substances such as hydro-

carbons give no trouble of taming, while the more watg

soluble the substances, the more the peaks draw the tail.

As a result of the further study for the improvement, a

satisfactory supporter which gives no such trouble could be

obtained by means of acid treating and calcining Celite,

* .Mitsubishi Rayon Co., Ltd.: No. 8, 2-chome, Kyobash'i, Chuo-ku, Tokyo, Japan.

Kogyo Kagaku Zasshi, 64, 8O6-8O9 (1961)

Gas-Liquid Chromatography-Stationary Phase and Number of Theoretical Plate in Two-Stage Column-

by Akira SHIMADA* and Hiroshi KAWAKAMI

Two-stage column consisted of diethylf ormamide (DEF) 4 m and silicone DC-703 2 m was used for the analysis of gaseous hydrocarbons, and the cause of deterioration in column efficiency was checked. The amount of each stationary liquid was varied within the range between 11$ and 30 / and thee change of the number of theoretical plate (n) with the lapse~of time was observed for each percentage. The result was that n de-creased linearly at a constant gradient regardless of the amount of stationary liquid. Since it was disclosed that this change of n was solely caused by the carrier gas regardless of the amount of sample introduced, the distribution of the stationary liquid in the column was checked by infra-red spectrophotometric analysis after the column was used. The results showed that silicone scarcely made any displacement, 'while DEF made displacement considerably, forming very irregular distribution. It can be concluded that decrease of n in DEF-silicone two-

stage column is caused mainly by the irregular distribution of stationary phase.

* Kawasaki Plant, Nippon Petrochemicals Co. , Ltd. No. 8543-3, Yakoh, Daishigawara, Kawasaki-shi, Kanagawa-ken, Japan.

Kogyo Kagaku Zasshi, 64, 81O'-814 (1961)

Life of Adsorption Column in Process Gas Chromatography An Attempt to Maintain the Separation Characteristics

of Molecular Sieve 13X Column

by Takao NGMURA* and Masami NUKADA

Continuous analysis of 02 in producer gas and water gas has been attempted by using Molecular Sieve l3 X column. It has been impossible to last it over 100 times because of decay of the separation characteristics, such as the increase of 02 peak, the decrease of the retention time and the separation efficiency between Os and N2.

According to the results of experiment, the troubles in the separation characteristics seem chiefly to be due to the small amount of water in these gases. Some special devices have been tried to decrease the water content in the process gases and the carrier gases, to the

grade of the dew point under --50°C. At present, it seems possible that continuotrs analysis can

\\!:e repeated without trouble over 10,000 times.

* Bef a Chemical Co. , Ltc.: 346, Miyanishi, Aemura, Kaho-gun, Hyogo-ken, Japan

Kogyo KagakuZasshi, 64, 814-819 (1961)

Column Efficiency in Gas Chromatography

by Tatsuro HARUKI*

The author has made an experiment to elucidate the relation between mean height equivalent to a theoretical

plate and flow rate of carrier gas, with respect to o-xylene and toluene in the mixture of benzene, toluene and xylene, taking column diameter, amount of liquid phase and particle size of support as parameters with benzyldiphenyl used as stationary phase and Helium as carrier gas.

Mean pressure drop across a theoretical plate and mean time necessary for a peak to pass through a theoretical

plate are discussed also. Results are as follows

1) Reduced amount of liquid phase, fine particles of support, column of small diameter and corresponding reduc-tion of size of sample are recommendable in order to mini-mize the mean height equivalent to a theoretical plate 2) Coarse size of support, long column and flow rate of

carrier gas not so fast are desirable to get a number of theoretical plate as high as possible within a given limit of

pressure drop across a column. 3) Reduction of amount of liquid phase is the best way

for the economy of operation time.

* Scientific Instrument Division, Shimadzu Seisakusho Ltd.: 18, Kuwabara-cho, Nishinokyo, Nakakyo-ku, Kyoto, Japan.

Kogyo Kagaku Zasshi, 64, 820^-825 (1961)

A Flame Ionization Detector for Gas Chromatography and Its Characteristics

by Tatsuro HARUKI* and Muneaki ITAYA

The authors have made a hydrogen flame ionization detector and studied on its characteristics. Some important factors which affect the sensitivity or

stability of the instrument have been found, although con-sidered not serious so far in many reports. Results are as follows :- 1) Small diameter of the nozzle brings high sensi t : ity. 2) Oxygen gives higher sensitivity than air does. 3) Peak area can be kept constant at proper ratio of

hydrogen to nitrogen even if the flow rate of nitrogen varies. 4) It seems better to replace well-used one in this detector

sensitivity "S" in mV. mi,lmg, had better be replaced by other one for this detector. 5) Temperature deviation of the detector can not be

ignored to keep its sensitivity stable. Some chromatograms were shown as examples of trace

,.

analysis by this detector.

* Scientific Instrument Division, Shimadzu Seisakusho Ltd.:

18, Kuwabara-cho, Nishinokyo, Nakakyo-ku, Kyoto, Japan.

