U.S. patent application number 09/206161 was filed with the patent office on 2003-07-31 for closed heat-decomposing appliance, pretreatment method of sample using it, analytical method and device thereof.
Invention is credited to MORINAKA, HIDEO, OKADA, TADASHI, TADA, YOSHIMITSU, TANIMOTO, NORIYUKI.
Application Number | 20030143115 09/206161 |
Document ID | / |
Family ID | 27590549 |
Filed Date | 2003-07-31 |
United States Patent
Application |
20030143115 |
Kind Code |
A1 |
TANIMOTO, NORIYUKI ; et
al. |
July 31, 2003 |
CLOSED HEAT-DECOMPOSING APPLIANCE, PRETREATMENT METHOD OF SAMPLE
USING IT, ANALYTICAL METHOD AND DEVICE THEREOF
Abstract
Disclosed are a closed heat-decomposing appliance comprising a
heating section with one side closed and other side having common
ground portion, screw portion or O-ring-mounted portion and a
closed introducing section that allows to connect to this heating
section and common ground portion, screw portion or O-ring via
O-ring-mounted portion and has cock or valve as a mechanism for
closing and introducing the absorbing liquid to absorb the testing
components from outside after heat-decomposition, or has packing or
septum to introduce the absorbing liquid with needle pipe as well,
and a pretreatment method of sample using this appliance. The
purpose is to provide a closed heat-decomposing appliance for the
pretreatment on accurate quantitative determination or detection of
the testing components in sample, which requires no combustion
assistant, which is not obstructed by ash present in sample
absorbing the testing components, which requires no complicated and
dangerous procedures, which can be used repeatedly, and which
allows to inject the absorbing liquid after heat-decomposition, and
a pretreatment method using it.
Inventors: |
TANIMOTO, NORIYUKI;
(HIROSHIMA-KEN, JP) ; TADA, YOSHIMITSU;
(TOKUYAMA-CITY, JP) ; MORINAKA, HIDEO;
(TOKUYAMA-CITY, JP) ; OKADA, TADASHI;
(SHINNANYO-CITY, JP) |
Correspondence
Address: |
JACOBSON PRICE HOLMAN & STERN
400 SEVENTH STREET N W
WASHINGTON
DC
20004
|
Family ID: |
27590549 |
Appl. No.: |
09/206161 |
Filed: |
December 7, 1998 |
Current U.S.
Class: |
422/68.1 ;
422/400; 422/78; 422/81; 422/83; 422/88; 436/124; 436/160; 436/174;
436/178 |
Current CPC
Class: |
Y10T 436/25 20150115;
Y10T 436/255 20150115; Y10T 436/19 20150115; G01N 1/44 20130101;
Y10T 436/25125 20150115 |
Class at
Publication: |
422/68.1 ;
436/124; 436/174; 436/178; 436/160; 422/78; 422/81; 422/88; 422/83;
422/99; 422/100; 422/102; 422/103 |
International
Class: |
G01N 001/00 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 5, 1997 |
JP |
HEI 9-336132 |
Claims
What is claimed is:
1. A closed heat-decomposing appliance being an appliance for
horizontally or slantly inserting heating section into a heating
device to heat, decomposing the inner organics in the presence of
oxygen gas, taking out from the heating device and cooling, then
introducing the absorbing liquid to absorb the testing components,
comprising a heating section with one side closed and other side
having common ground portion, screw portion or O-ring-mounted
portion and a closed introducing section that allows to connect to
this heating section by common ground portion, screw portion or
O-ring via O-ring-mounted portion and has cock or valve as a
mechanism for closing and introducing the absorbing liquid to
absorb the testing components from outside after
heat-decomposition, or has packing or septum to introduce the
absorbing liquid with needle pipe as well.
2. A pretreatment method comprising the steps of setting up the
sample which may sometimes contain organics in the closed
heat-decomposing appliance of claim 1, filling up oxygen and
closing, then heating to decompose the organics, followed by
cooling, and thereafter introducing the absorbing liquid into said
closed heat-decomposing appliance to absorb the testing components
in said sample.
3. The pretreatment method of sample of claim 2, wherein the
testing component(s) is(are) one kind or two or more kinds selected
from a group consisting of halogen and sulfur.
4. The pretreatment method of sample of claim 2 or claim 3, wherein
the amount of oxygen gas to be filled up is not less than 2.5 times
the amount of oxygen gas required for complete combustion of
sample.
5. A device for heat-decomposing the sample which may sometimes
contain organics using the closed heat-decomposing appliance of
claim 1, comprising an appliance-installing section to install said
closed heat-decomposing appliance, a heating means to
heat-decompose the sample in said closed heat-decomposing appliance
and a moving means to reversibly move said closed heat-decomposing
appliance installed at said appliance-installing section to said
heating means.
6. A pretreatment method of sample, comprising the steps of setting
up the sample which may sometimes contain organics together with
oxygen in the closed heat-decomposing appliance of claim 1 and
closing, and then heating said closed heat-decomposing appliance
with device of claim 5 to decompose the organics which may be
sometimes contained in said sample.
7. A device for heat-decomposing the sample and dissolving the
testing components produced, comprising, adding further to the
device for heat-decomposing sample of claim 5, a cooling means to
cool the closed heat-decomposing appliance after heat-decomposition
of sample in said closed heat-decomposing appliance, an injecting
means to inject the absorbing liquid into said cooled closed
heat-decomposing appliance, a mixing means to stir and/or shake for
making the absorbed liquid in said closed heat-decomposing
appliance uniform, and a moving means to reversibly move said
closed heat-decomposing appliance from appliance-installing section
to any of said heating means, cooling means, injecting means and
mixing means.
