( 69 )

CELLULOSE
THE JOURNAL

INDUSTRY

OF THE CELLULOSE
VOL.

INSTITUTE , TOKYO, JAPAN

15 August,

ABSTRACTS

FROM

THE TRANSACTIONS

STUDIES ON XANTHATE(1)
ON THE REACTIONSOF SOME XANTHICACIDSWITH
METALLICELEMENTS
by

K.

Atsuki

and

(Recived
A
their

number

formation

of

xanthates

and

their

of

various

characteristic

17th,

T. Takada.

June,

alcohols

1939)

and

properties

were

metals
studied.

were

prepared,

comparing

and

with

the

cellulose

reaction

of

xanthates.

Experimentals.
1.
alcohols
with

Preparation
were

carbon

of ether

was

xanthates

of

prepared

of

as follows.

The

alcohol

bisulphide

gradually

while

added,

and

sodium

by rubbing

were

obtained.

Then

the

and

crystallised

again

from

All these

crystals
ether.

salts are needle

ether,

and

soluble

weight

of alcohols.

in

the
were

alcohol.

Thus

like
Their

pure

various

cooling.
wall

the

crystals

After

of the

dissolved

in

following

having

solubility

alcohols.

was

saturated

The

sodium

xanthates

of

with

sodium

hydroxide

and

the

reaction

reaction

vessel,

beautiful

a small

quantity

of

6 kinds

completed,

decreases

were

the

or

used

unpleasant
with

a large

needle

alcohol

of xanthates

the characteristic

in water

was

flaky
in

various
added

quantity
crystals

xanthation,

prepared.

odour,

increase

insoluble
of molecular

in

(70)

U
.

Reactions

1.
the

Alkali

reaction

carbon

with

grroup.

of the

and

decreases,
of the

The

readily

and

elements.

Alkali

xanthates,

alcoholate

bisulphide.

in ether

metallic

of the

xanthates

soluble

the

degree

of

in
of

2. Copper

group. The

The greater

and their

K-,
or

are

yellowish

solubility

of

of xanthates

xanthates

the

decomposition

3.

Alkaline

suspension

colour,

and

4.

atomic

Ca-,

NH4-xanthates

a mixture

of

white

xanthates

increases

soluble

their

hydroxides

soluble

in water,

of

with

alkali

crystals
these

the

were

prepared

and

alcohol

which

alkali

are

insoluble

metals

increasing

by
with

in

molecular

water
weight

solution

c.c.

CS2

with

an

soluble
largest

to

alcoholic
in

of

added

all

water
the

water
and
other

the

alkaline

white

as

above.

in alcohol

decomposition

and sulphides

earth

carbon

metals

bisulphide.

crystalline

solution

was
of

of sodium

of
is
of

not

sodium

suspension

xanthates

prepared
soluble

They

are

and insoluble

of the
at room

salts.

The

temperature,

were

prepared

by

The

salts

of a yellow

are

shaking

beryllium

xanthate,

xanthate

with

which

is readily

addition

of a con

or BeSO4.

solution

It

easier the
alcohols

with

a yellowish
from

ether.

of

alcohol

xanthate
the

were
hardly

ether.

of Be(N03)2

Magnesium
was

xanthates

and

Beryllium;

the

corresponding

in

water

group

in ether,

by warming.

The

was precipitated

aqueous

Magnesium;
4.18g/50

in

copper

soluble

of metals,

into

are accelerated

group.

of
easily

of the

easily

weight

earth

Zinc group.

centrated

the

Na-,
alkali,

metals

The

colour,

salts of Au and Ag are decomposed

easily

alkali

water.

hydrolysis

of a yellow or orange

in water.

of

as

alcohol.

mostly

the

such

corresponding

MgO

interesting
this

obtained
xanthate.

group.

at

It
50.

that

or
the

when

the

was,

however,

Mg-ethyl
solubility

solution
prepared
alcoholate.
of

Mg-xanthate

of

MgCl2.6H2O
by

the

action

Mg-xanthate
in

is
water

is

(71)

5.