Kogyo Kagaku Zasshi, 64, 825830 (1961)

A New Design of Gas Chromatograph

by Tatsuro HARUKI*

This is the description on the new Shimadzu Gas Chromata

graph, Type GC-1 B and its applications. The features of the jnstrumept are 1) double column

Kogyo Kagaku Zasshi Vol. 54 No. 5 (1951) A 49

system in which differential signal between two sides of a detector, each of which is connected to an individual column, is measured, 2) high column temperature up to 350°C, 3)

high pressure up to 5 kg./cm2 gauge is permissible at the column inlet, 4) column bath, in which the mean value of

temperature at 3 points can be kept at any temperature 355°C, 5) detector bath, the temperature of which can be set up to 350°C and which has a space for another detector (hydro-

gen flame ionization detector, for instance) and 5) that it can analyze high boiling, especially solid sample by a unique sample introduction system which can introduce sample into the evaporation chamberf of high temperature, 500°C for in-stance, without loss of sample and deterioration of material. Some applications were presented. A differential gas

chromatogram between air and human breath, and gas chro-matograms of nylon bar, polyethylene film and polystylene were shown. And an example of simultaneous recording by thermal conductivity detector and hydrogen flame ioniza-tion detector were shown.

* Scientific Instrument' Division, Shimadzu Seisakusho Ltd. 18, Kuwabara-cho, Nishinokyo, Nakakyo-ku, Kyoto, Japan.

Kogyo Kagaku Zasshi, 64, 830^,834 (1961)

The Practical Design of a Process Gas Chromatograph

by Tatsuro HARUKI* and Kei ASAI

Current trends in process instrumentation are toward increasing use of composition analyzers. Especially gas-liquid partition chromatography is now widely used for monitoring chemical composition. .

In this paper, the practical design and the characteristics of a process chromatographic analyzer which has some advantages in the design of the sampling device and the

programmer are described.

* Scientific Instrument Division, Shimadzu Seisakusho Ltd . 18, Kuwabara-cho, Nishinokyo, Nakakyo-ku, Kyoto, Japan.


Measurements of the Permeability of Carbonaceous Materials and Their Pore Structures

by Takashi MUKAIBO* and Yoichi TAKAHASHI

The permeability for air of the carbonaceous materials was measured by means of a specially designed apparatus which was available over a wide range of the permeability such as 10* 1-v10-~ cm2/sec. The permeability was found to follow a linear relation to the average gas pressure, which implied that the gas flow consisted of viscous flow and molecular (slip) flow. The general equation of the flow was derived by intro-ducing a parameter Z, which was defined as the fraction of the viscous flow to the whole gas flow at standard conditions. This equation was verified experimentally, and a conventional method to determine Z was established. The structure of the pores effective to the gas flow was discussed in relation to the permeability and Z value. It was also pointed out that the average effective pore radius could approximately be determined from the inflection point of the

pressure-permeability curve z which was caused by the transi-

tion of they iscous flow to slip flow, when the mean free path

of the gas became nearly the same as the pore diameter.

* Department of Applied Chemistry, Faculty of Engineering, Uni-

versily of Tokyo: Motofuii-cho, Bunkyo-ku, Tokyo, Japan.

Kogyo Kagaku Zasshi, 64, 84O-844 (1961)

Plasticity of Carbon Mixes (IV) : Binder Content Required for Extruding Carbon Mixes Prepared with Various Fillers

by Jun OKADA*

,In the previous paper (III) an empirical formula w*(Pi) = bwo(Wi) (where P1= W1) derived from the experimental results of the extrusion of fillers of various particle sizes was presented, wt(Pi) is defined as a binder content re-quired for extruding the carbon mixes made by a given mixing process, by a given extruder with a given extruding pressure Pi and a given extruding velocity v,. wo( Wi) is defined as the binder content required to fill up

the vacant space among the filler particles compressed under the load W1. Several extrusion experiments were carried out in order

to verify the empirical formula. Fillers used in tie experi-ments were various brands of coke, mixtures of coke powder and carbon black, mixtures of calcined coke and graphitized coke, natural graphites, and cokes calcined at different tem-peratures. w1 (100 kg) and wo (100 kg) for these fillers were obtained, and a relationship between w~' and wo was studied. From the results the empirical formula was verified.

* Nagoya Plant, 7'okai Electrode Mfg. Co.: Horie-cho, Showa-ku, Nagoya-ski, Ale/ii-ken, Japan.

Kogyo Kagaku Zasshi, 64, 845-849 (1961)

Sequesterability of Sodium Polyphosphates for Manganese

(II) Ion 4

by Shiro UEDA,* Kazuo TERAISHI, and Tatsuro NAKAGAWA

Polarographic amperometric titration of Mnn{ with various sodium polyphosphate solutions was carried out, and it was cleared on the titration curves that the sequesterabilities of these sodium polyphosphates for Mn2+ depend on their chain length.

In other measurements the so-called soap-test which is the method of determining the hard-water softening capacity and the calorimetric method with formaldoxime were applied for the same object, however, the amperometric titration method seemed the best for determining the sequesterability with sufficient accuracy and reproducibility. According to the results obtained with these methods, it was found that the longer the chain of the sodium poly-phosphate, the less the sequesterability for Mns}.

The average chain length of these tested polyphosphates were 2, 3, 7, 13, and 59, respectively.

The tetraethylammonium bromide was suitable as the supporting electrolyte in this amperometric titration,

* Rinkogaku-Kogyo Co., Ltd.: Iu~ari 1, Toyama-ski, Toyanuz-ken, Japan.


Kogyo Kagaku Zasshi, 64, 849^•851 (1961')

Enhancement of Print-out Effect of Photographic Emulsions

with Silver Azide

by Yoshitada TOMQDA*

The printing-out effect of silver bromide is increased by the addition of excess silver nitrate into the emulsion, and

is remarkably increased by the simultaneous addition of

oxalic acid.