8. A pretreatment method of sample, comprising the steps of setting
up the sample which may sometimes contain organics together with
oxygen in the closed heat-decomposing appliance of claim 1 and
closing, then heating said closed heat-decomposing appliance to
decompose the organics which may be sometimes contained in said
sample, thereby producing the testing components, cooling said
closed heat-decomposing appliance, injecting the absorbing liquid
into said heat-decomposing appliance to dissolve the testing
components, and further stirring and/or shaking said closed
heat-decomposing appliance to make said absorbed liquid in the
closed heat-decomposing appliance uniform, with the device of claim
7.
9. A device for analyzing the testing components, comprising,
adding further to the device for heat-decomposing the sample and
dissolving the testing components produced of claim 7, an
analytical means to analyze the testing components in absorbing
liquid and a moving means to sample part of the absorbing liquid
inside the closed heat-decomposing appliance and to move to said
analytical means.
10. An analytical method, comprising the steps of setting up the
sample which may sometimes contain organics together with oxygen in
the closed heat-decomposing appliance of claim 1 and closing, then
heating said closed heat-decomposing appliance to decompose the
organics, followed by cooling, injecting the absorbing liquid to
dissolve the testing components, stirring and/or shaking said
closed heat-decomposing appliance to make the absorbed liquid in
the closed heat-decomposing appliance uniform, and then analyzing
the testing components in absorbed liquid with the device of claim
9.
11. A device in the device of claim 7 or claim 9, comprising a
needle pipe, a motor buret, a switchable valve with actuator, a
moving means of needle pipe to pierce through packing or septum of
the closed heat-decomposing appliance and to move to washing boat,
and a washing port to wash the contaminated needle pipe, as an
injecting means of absorbing liquid into the closed
heat-decomposing appliance.
12. A device in the device of claim 7 or claim 9, comprising a
means to reciprocate the closed heat-decomposing appliance in the
axial direction of closed heat-decomposing appliance, while
rotating it centering to the axis of closed heat-decomposing
appliance, leaving horizontal, as a mixing means.
13. A device in the device of claim 7 or claim 9, comprising a
cross type motor robot with mechanical hand or a mechanical hand
and cross type motor robot with axis for rotating it, as a moving
means.
Description
BACKGROUND OF THE INVENTION
[0001] The present invention relates to a closed heat-decomposing
appliance for the pretreatment on analyzing the components in a
sample which may sometimes contain organics and a pretreatment
method using it. In more detail, it relates to a closed
heat-decomposing appliance for heat-decomposing organics and then
absorbing the analyzed components into absorbing liquid on
analyzing quantitatively or detecting the components in a sample
which may sometimes contain organics by quantitative determination
or detection, and a pretreatment method for heat-decomposing the
sample and absorbing the testing components in sample using it.
Moreover, it relates to a device automating the decomposition of
sample, absorption of analyzed components and analysis, using the
closed heat-decomposing appliance.
[0002] So far, for the analysis of components like halogen and
sulfur in organics, usually pretreatment procedures of decomposing
the organics under heat or combustion and absorbing the analyzed
components has been done and then quantitative analysis has been
performed by ion chromatography, titration, colorimetry, ion
selective electrode method or the like. As the methods of this
pretreatment, closed flask combustion method, combustion-tube
method, sealed tube dry combustion method, hot-flask combustion
method and vertical closed tube method are known.
[0003] Thereamong, the oxygen-flask method is described, for
example, in "Yuki biryo teiryo bunseki" (Organic Quantitative
Microanalysis) edited by "Yuki biryo teiryo kenkyuu kondankai"
(Conversazione for Studying Organic Microanalysis), p. 383 (1969),
Nankodo. Procedures are as follows: Namely, absorbing liquid is
poured in a reaction vessel like Erlenmeyer flask, oxygen is filled
up in the vessel, around several tens mg of sample is weighed,
wrapped in filter paper being a combustion assistant, held between
platinum meshes and fired, then this is inserted swiftly into the
reaction vessel, which is turned upside down while securely
pressing down the stopper and reaction vessel. During combustion of
sample, the absorbing liquid blocks off the opening between flask
and stopper, and, after combustion, the reaction vessel is shaken
well to absorb the testing components into absorbing liquid. This
oxygen-flask method requires no particular appliance to be prepared
except reaction vessel, but has problems that the microanalysis is
impossible due to contamination from filter paper that wraps the
sample, a reaction vessel with size of an order of several hundreds
ml must be used to secure the quantity of oxygen required for
burning filter paper, thus requiring broad area for the space of
experiment, that the skill is needed for the procedures such as
firing the sample and burning it in the reaction vessel, and so
on.
[0004] The combustion tube-burning method is described in detail,
for example, by Honma et al in Analytical Chemistry, vol. 35, p.
536 (1986). Procedures are as follows: Namely, sample is inserted
into a tube made of quartz or the like installed in a
high-temperature furnace while flowing oxygen stream, and burned
completely through catalyst, thereby gasfying the testing
components to absorb into absorbing liquid. This combustion
tube-burning method is suitable for the automation due to simple
procedures, but, when ash content such as alkali metal is contained
in the sample, it has drawbacks that the analyzed components
transfer incompletely to absorbing liquid due to capture by ash
content to make it difficult to perform accurate analysis, and the
like.
[0005] The sealed tube-burning method is described in detail, for
example, by Hozumi et al in Analytical Chemistry, vol. 38, p. 259
(1989). Procedures are as follows: Namely, overall sealed tube with
the sample and oxygen sealed therein is inserted into a
high-temperature furnace to heat and, after allowed to stand for
cooling, the sealed portion is dropped into a vessel accommodated
with absorbing liquid to break. Since the absorbing liquid enters
forcibly into sealed tube due to negative pressure inside the
sealed tube, it is allowed to stand as it is to absorb the analyzed
components into absorbing liquid. This sealed tube-burning method
has advantages that there is little contamination due to no
combustion assistant used and that the quantity of sample is
sufficient with trace amount under 1 mg, but it has drawbacks that
troublesome operation of sealing tube is required for every sample,
that the used sealed tubes should be disposed, thus being
uneconomical, that heat-resistant materials such as quartz glass
cannot be used virtually due to difficult operation of sealing
tube, thereby heating of sealed tube becomes up to 600.degree. C.
at most, resulting in impossibility to decompose fire-resistant
sample, and the like.