Aluminium-Group.

when the solution

of xanthate

decomposed

aluminium

and stability

It may

salts does not follow

a yellowish

on warming.

: Aluminium

xanthate

was added to a saturated

by hydrolysis.

of the aluminium

Cerium;
xanthate

Aluminium

white

assumed

It is easily
that

law because

as a yellow precipitate
soluble

the coagulation

in water
of viscose

of the

characteristic

solubility

a white

precipitate

of cerrous

itself.

precipitate,

was precipitated

A1C13 solution.

be reasonably

the Hoff-meister's

xanthate

was obtained

which

changes

from the solution

into

of xanthate

by the addition

of the saturated

Ce(NO3)3 solution.
Erbium
no reaction
6.
dilute

, Dysprosium

was observed

at room

Thallium

inorganic

7.
the

Er(NO:

Group.

of santhate

Tin

The

Lanthanium

La(-NO:,)::, Ytterbium

Yt(CH3CO2)s;

temperature.
salts

of

this

group

are

insoluble

in

water,

and

not

attacked

by

acids.

Titanium

solution

8.

Group.

Dy(CH;jCO2);.,

Group.

Titanium:
with

the

addition

A mixture
of an

of Titanium
acidic

solution

and

xanthicc

of titanium.

acid

was

produced

from

(72)
.
of this

Vanadium

Group.

Tantalum

The
:

which

10.

Nitrogen

11.

Cromium

12.

Sulphur

occur

in

the

case

of

non-metallic

elements

14.
alcohol
the

and

produces

Group.

in

the

reaction

can

not

be clear.

element.

dark

alcohol

that

brown
and

precipitate

ether.

of

showing

xanthate

a reddish

from
brown

the

solution

of

colour.

the

Group.
ether.

Terbium

Due

to the

non-metallic

properties

of these

metals,

to occur.

The
As

radicals.

Manganese:

solution

is soluble

xanthie

Selenium,

Group.

from

Iron

is so acidic

Group.

Mn-methyl-xanthate

detect

to

Group.

Manganese

obtained

of Niobium

is soluble

is expected

13.

in

is expected

is a non-metallic

V02C14

sodium-xanthate,

reaction

solution

Tantalum

Vanadium:

was

reaction

group.
Niobium

no

No

the

of
in

sodium

water,

xantic
colour

salts
of

yellowish

white

xanthate

and

the

other

of

this

group

Cobalt

with

precipitate

the

alcoholic

xanthate

have

addition
xanthates

of

of the
are

a characteristic
is

so

manganese

characteristic,

xanthate

solution

soluble
colour,
it

of MnC12.

in

hot

water.

and

are

soluble

may

be

used

to

(73)
15.
solution

Platinum

xanthate,

and

in alcohol

and

solution

show

radical
is

is

K_
Cu,

The

supposed

were
TL

to

Au

Zn,

A)

were

Co,

W
.

solubility

The

He.

relation

of

On adding

the

orange ether

soluble

immediately

to a white

B)

the

ether

with

salt

in
The

but

valency

of

metals

propyl,

butyl.

the alcohol
cellulose

amyl,

radical

are the same

with increasing
the presence

The

the

xanthate

other

trivalents
law

white.

to the
of alcohol

xanthates

of

Pt

of

various

with

of Au,

by our

the colour

radicals,

Ca,

in

ether.

Sr,

Ba,

of Na-xanthate,

an

but it changed

ROCS,,

Au.

The

same

vanadyl salt were added

the

as

the

cellulose

affects the colour

xanthate

of xanthate

the colours

But

has

studies

stability

ethyl,

no connection

with

of alcohol

of xanthate

and

decreases

easily decomposes,

cellulose

that

of methyl,

of xanthates

xanthate

of pure

, Bi: 29.5%,

spectrochemical

the sodium

It is proved that
same metal.

as

Na,

salts as follows.

It was found

and that

there
as

Xanthates.

The yield was as follows. Co: 89.8

is identical

relation

such

An was obtained,

xanthate

this

acid

metals,

soluble

to the solution

(RoCS2)j

same

and

such

were

from

the

metals

metals

V02,

of

various

monovalent

polivalent
Tl,

formation

polivalent

alcoholic

Fe-Cellulose

Pt-Cellulose
may

example,

in the

the

of the

metals.

alcohols

yellow,

consideration
For

soluble

and

xanthate.