Silver nitrate added excessively can be replaced by sodium azide, and the intensification of print-out effect with oxalic

acid was also observed. The increase of print-out effect of

photographic materials such as cine-posi film or gaslight

paper can be carried out by immersing the materials ` in sodium azide solution,

* Government Chemical Industrial Research Institute, Tokyo :

Shinshuku, Hiratsuka-shi, Kanagaura-ken, Japan.

Kogyo Kagaku Zasshi, 64, 851- 855 (1961)

Electrolytic Preparation of Sodium Stannate Solution

by Masayoshi KATOII*

The electrolytic preparation of sodium stannate solution

was studied.

.

For this purpose, the anodic behavior of tin, relations between limiting current density and alkaline concentration, current efficiency (C. Eff.), rate of dissolution and diaphragm materials were studied. The anodic polarization curves showed three stages of the dissolution potential. In the first two stages the anodic C. Eff. . and the rate of dissolution were comparatively high. The final stage which has become passive, however, showed very low C. Eff. . and poor dissolution rates. Up to 0.5 N NaOH solution the limiting current density reaching the passive state was found to . increase proportion-ally with increasing alkaline concentration. In higher concentration, however, the increasing rate rather decreased, because the anodic film grew to thick and the transfer of hydroxyl ion in the film was supposed to have become a rate determing step.

As a result of these experiments, a preferable condition was found out and the concentrated sodium stannate solution was able to prepare in a short time by this condition, in which tin was anodically dissolved in 5 °v NaOH solution at 50°C under constant anodic potential such --0.800 V vs. N. Hg-HgO reference electrode. Synthetic fiber of acrylonitrile-vinyl chloride type was used as the diaphragm, which showed an excellent separation effect.

* Tokyo College of Science: 1-3, Kagurazaka, Shinjuku-ku, Tokyo, Japan.


Electrical Conductivity of Synthetic Mica Melts

by Yoshihiro SUMIYOSHI* and Tokiti NODA

The electrical conductivity of synthetic mica melts was measured by a simple Wheatstone bridge using plain platinum plate electrodes set in the melt which was contained in a cylindrical platinum vessel. An audio-frequency oscillator with a frequency range of 2000 to 8000 c.p.s, was used as an electrical source and the bridge balance was obtained by using a magic-eye. Cor ect resistivity values were obtained by extrapolating resist vity values measured at various frequencies to the infinite frequency value in order to eliminate the polarization effect, assuming that the R (resistivity) -f1/2 (frequency) relation was valid in this case,

Samples used for the measurements were fluor-phlogopite

(KMgSA1SiSOl0F2), boron-phlogopite (KMg3ESiSO1OF2) and POM2 composition (KMgSAISiSOs.$8F2.24). POM2 composition was a raw material mixture frequently used to prepare synthetic mica crystals in the author's laboratory. The samples were first melted at temperatures about 50°C above their melting temperature. After the temperature of the melt was kept at a definite temperature for one hour, the resistivities at various frequencies were measured at the temperature. The measurements were carried out succes-sively at several temperatures by cooling or heating the melt. The electrical conductivities of the melts of both fluor-phlogopite and POM2 composition were 0.160.18 f-1 • cm-1 at temperatures from 1400 to 1420°C and that of boron-

phlogopite melt was 0.100.14 ci -1 • cm-1 at temperature from 1180 to 1250°C. The electrical conductivities of the melts changed abruptly in the vicinity of their crystallizing tempetatures : the conductivity of fluor-phlogopite decreased from 0.12 f-r • cm-1 at 1388°C to 0.12 x 10-2 at 1381°C, while that of POM2 com-

position decreased less abruptly and the change of the conductivity of boron-phlogopite was more or less vague. Active energies of the conduction of the melts of fluor-

phlogopite, boron-phlogopite and POM2 composition calculated from log k-1/T relation were 30, 30 and 24 kcal./mole, respectively.

* Department of Applied Chemistry, Faculty of Engineering, Nagoya University : Furo-cho, Chikusa-ku, 1Vagoya, Aichi-ken, Japan,


The System Fluor-Phlogopite-Potassium Fluoride (3) Results of Quenching Experiments

by Shigeharu NAKA,* Naoki HAGIHARA, Hiroo IIDA, and Tokiti NODA

Crystal phases of fluor-phlogopite compositions containing KF less than 58 wt./ were investigated in the temperature ranges from their liquidus temperatures to room temperature by the quenching method' in order to study the fluor-phlogo-

pite-KF system. Minerals of MgF2-KF system also appeared in the fluor-

phlogopite-KF system and greatly affected the crystallization of minerals of the present system. , In the compositions containing KF less than 20'-30 wt./, fluor-phlogopite crystallized as the primary and a small amount of KF • MgF2 appeared at lower temperatures. In the composition containing 35.6 wt./ of KF where the largest amount of KF •MgF2 was found, K20 • A120g • 2 SiOz and K2O A12O3.4 Si02 crystallized at the first stage, as well as in the composition containing KF above 35.6 wt.% where 2 KF • MgF2 was found along with KF • MgF2. The amount of K20 • A1203 4 Si02 crystallized was found to increase at temperatures lower than the crystallization temperature of KF • MgF2. 1(20 • MgO • Si02 and I-K20 . MgO.3 Si02 deposited after the crystallization of KF • MgF2. They crystallized almost simul-taneously in the compositions containing KF less than 35.6 wt.$. In the compositions containing KF above 35.5 wt.$, Q-KzO • MgO.3 Si02 deposited after the crystallization of K20 ' MgO • SiO2 and the amount of this mineral was found to decrease with the increase of KF.