[0006] For the hot flask method, three ways of decomposing and
absorbing methods are known and these are referred conveniently to
as "horizontal-rotating system", "vertical system" and "horizontal
system".
[0007] Thereamong, the "horizontal-rotating method" is described in
detail, for example, by W. J. Kirsten in Microchem. J., vol. 7, p.
34 (1963). Procedures are as follows; Namely, a one-sidedly closed
quartz tube with a bulge provided near entrance, in which bulge an
absorbing liquid is accommodated, is inserted horizontally into a
furnace of 850.degree. C. until this side of the absorbing liquid
portion to heat, and oxygen is filled up. Then, a quartz bar having
the sample thereon is inserted swiftly to close the quartz tube
therewith. The closed portion is allowed to rotate downward by
90.degree. together with furnace to decompose the sample. After
heated for several minutes, the quartz tube closed with quartz bar
is taken out from furnace, cooled, and shaked to absorb the
analyzed components into absorbing liquid. This
"horizontal-rotating method" has advantages that there is little
contamination due to no combustion assistant used and that the
quantity of sample is sufficient with trace amount under several
mg, but has drawbacks (1) that, since the inner pressure increases
due to evaporation of absorbing liquid which is closed in vessel,
possibility to cause the leakage is high, (2) that it is dangerous
to swiftly insert the quartz bar having organics thereon into the
tube heated to 850.degree. C., (3) that, since the tube of which
absorbing liquid portion exists nearby furnace is kept heated at
850.degree. C., there is a possibility for absorbing liquid to
evaporate up, and (4) that, since the overall furnace is rotated by
90.degree., a robust material is required.
[0008] The "vertical system" is described in detail, for example,
by W. J. Kirsten in Microchem. J., vol. 7, p. 34 (1963). Procedures
are as follows: Namely, oxygen is filled up in a one-sidedly closed
quartz tube installed vertically in a furnace of 850.degree. C. A
vessel with the absorbing liquid accommodated therein is inserted
swiftly from bottom of quartz tube together with quartz bar having
the sample thereon and closed to decompose the sample. Through the
diffusion of combustion gas, the testing components are absorbed
into absorbing liquid. This "vertical system" has advantage that
there is little contamination due to no combustion assistant used
and that the quantity of sample is sufficient with trace amount
under several mg, but has drawbacks (1) that the memory effect is
observed due to residual ash and, since the quartz bar having the
sample thereon is not washed with absorbing liquid, it is
unsuitable for a sample containing ash, (2) that, since the inner
pressure increases due to evaporation of absorbing liquid which is
closed leaving accommodate as it is, possibility to cause the
leakage is high, and (3) that it is dangerous to swiftly insert the
vessel, which accommodates absorbing liquid therein, into the tube
heated to 850.degree. C. together with the quartz bar having the
sample thereon.
[0009] The "horizontal system" is described in detail, for example,
by M. E. Fernandopulles et al in Microchem. J., vol. 11, p. 41
(1966). Namely, comparing with "horizontal-rotating system",
modifications are made to raise the temperature of furnace from
1000 to 1050.degree. C. and not to rotate by 90.degree. after
closure. This "horizontal system" has advantages that there is
little contamination due to no combustion assistant used and that
the quantity of sample is sufficient with trace amount under
several mg, but has drawbacks (1) that, since the inner pressure
increases due to evaporation of absorbing liquid which is closed
leaving accommodated as it is, possibility to cause the leakage is
high, (2) that it is dangerous to swiftly insert the quartz bar
having organics thereon into the tube heated over 1000.degree. C.
and (3) that, since the vessel with absorbing liquid portion
existing nearby furnace is kept over 1000.degree. C., there is a
possibility for absorbing liquid to evaporate up.
[0010] As described, the hot flask method has advantages of little
contamination due to no combustion assistant used and the quantity
of sample sufficient with trace amount under several mg, but has
drawbacks due to the existence of absorbing liquid in the vessel on
decomposing the sample, and the like.
[0011] The vertical type closed tube method is described in detail,
for example, by Kikushige Ono, in Summary of Presentations, p. 9
(1996) at Joint Symposium of 63rd Conversazione for Studying
Organic Microanalysis of The Japan Society for Analytical Chemistry
and 7th Sectional Meeting for Measuring Mass and Force of the
Instrumentation and Automatic Control Society. Procedures are as
follows: Namely, sample wrapped in combustion assistant is dropped
from the top of vertical closed combustion tube heated in furnace,
oxygen is blown in from oxygen blowoff port at the upper portion of
tube to burn while rotating the sample in the circumferential
direction, and combustion gas is passed additionally through filler
portion to burn completely. Then, the absorbing liquid is injected
from a mechanism for injecting absorbing liquid and all portions
including combustion section is washed to absorb the testing
components. This vertical type closed tube method has an advantage
of less obstruction by ash content etc. because of washing
combustion section, too, but has drawbacks that there is a
possibility for the washing of filler placed in combustion tube to
become insufficient, which remains a memory to contaminate next
sample, that the mechanism of washing is complicated, and that the
microanalysis is impossible due to contamination from combustion
assistant.
[0012] As described above, conventional decomposition methods
aiming at the analysis of components in organics has their merits
and demerits. Moreover, as for the devices automated each method,
there have been problems for each method.