The colour

xanthate;

dark

was as follows :

xanthate:

xanthate.

the

of

salt

respectively and the corresponding xanthates

xanthate.

weight

different,

also

bismuth salt, and quardvalent

xanthate

respect

propyl

precipitate

is

Au,

of An...

of other

and thiocarbonate

xanthate:
same

Hoffmeister's

with

molecular

Cu-Cellulose
7.n_f!Plln1es,

forms

of sulphide

of pure cellulose

cellulose

and benzyl
which

or

colour

solvent

Au salt, HAuCl,

precipitate

of various
cellulose

the

are

yellow

of

of

Cr,

to

of the xanthate
insoluble

xanthate

salts

orange

metal

xanthates

xanthates
Bi,

an

of golden

of

of

the

the
Hg,

of trivalent

the reaction

of sodium

from

ethyl-,

platinum

produced
are

valency

solubility

precipitate, which were filtered and weighed.

precipitate

from

These

and

specific

All

Pb,

to 3/100 Mol solution of Na-xanthate

V.

orange

precipitate

H2IrC16

the

some

The bivalent cobalt salt, trivalent

the constitution

yellowish

orange

in ether.
As

solvent.

U02,

solution

xanthate.

Iridium

ether.

ether,

Sn,

precipitate

results were obtained

the

as
in

Mn.

an

benzyl

soluble

xanthates.

ether

insoluble

Ni,

are
in

of

with

and

from

H2PdCI6i

xanthate

. using

produced

colour.

which

of

exist

examined,

Ag,

Cd,

golden

palladium

solubility

H2PtCl6

xanthate

precipitate

xanthate,

the

amyl

white

H2RhC16,

different,

easily

fore,

or

a bright,

of ethyl

Platinum

butyl-,

a yellowish

Rhodium
the

Group.

of methyl-,

be

xanthate;
possible

aluminium
xanthates,

coagulation

xanthate;

in

orange,
case

alcoholic
so

of viscose.

brown,

green,

etc.

of the
xanthate

aluminium

Co-Cellulose

solubility

and

is more

cellulose

stability

soluble

xanthate

and
does

of alcohol
less
not

stable
obey

and
than
the

(74)

Summary.
1.

The

alcohols

formation

of

xanthate

with

48

kinds

of the

metallic

elements

and

6 kinds

of

of metals

or

were studied.

2.

The

indirectly

of metallic

from the inter-reaction

3.
existing

xanthates

The

colour

elements,.

of sodium

of xanthate

are

formed

xanthates

is characterised

directly

from

alcoholate

and metals.
by its salt but not by the sulfide

of the

metal,

in common.
4.

xanthate
the easier
5.
which

When
in

the molecular

water

decreases.

the decomposition
The xanthates

weight

of alcohol

which

If the

xanthate

radicals

of the salt, forming

of metals

are generally

forms

xanthate

increases,

are the same,

the larger

the
the

solubility

of

atomic

weight

of the alcohol

radical

sulfide.
of the same

colour,

regardless

forms xanthate.
6.

of cobalt
7.
xanthates
8.
polivalent
9.

Besides

the

reaction

of copper,

as the method

of the detection

of xanthate,

the

reaction

is interesting.
The

univalent

alcoholic

xanthates

are

insoluble

in

ether

while

of metal

increases,

the

formation

of xanthate

the

polivalent

alcoholic

are soluble.
As

the valeney

metals, the xanthate

becomes

of alcoholic

harder.

xanthate

With

the

with respect

to the same metal.

Cellulose
to the

Department
Cellulose

xanthate

stability

Research

of

sometimes

and solubility
Applied

Laboratory.

does not obey the

Chemistry.
Faculty

Hoffmeister's

law.

the cause

of which is

of xanthate.
Faculty

of Applied

of Engineering.
Chemistry,

Tokyo

Tokyo
Technical

Imperial
University

University
College.