* Department of Applied Chemistry, Faculty of Engineering, Nagoya University : Furo-cho, Chikusa-ku, Nagoya, Aichi-ken, Japan.

Kogyo Kagaku Zasshi "dol. 64 No. 5 (19.1) A 51

Kogyo Kagaku Zasshi., 64, 865^871 (1961)

On a Ternary Compound Formed in the System CaO-A1203-CaSO4

by Nobue FUKUDA*

A ternary compound which may be formed in the system CaO-A1208-CaSO4 by solid-phase reaction was studied.

The expriments were carried out as follows Six samples were prepared by mixing pure CaCO3, a-A12Os and Ca5O4.2 H2O in the ratios,

(1) 3CaO A1203-nCaSO4; n=0.13.0, (2) 3 CaO-3 A1203-CaSO4, (3) 3 A1203-4 CaSO4, (4) 4 CaO-3 A1203 with S02 Gas, (5) 5 CaO-3 A1203-CaSO4, (6) n(CaO-A1203)-CaSO4; n=1--5.

These samples were heated in an electric furnace at 900 1400°C for several hours, and were investigated by chemi-

cal analysis, X-ray diffraction, X--ray quantitative analysis, and high temperature X-ray diffraction.

It has been confirmed that the formation of a ternary compound in the system CaO-A1203-CaSO4 by solid-phase reaction takes place at about 900°C, and the compound is stable at least up to 1400°C, and composition can be repre-sented by a formula 3 Ca0.3 A1203. CaSO4.

The X-ray diffraction gave the following data ; 200 23.7 27.5 30.7 33.8 36.6 39.1 41,7 56.7 58.5

d A 3.75 3.24 2.91 2.65 2.46 2.30 2.17 1.62 1.58 int. 100 7 6 29 7 4 24 7 4

* Tokuyama Soda Ltd.: Tokuyama-shi, . Yamaguchi-ken, Japan.

Kogyo Kagaku Zasshi, 64, 871^-•878 (1961)

Glass with High Bismuth-Lead Contents

by Minoru IMAOKA*

Studies have been made on the glass formation range and physical properties of glasses with high bismuth-lead con-tents. These systems are glassified easily in the presence of a little amount of glassf orming oxide. In B203-CdO-PbO-Bi203 system the amount is only 5 mol./ (1.4 wt.)j of B203. The results of the measurement of physical properties are as follows : density, 7.08.4; expansion coefficient, 11.1 - -443x106; .deformation temperature, 255377°C; refractive index, 2.182.42, Abbe's number, 1116; dielectric constant, 23.834.6. The additive property of these physical charac-ters was studied and the component factors were calculated. Then the structuree of glass was studied to explain the glass formation ranges and the following conclusion was obtained. When some b-group metal ions are added to the system, the number of b-group ions interconnecting B atoms in the glass increased.

* Institute of Industrial Science, University of Tokyo:. Yayoi-cho, Chiba-shi, Ghiba-ken, Japan.


Separation of Thorium from Rare Earths by N-Benzyl and

N-Cyclohexyl rt-dodecylamine

by Ichiro YAGI*

The separation of thorium from rare earths ('44Ce-'44Pr, 91Y) in 0.037.0 N sulfuric acid solution has been studied with

N-benzyl n-dodecylamine (BDA) and N-cyclohexyl n--dodecyl-amine (CDA).

In the preliminary tests with 11 samples of secondary and tertiary alkylamines having one N-benzyl or one N-cyclo-hexyl branch, it was seen that BDA and CDA show good behaviors for the extraction of thorium. Thorium was sufficiently extracted into benzene solution

of CDA from about 0.1 N-H2SO4 solution or into benzene solution of BDA from about 0.11.0 N-H2SO4 solution, but this abilities decreased gradually with addition of more than 0.1 mole/i. ammonium sulfate solution. The amount of

thorium absorbed by 1 ml. of amine was about 150 mg. (BDA) or 130 mg. (CDA) in the case of 0.1 N-H2SO4. Amount of rare earths extracted into BDA increases with decrease of lowering of thorium concentration in organic

phase'. Therefore the author considered that organic phase must be saturated by thorium to avoid contamination with rare earths during extraction. Decontamination factor of CDA was higher than that of

BDA.

* Research Department, Asahi Electro-Chemical Co. , Ltd. 2850, 9-chome, Ogu-machi, Arakawa-ku, Tokyo, Japan.

Kogyo Kagaku Zasshi, 64, 881'-'884 119611

Retarding Action of Various Aldehydes, Polyhydric Alcohols,

Phenols and Quinones on the Reaction between Aluminum

Particles and Carbon Tetrachloride

by Tadatomo ASAOKA,* Saburo YASUKAWA, Yuxo

HIROTA, Hitoshi NAGASAWA, Toyoji KIKUGA, and

Yutaro ISHIGURO

Aluminum metal reacts with boiling carbon tetrachloride to produce hexachloroethane and aluminum chloride. This aluminum chloride catalyzes this reaction to proceed succes-sively i. e. this reaction is autocatalytic and needs an induc-tion period. As, recently, washing of operated aluminum or aluminum alloy have been carried out with various chlori-nated hydrocarbon to remove oily dirt from them, many troubles caused from corrosive degradation of aluminum surface or explosivly severe reaction are reported owing to analogous autocatalytic reaction. To prevent these troubles we can utilize some inhibitors which are effective to prolong the induction period. As it seems that aldehydes added as inhibitors may form a stable addition compound with aluminum chloride produced in the reaction and give subsequent destructive effect for its

catalytic activity, the reactivity of organic molecules derived from electronic theory was compared with the experimental results concerning the delay of the induction period.