[0013] The purpose of the invention is, replacing the conventional
appliances used for the pretreatment on analyzing the components of
halogen and sulfur in a sample which may sometimes contain
organics, methods using them and devices automated them, to provide
a closed heat-decomposing appliance (hereinafter referred to as
"inventive appliance") for the pretreatment on accurate
quantitative analysis or detection of the analyzed components in
sample, which requires no combustion assistant, which is not
obstructed by ash content present in sample absorbing the analyzed
components, which requires no complicated and dangerous procedures,
which can be used repeatedly, and which allows to inject the
absorbing liquid after heat-decomposition, a pretreatment method
(hereinafter referred to as "inventive pretreatment method") using
it, for heat-decomposing the sample which may sometimes contain
organics and further dissolving the testing components in sample, a
pretreatment device (hereinafter referred to as "inventive
pretreatment device") automates it, further a method (hereinafter
referred to as "inventive analytical method") for analyzing the
testing components after pretreatment, and a device (hereinafter
referred to as "inventive analytical device") therefor.
SUMMARY OF THE INVENTION
[0014] As a result of diligent investigations to solve the problems
aforementioned, the inventors have developed a closed
heat-decomposing appliance being an appliance for horizontally or
slantly injecting heating section into an electric furnace to heat,
decomposing the inner organics in the presence of oxygen gas,
taking out from the electric furnace and cooling, then introducing
the absorbing liquid to absorb the analyzed components, comprising
a heating section made of quartz, hard glass or ceramic with one
side closed and other side having common ground portion, screw
portion or O-ring-mounted portion and a closed introducing section
that allows to connect to this heating section and ground glass
joint screw joint or O-ring-mounted joint via O-ring-mounted
portion and has cock or valve as a mechanism for closing and
introducing the absorbing liquid to absorb the testing components
from outside after heat-decomposition, or has packing or septum to
introduce the absorbing liquid with needle pipe as well. Further,
they have found following knowledges by implementing a method for
heat-decomposing a sample which may sometimes contain organics
using this appliance and for absorbing the testing components in
sample, leading to the completion of the invention.
[0015] 1) There is little contamination due to no combustion
assistant used.
[0016] 2) Since the heat-decomposing section of sample is also
washed, there is no obstruction due to ash present in the sample
absorbing the testing components.
[0017] 3) There are no complicated dangerous procedures such as
firing of sample and combustion in flask, sealing tube operation,
insertion of sample into heating area and rotation of
heat-decomposing tube together with furnace.
[0018] 4) Since the absorbing liquid is injected after heating,
there are no anxieties of increased inner pressure due to
evaporation on heating and evaporation of absorbing liquid.
[0019] 5) The inventive appliance can be used repeatedly.
[0020] 6) The quantity of halogen and sulfure in sample can be
quantitatively analyzed accurately.
[0021] Furthermore, they have developed a device automating the
pretreatments of heat-decomposition of sample and dissolution of
testing components produced into absorbing liquid, using the
inventive appliance, and a device automating also the analysis of
testing components, leading to the completion of the invention.
[0022] Besides, in this specification, "inventive method" is
sometimes quoted in the case of describing both "inventive
pretreatment method" and "inventive analytical method", and
"inventive device" is sometimes quoted in the case of describing
both "inventive pretreatment device" and "inventive analytical
device".
DETAILED DESCRIPTION OF THE INVENTION
[0023] In following, the invention will be explained in detail.
[0024] The material for heating section of the inventive appliance
is not particularly restricted, provided 1) that no testing
components are retained onto that material through adsorption etc.
so that overall amounts of them transfer to the absorbing liquid on
next absorbing treatment, 2) that the material is hard to be
corroded with oxygen to be filled up in the inventive appliance and
corrosive gases such as hydrogen halide, halogen gas and sulfur
dioxide capable of generating from decomposed sample, 3) that the
material can withstand enough to heating during treatment, and
further 4) that the material can be molded as the heating section
of the inventive appliance, and, for example, quartz, hard glass,
ceramics such as alumina, zirconia and titania, and the like can be
used depending on the purpose. Thereamong, since the sample inside
the appliance can be observed and also heat resistance is
excellent, quartz is used preferably.
[0025] The thickness of heating section of the inventive appliance
may be such that taking in and out of sample are easy and the heat
from furnace that is the heating device to heat the inventive
appliance is transferred sufficiently, thereby causing no
unevenness of temperature in heating section and incomplete
combustion of sample, and usually thickness of around not less than
5 mm and not more than 30 mm is used.
[0026] The length of heating section of the inventive appliance is
not particularly restricted, if the sample can burn completely.
However, in the case of thicker heating section of the inventive
appliance, the sample in appliance is heat-decomposed and the
generating gas sometimes comes out of furnace without burning
completely, thus the length is preferable to be not less than 10 cm
to avoid this.
[0027] The quantity of oxygen gas to be supplied to heating section
of the inventive appliance is preferably not less than 2.5 times,
more preferably not less than 3 times the quantity of oxygen
(hereinafter referred to as "theoretical quantity of oxygen")
required for the complete combustion of sample. In case of this
range, sample burns completely, resulting in improved analytical
accuracy of sample. Besides, the theoretical quantity of oxygen is
a quantity of oxygen required to oxidize the constituting elements
in sample with oxygen, and can be calculated theoretically from the
chemical composition of sample.
[0028] The shape of heating section of the inventive appliance is
not particularly restricted and, for example, cylindrical tube,
conical tube with heating section bulged, prismatic tube, etc. can
be mentioned.