Inhibiting powers of di- and tri-hydric alcohols were observed as 1001000 fold as those of fatty monohydric alcohols or aldehydes in spite of their sparing solubility in carbon tetrachloride. And the adsorption on the aluminum surface was mainly presumed as the mechanism of inhibi-tion. No inhibiting powers were observed with tetra--v hexa-hydric alcohols. Inhibiting powers of various phenols and quinones were observed as 101000 fold as those of fatty monohydric alco-hols or aldehydes. And it seems that phenols and quinones

may form a more stable addition compound with aluminum chloride than that of aldehydes.

* Faculty of Engineerini~, Toyama University : Furujo¢, Takaoka-shi, Toyama-ken, Japan .

A 52 Kogyo . Kagaku Zasshi Vol. 64 No. 5 (1961

Kogyo Kagaku Zasshi,' 64, 883^,888 (1961)

The Structure of fl-Butyl Titanate Polymers

by Kazunobu SHIOSAWA*

To clarify the molecular structures of n-butyl titanate

polymers (A), prepared by the ordinary method of polymeri-zation from 1 mole Ti (OBu)4 (hereafter abbreviated as TnBT) with less than 1 mole H2O, investigation was made and the following results obtained.

(1) The viscosities of dilute solutions of (A) did not satisfy Einstein's equation, and K constant in the equation approached 2.5 as h (h=reacted mole ratio of H2O/TnBT calculated by Ti content of the polymer) moved from 0 to 1 and the following relation was obtained,

[']=1.88x10-4 Mno.°7 (1) (2) A series of measured average molecular weights (M7)

of (A) were in close agreement with that calculated from stoichiometrical yields of (A), which were assumed to consist of the mixture of TnBT (h=0) and n-butyl titanate cyclic tetramer (h=1). But it was not consistent to assume linear polymers or cyclic tamer or pentamer for (A). (3) Infra-red absorption spectra of (A) gradually changed

as h increased from 0 to 1 only in the range from 930 cm-' to 700 cm-1, and showed that (A), with 0 < h '( 1, probably consisted of the mixtures of TnBT and n-butyl titanate

polymer (h=1). Judging from the above results, (A), with O<h(1, consists

mainly of mixtures of TnBT and n-butyl titanate cyclic tetramer.

* Research Laboratory, Takaoka Factory, Nippon Soda Co., Ltd.: No. 300, Mukaino-honmachi, Takaoka-shi, Toyama-ken, Japan.


The Removal of Thiophene in Synthesis Gas

by Kazuo KONO,* Hajime OGORO, and Tetsuo INABA

The investigation has been made with the object of getting some information on removing thiophene from synthesis gas .

Hydrogen containing C4H4S, with and without CO, was passed through a reactor maintained at 250°C and 400°C with the space velocity of about 1200.

The catalyst consisted of tripoli containing 20 o~z by weight of an oxide of a the metal such as Fe , Ni, Co, Cu, Mn, Cd, Cr, Mo, V, Al, or Mg. C4H4S in the gas was fixed slightly by the sulfur-free Ni

catalyst but hardly by other catalysts . Mo catalyst treated with H2S was more active than the sulfur-free Ni catalyst. On the other hand, C4H4S in the gas was converted con-siderably to H2S by Ni and Co catalysts sulf urized by hl2S, but slightly by other self urized catalysts.

In the comparison with results between present and pre-vious works, it became clear that the removal of C4H4S was the most difficult of organic sulfur compounds . The difficulty was explained assuming that thiophene ring was thermally stable and hydrogenating activity of catalysts was decreased being poisoned by thiophene itself or its hydro enated derivatives.

* niuersity of Osaka Prefecture , Fact lty of General Educatio~i Mozu-Umecho, Sakai, Osaka; fu, Japan,


The Chromatographic Behaviors of Naphthalene Derivatives

by Toshikazu NAGAI* and Eiichi FUNAKUBO

The adsorption isotherms, mainly on aluminum from hexane, were measured of or-methyl (Me), /9-Me, 1, 2-diMe, 2,6-diMe-naphthalene, 1-(2',3',4',5'-tetrahydrophenyl)naphthalene, 1--phenylnaphthalene, 1,1'-binaphthyl, 1, 2- and 1, 4-naphthoquinone.

The values of rate of growth Rg and characteristic ratio of developement E were obtained on these compounds.

Methyl groups did not influence significantly the adsorba- bility of the parent compound. However, the adsorbabilities of naphthalene, hexenylnaphthalene, 1-phenylnaphthalene, 1,1'-binaphthyl were not identical to each other. This seems to be attributed to the number of conjugation system, because the U. V. spectra of the above compounds indicate appreciable contribution from coplanar resonance structures.

Adsorbabilities of quinones were very greater than those of hydrocarbons.

* Department of Applied Science, Faculty of Engineering, Osaka Unioersity; 9-Chome, Higashinoda, Miyakojima-ku, Osaka, Japan.