[0029] The heating device with heating means to heat the inventive
appliance and to heat-decompose the sample is not particularly
restricted, if it has a heating mechanism capable of completely
burning the sample and can install the inventive appliance, but one
provided a furnace shaped so that it can evenly heat the inside of
appliance by coming close to the inventive appliance is preferable,
and further a heating device provided with electric furnace easy to
control the heating temperature is used preferably. While depending
also on the shape of heating section of the inventive appliance,
for example, if the shape is circular, a heating device provided
with circular furnace is used preferably. In this way, use of the
heating device provided with furnace shaped complementarily with
the shape of heating section of the inventive appliance as
described above makes it possible to heat evenly, which is
preferable.
[0030] The material of an area contacting with decomposition gas of
the sample in the closed introducing section of the inventive
appliance is not particularly restricted, provided 1) that no
testing components are retained onto that material through
adsorption etc. so that overall amounts of them are transferred to
the absorbing liquid on next absorbing treatment, 2) that the
material is hard to be corroded with corrosive gases such as
hydrogen halide, halogen molecule gas and sulfur dioxide capable of
generating from decomposed sample, 3) that the material can
withstand enough to the heat of radiation from furnace during
treatment, and further 4) that the material can be molded as the
closed introducing section of the inventive appliance, and, for
example, quartz, hard glass, platinum, ceramics such as alumina,
zirconia and titania, noncorrosive materials such as fluororesin
like polytetrafluoroethylene, and the like can be used. These can
be used with one kind solely or two or more kinds in combination
depending on the structure and shape of closed introducing section
of the inventive appliance. For example, when using two-way cock as
the closed introducing section, a combination of glass for the
basic portion and fluororesin such as polytetrafluoroethylene for
the cock portion, or the like is also used.
[0031] The material of an area not contacting with decomposition
gas of the sample in the closed introducing section of the
inventive appliance is not particularly restricted, if the material
can withstand to the heat of radiation from furnace, and, for
example, various metals such as stainless steel, brass, iron and
aluminum, various glasses such as quartz and hard glass, various
resins such as polyethylene, polypropylene, polystyrene, PET, PBT,
polyamide, polyimide, phenol resin, fluororesins like
polytetrafluoroethylene etc. various rubbers such as silicone
rubber, NBR, chloroprene rubber and butyl rubber, and the like can
be used.
[0032] It is preferable to separate the closed introducing section
of the inventive appliance from furnace to some extent to suppress
the effect of the heat of radiation from furnace. The distance
cannot be determined sweepingly because of being different
depending on the temperature of furnace, and may be determined
taking the temperature of furnace, distance between furnace and
closed introducing section and material of closed introducing
section into account. For example, when using resin for the
material of closed introducing section, the temperature of closed
introducing section may be made not to exceed around 70.degree. C.,
and, when the temperature of furnace is 600.degree. C., the
distance may be made to separate 3 cm or more. As exemplified, the
distance may be determined appropriately taking the temperature of
furnace, material of each section and distance into account.
Moreover, when using more heat-resistant material such as quartz
for the material of closed introducing section, it is possible to
implement under conditions wherein the temperature of closed
introducing section is higher.
[0033] The connecting form of closed introducing section to the
heating section of the inventive appliance is not particularly
restricted, provided that, even if the inner pressure inside the
appliance may somewhat fluctuate during treatment of sample, the
connection can be achieved leaklessly, and, for example, common
grinding, screw, O-ring etc. are mentioned. Here, the shape of
O-ring is not particularly restricted and, in short, it is only
necessary to have a circular hole at central portion and to be able
to connect the closed introducing section to the heating
section.
[0034] The method for introducing the absorbing liquid into the
closed introducing section of the inventive appliance is not
particularly restricted, provided that, even if the inner pressure
may somewhat fluctuate, the absorbing liquid can be introduced
without causing the leak, and such methods that cock or valve is
used to close and it is opened and shut an introducing absorbing
liquid, that packing or septum is used to close and needle pipe is
used to introduce absorbing liquid, and the like can be mentioned.
Moreover, the material of needle pipe to inject the absorbing
liquid is not particularly restricted, provided that it is hard to
be corroded with combustion gas and absorbing liquid and has
sufficient strength and stainless steel, stainless steel with
surface-inactivating treatment such as silica coating, and the like
can be mentioned.
[0035] The heating temperature and heating time on decomposing the
sample by using the inventive appliance is not particularly
restricted, if the conditions allow to completely decompose the
sample, but conditions of preferably not lower than 600.degree. C.
and not shorter than 3 minutes, more preferably not lower than
1000.degree. C. and not shorter than 3 minutes are suitable. In
particular, for a fire-resistant sample etc. containing high level
of ash, heating over 1000.degree. C. is preferable.
[0036] For setting up the sample in the inventive appliance, such
methods that a vessel made of noncorrosive material such as
platinum boat, ceramic boat, quartz boat or hard glass boat is
used, that the sample is set up directly in the inventive
appliance, and the like can be mentioned.
[0037] As the method for installing the inventive appliance in
furnace, it is desirable to insert it horizontally or slantly into
the furnace of heating device. More preferably, it is desirable to
insert it horizontally or by slanting the closed introducing
section downwards so that the decomposition gas of sample does not
rise rapidly by convection to come out of furnace.
[0038] As for the oxygen to be filled up in the inventive
appliance, such methods that pure oxygen, moist oxygen or oxygen
mixed with inert gas such as nitrogen, helium or argon is filled
up, and the like are mentioned.
[0039] The sample for pretreatment using the inventive appliance
may or may not contain halogen and/or sulfur therein, and it is
only necessary to determine depending on the purpose. When halogen
and/or sulfur are contained in the sample, the inventive appliance
can be used for quantitative determination of the content of
halogen and/or sulfur in sample. Here, the contents of halogen
and/or sulfur in sample mean that compound contained in sample may
be single compound or a mixture of two or more compounds, and, in
the case of single compound, compound contained therein can also be
identified by comparing with the theoretical content of halogen
and/or sulfur presumable from the structure of that compound.
[0040] The components in sample may or may not contain organics,
and, when organics are contained, the organics are heated and
burned by the inventive method, which is more effective. The sample
is heat-decomposed by the inventive method, thereby the analyzed
components are mineralized. The analyzed components are one or more
kinds selected from a group consisting of halogen and sulfur, and,
despite that the testing component(s) is solely one kind of halogen
and sulfur or are two or more kinds, it(they) can be pretreated by
the inventive method allowing to be submitted to the analysis.
[0041] Moreover, the inventive method can also be used to identify
that one or more kinds of halogen and sulfur are not contained in
the sample. In this case, it is possible to identify when neither
halogen nor sulfur is contained in the sample and also to identify
that either of particular halogen and sulfur is not contained in
the sample. On that identification, while depending on the
analytical method used, it is judged usually that it(they) is(are)
not contained, if being not recognized within the sensitivity of
that analytical method.
[0042] Moreover, the sample heat-decomposed by the inventive method
is next submitted to the measurement of halogen and/or sulfur being
the testing components. At this time, the analytical sample which
may sometimes contain the testing components is prepared by
introducing the absorbing liquid into the inventive appliance.
[0043] Here, the absorbing liquid to be used in the inventive
method is not particularly restricted, if it can quantitatively
dissolve the gas etc. containing halogen and sulfur originating
from the heat-decomposed sample and keep them in a single form. For
example, solution containing solely one kind, combined solution of
arbitrary two or three kinds of hydrogen peroxide solution,
hydrazine hydrate solution, aqueous solution of alkali metal
hydroxide such as sodium hydroxide or potassium hydroxide, alkali
solution such as aqueous ammonia, and the like, or pure water can
be used. Thereamong, from the simplicity, it is preferable to use
solely one kind of hydrogen peroxide solution, hydrazine solution,
alkali solution and pure water as the absorbing liquid, and, for
more highly exerting the effect as an absorbing liquid, it is
preferable to use combination of arbitrary two kinds of hydrogen
peroxide solution, hydrazine hydrate solution and alkali solution
as the absorbing liquid.
[0044] In addition, upon using the absorbing liquid, it is also
possible to select the type depending on the kind of halogen and
sulfur to be analyzed after implementing the inventive pretreatment
method. For example, when analyzing fluorine as a halogen, only
pure water may be used, and, when analyzing chlorine, bromine or
iodine as a halogen, it is preferable to use hydrogen peroxide
solution or hydrazine hydrate solution to reduce halogen molecule
gas generating after combustion, to which alkali solution can be
added, if need be, when analyzing sulfur, hydrogen peroxide is
preferably used to oxidize sulfur oxides generating after
combustion, to which hydrazine hydrate solution or alkali solution
can also be added, if need be. Further, for a compound having two
or more kinds of these halogen and sulfur, the type of absorbing
liquid may be selected appropriately depending on the composition
of that compound.
[0045] On the other hand, when inorganic components such as alkali
metal exist in the sample, halogen and sulfur originating from
sample are often caught by this metal component as, for example,
sodium chloride or iron sulfate, hence an absorbing liquid that can
dissolve this caught component, too, is preferable.
[0046] Moreover, after introduction of absorbing liquid, the
absorbing liquid contacts with the components originating from the
heat-decomposed sample to absorb them into the absorbing liquid. At
this time, it is possible to shorten the time by applying vibration
etc. to appliance to increase the absorbing speed. As for the
methods for vibration, any method of manual shaking, automated
treatment with suitable device, and the like may be used.
[0047] The pretreated absorbed liquid thus obtained can be used as
a sample for quantitative analysis and, as the methods for
quantitative analysis, ion chromatographic method, titration
method, calorimetric method, ion electrode method, etc. are
mentioned.
[0048] Moreover, after the treatment as describe above, the
inventive appliance can also be used again for the treatment of
another sample after washing.
[0049] Examples of the inventive appliance comprising each section
as described are shown in FIG. 1, FIG. 2, FIG. 3, FIG. 4 and FIG.
5. In following, the inventive appliance will be illustrated more
concretely using figures. Besides, in the figures, mark showing
each section is shown as a common number.
[0050] FIG. 1 is a schematic diagram of cross section of the
inventive appliance in the axial direction. In FIG. 1, number 1 is
an example using quartz tube with one side closed and other side
having common grinding 2. In place of this quartz tube 1, those
made of said materials such as hard glass tube and alumina ceramic
tube can also be used. To this common grinding 2, absorbing
liquid-introducing section made of hard glass etc. and provided
with two-way cock 3 and absorbing liquid reservoir 4 is connected.
On actual pretreatment, after oxygen and sample were set up in the
quartz tube 1, two-way cock 3 is closed, heat-decomposition is
performed followed by cooling, then absorbing liquid is
accommodated in the absorbing liquid reservoir 4, and two-way cock
3 is opened to introduce the absorbing liquid into tube for
use.
[0051] FIG. 2 is a schematic diagram of cross section of the
inventive appliance in the axial direction. In FIG. 2, numeral 1 is
an example using quartz tube with one side closed and other side
having common grinding 2. To this common grinding 2, absorbing
liquid-introducing section as described above, made of hard glass
etc. and provided with absorbing liquid reservoir 4 and solenoid
valve 5 is connected. On actual pretreatment, operation may be made
similarly to the case of appliance shown in FIG. 1.
[0052] FIG. 3 is a schematic diagram of cross section of the
inventive appliance in the axial direction. In FIG. 2, numeral 1 is
an example using quartz tube with one side closed and other side
having thread ridge. A screw cap 6 fitted accurately to this thread
ridge is connected to the quartz tube 1, interposing a septum 7
made of NBR rubber and stretched with Teflon membrane, the side of
Teflon being directed to the inside of tube. On actual
pretreatment, the absorbing liquid is injected with needle pipe
from a small hole opened at the upper portion of screw cap 6,
piercing through the septum 7 for use.