Catalytic Activity of Supported Nickel Catalyst for Hydro»

genation of Toluene Ii. Variation of Activity with the Methods of Preparation and the Composition of Catalysts

by Kiyoshi MORIKAWA* and Fumio NOZAKI

Nickel oxide was dispersed on silica or alumina gel by the following methods ; (1) kneading the mixture of+ nickel hydroxide and carrier, (2) heating the mixed gels with water under high pressure, (3) co-precipitation of gels, (4) soaking the carrier gel with nickel nitrate solution, (5) extraction of free nickel oxide from the alumina-supported . catalyst with dila HCI.

The catalysts were reduced with H2 at 480500°C for 2 hr, and subjected to the following two reactions, (I) nuclear hydrogenation at 200°C, CsH5.CHs+3112=C°H1j.CHs, (II) hydro-demethylation at 460°C, CsH5 CHs+H2 = Cs1s+CH4. All the catalysts were active for the reaction (I) regardless of their methods of preparation and composition.

For reaction (II), only the silica-supported catalysts pre-pared by method (1) and (4) were very active.

The addition of Si02 or MoO3 to alumina carrier induced the activity of Ni catalyst for reaction (II) .

The activities of both silica- and alumna-supported cata-lysts for reaction (I) rapidly increased at above the nickel content of 5-6$ (wt.), and for reaction (II) increased pro-

portionally to the content of nickel in the catalysts. The catalysts prepared by (2), (3) and (5) are fairly

active for reaction (I), but completely inactive for reaction (II).

e

The authors discussed on the possibility of chemical com-

bination between nickel oxide and carrier-substances and

on its correspondence with the selective` activity of the

surface.

* Tokyo Institute of Technology, Research Laboratory of Resources

Utilization : 1-Ookayama, Meguro-ku, Tokyo, Japan.

Kogyo Kagaku Zasshi Vol. 64 No. S (1961 la

Kogyo Kagaku Zasshi, 64, 902' 906 119611

Corrosion inhibiting Effect of Imidazoline Compounds

(Part 1)

by Tomio BABA` and Tsutomu YOSHIN4 :

Substituted imidazoline compounds were synthesized by the condensation reaction of fatty acids and polyethylenepoly-amines such as NH2CH2CH2NHCH2CH2OH and NH2CH2CH2-NHCH2CH2NH2, and corrosion inhibiting effect of their organic acid salts on mild steel were tested in neutral media. The results obtained in respect to the influence of their alkyl chain, side chain and organic acid were as follows (1) the effect of alkyl chain increased in the order of heptade-cenyl > heptadecyl > undecyl, (2) no appreciable, difference was recognized between two side chains (-CH5CH2OH, -CH2-CH2NH2), (3) unsaturated dicarboxylic acid, such as maleic acid and fumaric acid, were the most effective of all the organic acids examined, and in the case of imidazoline-maleic acid salt, it was the most effective at the molar ratio of 1 :1.5 -4 : 2.0. The corrosion inhibiting mechanism was assumed that the compound acted as an anodic inhibitor and caused the forma-tion of protective oxide film on the substratum with dissolved oxygen.

* The Nitto Institute of Chemical Research: 163 Kamikizaki, Urawa- shi, Saitama-hen, Japan.

Kogyo Kagaku Zasshi, 64, 907^909 ( 1961)

Corrosion Inhibiting Effect of Imidazoline Compounds

(Part II)

by Tomio BABA* and Tsutomu YQSHINO

The corrosion and rust preventive property of Imidazoline salts on mild steel was tested for various "corrosive condi-tions. The corrosion inhibiting effect of 1-aminoethyl-2-hepta-decenyl imidazoline maleic acid salt (molar ratio l :1.5) was

found to increase when mineral oil or fatty oil was mixed . in the form of emulsion.

Then, the corrosion tests were carried out with this emulsified inhibitor for several corrosive conditions. The results obtained were as follows : the inhibitor was effective in hot water (80 °o prevention or more), or in running water (70 0 or more), but it was almost ineffective in salt water or acidified water (pH 3-'5).

It was also found that the rust preventive property of oil containing 4 / of the imidazoline oleic acid salt (molar ratio 1 : 1--1 : 3) was excellent in evaluating in by the salt water immersion test, the humidity cabinet test and the polarographic method.

* The Nitto Institute of Chemical Research: Kamikizaki, Urawa-shi, Saitama-ken, Japan.

Kogyo Kagaku Zasshi, 64, 910--'912 119611

Studies on the Crystallization of Sugar with a Crystallizer

in the Presence of a Minute Quantity of Manganese and

Cobalt Salts

by Kakuo SUZUKI*

As it had been ascertained that the addition of a minute

quantity of manganese and cobalt salts favors the crystal-

lizing out of sucrose from a sugar solution of good quality,

the experiments described here were conducted employing

the last massecuite and the last molasses as samples. The

amount of salts added was 10-2~-10-¢ ~o of the sampler For

comparison the blank tests were made under the same condi-

tion in another crystallizer whose stirrer was fixed to the

same revolving axis.

The result of the experiments shows that the addition of

the mixture of the salts favors the crystallization of sugar

in this case. Namely the yield of the product is better, the

content of reducing sugar less and its color lighter. Also

the molasses separated after sugar boiling has lower viscosity

than those of the normal method.

Accordingly, it was proved that the addition of manganese

and cobalt salts has good results for the treatment of molasses

of inferior quality.

* Department of Liberal Arts and Education of Gunma University :

Seioji 146, Maebashi, Gumma-ken, Japan.