[0053] FIG. 4 is a schematic diagram of cross section of the
inventive appliance in the axial direction. In FIG. 4, numeral 1 is
an example using quartz tube with one side closed and other side
having O-ring receiver 8. To this O-ring receiver 8, the absorbing
liquid-introducing section made of hard glass and provided with
absorbing liquid reservoir 4 and two-way cock 3 is connected via
O-ring 9, which is tightened with clamp 10 for use.
[0054] FIG. 5 is a schematic diagram at the time of heating with
circular electric furnace by using the inventive appliance. The
inventive appliance with sample 11 placed therein is placed in the
circular electric furnace 12 and, while measuring the temperature
with thermocouple 13, temperature is controlled with
temperature-controlling device to heat, thereby allowing to
heat-decompose the sample 11 in the inventive appliance.
[0055] Next, the inventive device will be illustrated in
detail.
[0056] The inventive device comprises a device for the inventive
pretreatment of sample, consisting of appliance-installing section
for installing the inventive appliance, heating means to
heat-decompose the sample in the inventive appliance, cooling means
to cool the inventive appliance after heat-decomposition of sample
in the inventive appliance, injecting means to inject the absorbing
liquid into the inventive appliance after cooling, mixing means to
stir and/or shake for making the absorbing liquid in the inventive
appliance uniform and moving means to reversibly move the inventive
appliance from appliance-installing section to any of cooling
means, injecting means and mixing means and from there to any of
others thereamong. Further, in addition to this pretreatment device
of sample, sampling means to sample part of the absorbed liquid in
the inventive appliance and to move to analyzing means, and the
inventive analytical device having analyzing means to analyze the
testing components in absorbed liquid are also within a range of
the invention.
[0057] The material of appliance-installing section to be used for
the inventive appliance is not particularly restricted, and it is
only necessary to have a structure that holds the inventive
appliance one by one, and that can move the inventive appliance
with the measuring sample accommodated therein by moving means
shown below after start of pretreatment, or can install the
inventive appliance to its appliance-installing section by moving
means after pretreatment.
[0058] The heating means to be used in the inventive device is not
particularly restricted, provided that it has a capacity capable of
heat-decomposing the measuring sample as described above and that
one or a plurality of the inventive appliances are moved by moving
means shown below after start of pretreatment to set up the heating
section of the inventive appliance. As a heating device with such
heating means, for example, electric furnace easy to control the
heating temperature is used preferably and, as for the shape
thereof, it is preferable to be a furnace shaped complementarily
with the shape of heating section of the inventive appliance.
[0059] The cooling means to be used in the inventive device is not
particularly restricted, if it has a mechanism that, after
heat-decomposing the measuring sample in the inventive appliance by
said heating means, the inventive appliance is taken out from the
heating means by moving means, and thereafter the heated inventive
appliance is held above this cooling device to allow to cool to a
temperature as low as the room temperature, but, for avoiding the
failure of the inventive appliance due to rapid cooling, air
cooling with fan, air shower or the like is preferable. As for the
distance between the inventive appliance and the cooling means
during cooling, it is only necessary to be a distance capable of
rapidly cooling the heated inventive appliance, depending on the
size of cooling means, exhaust capacity of air etc. and the like.
Moreover, without using the device with such cooling mechanism, the
inventive appliance may be allowed to stand for cooling by holding
it as it is after taken out the heated inventive appliance by
moving means.
[0060] The injecting means to be used in the inventive device is
not particularly restricted, if it can hold the inventive appliance
cooled by said cooling means and inject the absorbing liquid
without leak of gas of the testing components produced by
decomposition of sample set up in the inventive appliance. For
example, when using the inventive appliance that opens and shuts
the closed introducing section closed with cock or valve on
introduction of the absorbing liquid, a mechanism for injecting
under pressure from tube connected to cock or valve using various
pumps etc., a mechanism for sucking the absorbing liquid from tube
connected to cock or valve, making the inside negative pressure by
cooling the inventive appliance, and the like can be used.
Moreover, when using the inventive appliance that is closed with
packing or septum and introduces the absorbing liquid with needle
pipe, a mechanism for injecting under pressure from tube connected
to needle pipe using various pumps etc. and the like can be used.
Thereamong, preferably, in the case of appliance comprising the
closed introducing section with packing or septum to introduce the
absorbing liquid with needle pipe as a mechanism for introducing
the absorbing liquid for absorbing the testing components from
outside, an absorbing liquid-injecting mechanism comprising needle
pipe, motor buret, valve with actuator, moving mechanism of needle
pipe and washing port, wherein the needle pipe is pierced through
the packing or septum of the inventive appliance by moving
mechanism, the absorbing liquid is introduced by switching the
valve with actuator and working the motor buret, and then needle
pipe is moved to the washing port by moving mechanism to wash the
contaminated needle pipe, is preferable for use.
[0061] The mixing means to stir and/or shake for making the
absorbing liquid in the inventive appliance uniform to be used in
the inventive device is to mix gaseous halogen and/or sulfur being
the testing components generated by decomposition of the inner
measuring sample during heating of the inventive appliance, with
the absorbing liquid injected into the inventive appliance by said
injecting means, and to make the concentration of the testing
components being dissolved into the absorbing liquid and existing
in that solution uniform, and is not particularly restricted, if it
can wash out the wall of vessel and all with absorbing liquid so
that all including the testing components stuck onto the wall of
vessel are taken into the absorbing liquid and can make the
absorbed liquid in the inventive appliance uniform. For example, a
mechanism for rotating the inventive appliance installed
horizontally centering around axis, a mechanism for moving the
inventive appliance installed vertically up and down centering
around axis, a mechanism for rotating the inventive appliance
installed vertically in parallel with axis, and the like can be
mentioned. Thereamong, preferably, one with a stirring mechanism
for reciprocating the inventive appliance installed horizontally in
the axial direction while rotating centering around axis is
preferable for use.