Kogyo Kagaku Zasshi, 64, 912'915 119611

Viscosity of Branched Silicone Solution

by Hiroyoshi YAMAMOTO*

The viscosity behaviors of branched and linear silicones were studied. In part 1, the viscosities of benzene solutions of silicone of the concentrations from 0 °o to 100 were

measured. In the low concentration range, the viscosity of the benzene solution increased with concentration more notably in the case of linear silicone than in branched silicone.. In the high concentration range, the viscosity of the benzene solution of branched silicone decreased with the addition of small quantity of benzene more remarkably than that of linear silicone. In order to express the concentration dependence of viscosity over the whole range of concentration, the author defined " Normalized relative viscosity index

(zn)" by the following equation, log r

7N _ log 1r°

where 7r is the ratio of the viscosity of solution to the viscosity of solvent, and

?r" is the ratio of the viscosity of solute to the viscosity of solvent.

72N was independent on the bulk viscosity of silicone itself, and its concentration dependence indicated clearly the branching of silicone molecules. In part 2, the temperature dependence of the viscosity of

dilute solutions was measured in order to know the effect of branching. The intrinsic viscosities of all the samples increased with temperature, and the intrinsic viscosity of the silicone having many branchings showed small tempera - ture dependence.

* Shin-Etsu Chemical Industry Co., Ltd.; Togin-Building, Chiyoda- ku, Tokyo, Japan.

A 54 Kogyo Kagakn Zasshi Vol . 64 No. 5 (1961)


The 'Hydra-cracking of Lignin

by Kan KASHIMA* and Takeshi OSADA

The optimum condition for producing the raw material of the hydro-cracking was examined.

In the hydra-cracking of lignin in the medium of phenol, cyclo-hexanol or tetralin, the effect of reaction condition, material balance and constitution of oil were studied. The neutral oil (especially aromatic hydrocarbon) produced consisted of o-xylene 6.6 U~, m-xylene 53.4 /, p-xylene 26,7 o, etc. When lignin was hydro-cracked with petroleum, naphthene hydrocarbon in petroleum was converted to aromatic hydro-carbon by the dehydrogenation action of lignin.

* The Juridical Foundation, The Noguchi Institute : 6-3569, Itabashi- cho, Itabashi-ku, Tokyo, Japan.

Kogyo Kagaku Zasshi, 64, 919 - 921 119611

On the Study of the Acidic Constituents of Lignin

Liquefied Oil

by Kan KASHIMA,* Haruro TABATA, and Hiroshi

WATANABE

In the last report, high pressure hydrogenation of lignin

obtained from the sulfite spent liquor and the composition of the oil produced were investigated. In this report, the authors studied on the acidic constituents

of liquefied oil and found that the low boiling point fraction

(b, p. 185--230°C) consists of p-cresol, o-cresol, 4-ethyl-phenol, and 4-(n-propyl)-phenol, and cateehol exists in the high boiling fraction (b. p. 230^260°C).

Feature of this process is that the acidic fraction consists of the phenols having no methoxyl group and containing no m-isomers.

* Juridical Foundation, The Noguchi Institute : 6-3569, Itabashi-cho, Itabashi-ku, Tokyo, Japan.


Studies on the Hardwood Lignin (l ) Fractionation of Hardwood Lignosulfonate and Properties of Each Fraction

by Yojuro KYOGOKU,* Hirotoshi IDA, and Yoshikazu

HACHIHAMA

Lignosulfonate (LSA) was purified by repeated dialysis from a waste liquor of pilot plant scale sulfite cook of beech wood (Fagus crenata Blume), and was converted to barium salt (LS-Ba) . Beech LS-Ba was fractionated into 13 frac-tions by fractional precipitation using water and ethanol as solvent and precipitant, respectively.

Degree of sulfonation (DS), ultraviolet absorption and oxidizability by alkaline nitrobenzene were determined with each fraction. Relative order of the molecular weight (MW) was estimated by U.V. absorption. As the results, MW de-creases and DS incr ses by the order of fractional precipi-tation. The yields f syringaldehyde (S) and vanillin (V) differ from fraction to fraction, and S/V ratio increases by the order of fractionation. These results indicate that beech LSA has similar hetero-

geneity as softwood LSA with respect to its MW and DS.

In taddition to this, beech LSA is `heterogeneous with respect to its S- and V-yielding units. Fractional precipitation with LS-Ba-water-ethanol system has a triple dependence on MW, DS and S/V ratio.

* Department of Applied Chemistry, Faculty of Engineering, Osaka University: Higashinoda-cho 9, Miyakojima-ku, Osaka, Japan.

Kogyo Kagaku Zasshi, 64, 925^928 (1961) ,

Graft Copolymerization of Vinyl Acetate on Cellulose

by Fumio IDE*

The graft copolymerization of vinyl acetate on cellulose was carried out under various conditions using ceric ammo-

nium nitrate as an ' initiator. The effects of polymerization temperature, polymerization time, catalyst concentration, monomer concentration, and

nitric acid concentration on the graft copolymerization were studied. The results obtained were as follows

(1) The overall polymerization yield decreases with increase of the nitric acid concentration; while it shows

maximum value at certain regions of the catalyst concen-tration and the polymerization temperature.

(2) The graft efficiency is inversely proportional to the nitric acid concentration, the polymerization temperature, and the catalyst concentration. It is, however, independent upon the monomer concentration eicept when the latter is extremely low.

(3) The amount of homopolymer produced is rather high as compared with the case of methyl methacrylate.

, Mitsubishi Rayon Co. , Ltd.: 2-8, Kyobashi, Chuo-ku, Tokyo, Japan.

Kogyo Kagaku Zasshi, 64, 929^932 119611

Studies on Vinyl Sulfonic Acid, I. Syntheses of Vinyl Sulfonic Acid (VS), and the Monomer Reactivity Ratio (MRR) and Dyeability of Its Copolymer with Acrylonitrile

by Sango KUNICHIKA * and Takao KATAGIRI

As the chemistry of VS has not been sufficiently studied, the authors have been studying it, and now wish to report a part of the data. 1) There are many methods for the synthesis of VS and

some of them were investigated. It was found that the following method was the best one for the laboratory scale:

PCI6 BrCH2CH2Br 2Na2S03 ~ NaO3SCH2CH2SO3Na -~-

C102SCH2CH2SO2C1 x-2- CH2=CHSO3H 2) For the purpose to find the MRR, VS was copolymerized

with acrylonitrile. And MRRs which were calculated by the Fineman-Ross' method, were r1=1.5 (AN) and r2=0.15 (VS) . From these data Q and a values of VS were estimated as Q=0.09 and e=+1.3. 3) The dyeability of AN-VS copolmer with the cathionic

dye (Sevron Blue B) was very good as authors expected. The initial adsorption rate was very high for the copolymer containing 4.3 mole pa of VS.

* The Institute for Chemical Research, Kyoto University : Kosobe, Takatsuki-shi, Osaka, Japan.

Kogyo Kagaku Zasshi "Vol. 64 No. 5 (1961) A 55


Synthesis of p-Vinylphenethyl Alcohol and Its Polymerization

by Shigeo TANIMOT0# and Ryohei ODA

In the presence of tetrahydrof uran as solvent, p-vinyl-

phenyl magnesium chloride reacted with ethyleneoxide at 0 -10°C and p-vinylphenethyl alcohol was obtained . The yield was 29 0 of calculated value. When a mixture of 8.59 g, of p-vinylphenethyl alcohol and 44.1 mg. of benzoyl peroxide was heated at 75°C for 2.5 hr. in the atmosphere of nitrogen, p-vinylphenethyl, alcohol poly-merized in ca. 40 $ yield of calculated value. The polymer was acetylated by warming at 90°C with acetic anhydride and pyridine for 1248 hr, and the polymer thus treated was soluble in acetone, benzene, and other organic solvents.

* Department of Industrial Chemistry, Faculty of Engineering, Kyoto University : Yoshida, Sakyo-ku, Kyoto, Japan.

instance, of mechanical strength of injection-molded articles, the degree of molecular orientation, as well as mechanical strength, knowledge of which is important for good designing of the mold, may be estimated.

In this report injection molded plates of PMMA were used to measure the anisotropy of tensile strength, elasticity, etc., especially in relation to the effect of water absorbed by the

polymer. The following results were obtained; tensile strength and elasticity of the molded plates decrease linearly as the amount of the absorbed water increases. The aniso-tropy in the plates can be observed from the fact that specimen parallel to the flow direction showed higher qualities

than that perpendicular to it. A slower velocity of tensile loading has a larger influence on the strength perpendicular

to the flow direction than that parallel to it. This can be explained by an experimental fact from tensile stress relax-ation that the former has a distribution of shorter relaxation times than the latter.

* Research Division, Fuji Electric Mfg. Co., Ltd.: Tanabeshinden, Kawasaki-shi, Kanagawa-ken, Japan.


Influence of Residual Strain on Crystallinity of Polyvinyl

Chloride

by Kirokuro HQSODA*

This report deals with the change of the degree of crystal-

linity, estimated by X-ray diffraction, of polyvinyl chloride

compound with the residual strain induced by stretching..

Several items as follows are clarified by this study.

The degree of crystallinity of polyvinyl chloride increases

with the increase of the stretching temperature, of the

stretching time and of the residual strain.

The crystallinity of polyvinyl chloride scarcely changes

with the plasticizer added.

* Research Center of the Furukawa Electric Co. , Ltd.: 520, 3-chome, Futaba-cho, Shinagawa-ku, Tokyo, Japan.


Anisotropy of PMMA Injection-Molded Articles and its Relation to Water Absorption

by Takehisa SAKURA*

In the injection molding, linear polymer is known to show so-called frozen orientation during its flowing and subsequent cooling. This is especially indicated by the anisotropy in the injection molded articles. By measuring the anisotropy, for

Kogyo Kagaku Zasshi, 64, 942^-'943 (1961)

Reversion of Glucose to Oligosaccharides by a Commercial

Enzyme

by Shiro KUROIWA and Matao NAKAMURA

It seems not to be unreasonable to consider that sacchari-fing enzyme of starch is a catalyst of reversions of glucose to oligosaccharides; because these reversions are catalysed by acids. ` The object of the work described here is to know whether the reversion of glucose occurs by a commercial enzyme. Glucose solution containing commercial enzyme was kept

at 55°C for 5 days. The reactant was fractionated by paper

chromatography. At least 5 spots were detected on the chromatogram by AgN4s reagent. Quantitative estimation of fractions is carried out by colorimetry using anthrone. The results obtained indicate that glucose is converted into

oligosaccharides by commercial enzyme as by acids. The fact of reversion of glucose by commercial enzyme may explain the phenomenon of depression of D. E, and the increasing tendency of oligosaccharide components at the last stage of saccharification.

* Institute of Industrial Science, University of Tokyo: Yayoi-cho, Chiba-shi, Chiba-ken, Japan.

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Kogyo Kagaku Zasshi