[0062] The moving means that supports the inventive appliance and
moves it reversibly to each portion of appliance-installing
section, heating means, cooling means, injecting means, mixing
means or the like to be used in the inventive deice is not
particularly restricted, if it has a mechanism for transporting the
inventive appliance while holding it. Among the moving means with
such mechanism, it is preferable to equip a mechanical hand that
holds the inventive appliance and to utilize one or more of cross
type motor robot, cross type multiaxial motor robot, multijoint
type robot, belt conveyer, air cylinder, hydraulic cylinder, etc.
Further, it is preferable to use cross type motor robot with
mechanical hand or cross type motor robot with mechanical hand and
axis for rotating this.
[0063] With a device provided with such each means, the inventive
pretreatment device for performing the pretreatments such as
heat-decomposition of sample and dissolution of analyzed components
producing by heat-decomposition into absorbing liquid is
constituted.
[0064] Furthermore, by combining an analytical device provided with
sampling means shown below with this inventive pretreatment device,
the inventive analytical device is constituted.
[0065] Namely, the sampling means for sampling part of the absorbed
liquid inside the inventive appliance and moving to the analyzing
means to be used in the inventive device is not particularly
restricted, if it can sample part or all of the absorbed liquid
from absorbed liquid with the analyzed components dissolved
uniformly in the inventive appliance by said mixing means. For
example, a mechanism for sucking the absorbed liquid by inserting
the needle pipe into the inventive appliance, a mechanism for
discharging the absorbed liquid by pressurizing the inside, and the
like can be mentioned.
[0066] The analytical device with analyzing means to analyze the
testing components in the absorbed liquid to be used in the
inventive device is not particularly restricted, if it can analyze
the testing components by interlocking with the mechanism for
sampling the absorbed liquid from the inventive appliance and
feeding. For example, ion chromatograph, automatic titrator,
automatic spectrophotometer, ion meter, etc. are mentioned.
[0067] In following, said each section to be used in the inventive
pretreatment device and the inventive analytical device will be
illustrated more concretely, referring to drawings.
[0068] FIG. 6 is a schematic diagram of the inventive pretreatment
device. In FIG. 6, numeral 15 is the inventive appliance and, by
cross type motor robot 16 and mechanical hand 17, the inventive
appliance 15 is transported from appliance-installing section 18 to
circular electric furnace 12.
[0069] FIG. 7 is a schematic diagram of the inventive pretreatment
device. In FIG. 7, numeral 15 is the inventive appliance and, by
multijoint type motor robot 19 and mechanical hand 17, the
inventive appliance 15 is transported from appliance-installing
section 18 to circular electric furnace 12.
[0070] FIG. 8 is a schematic diagram of the inventive pretreatment
device. In FIG. 8, numeral 15 is the inventive appliance and, by
belt conveyer 20, air cylinder 21 and mechanical hand 17, the
inventive appliance 15 is transported from appliance-installing
section 18 to circular electric furnace 12.
[0071] FIG. 9 is a schematic diagram of the mechanism for injecting
the absorbing liquid into the inventive appliance. In FIG. 9,
numeral 15 is the inventive appliance with packing or septum,
numeral 22 is needle pipe, numeral 23 is motor buret, numeral 24 is
valve with actuator, numeral 25 is moving mechanism of needle pipe
and numeral 26 is washing boat. The needle pipe 22 is pierced
through packing or septum of the inventive appliance 15 by moving
mechanism 25, and, after injected the absorbing liquid in absorbing
liquid reservoir 27 by switching valve 24 with actuator and working
motor buret 23, the needle pipe 22 is moved to washing port 26 by
moving mechanism 25 to wash the contaminated needle pipe with
washing liquid in the washing liquid reservoir 28.
[0072] Further, in the mechanism for injecting the absorbing liquid
into the inventive appliance, the inventive appliance is connected
to cock (solenoid valve) and the cock is connected to motor buret
accommodated with absorbing liquid via tube to inject the absorbing
liquid into the inventive appliance by opening cock and working
motor buret. Or, the inventive appliance is connected to cock and
the cock is connected to plunger pump via tube to inject the
absorbing liquid into the inventive appliance by opening cock and
working plunger pump. Or, the inventive appliance is connected to
valve and the valve is connected to motor buret accommodated with
absorbing liquid via tube to inject the absorbing liquid into the
inventive appliance by switching valve to connect the motor buret
to the inventive appliance and working motor buret. Or, the
inventive appliance is connected to valve and the valve is
connected to absorbing liquid reservoir accommodated with absorbing
liquid via tube to inject the absorbing liquid into the inventive
appliance by cooling the inventive appliance to make the inside of
appliance negative pressure and switching valve to connect the
absorbing liquid reservoir to the inventive appliance.
[0073] FIG. 10 is a schematic diagram of the inventive pretreatment
device. In FIG. 10, numeral 15 is the inventive appliance and, by
cross type motor robot 16 and mechanical hand 17, the inventive
appliance 15 is transported from appliance-installing section 18 to
circular electric furnace 12. Thereafter, the heated inventive
appliance 15 is transported to fan 29 to be cooled and then
transported to absorbing liquid-injecting mechanism 30 to receive
injection of absorbing liquid.
[0074] FIG. 11 is a schematic diagram of the inventive pretreatment
device. In FIG. 11, numeral 15 is the inventive appliance and, by
belt conveyer 20, air cylinder 21 and mechanical hand 17, the
inventive appliance 15 is transported from appliance-installing
section 18 to circular electric furnace 12. Thereafter, the heated
inventive appliance 15 is transported to air shower 31 to be cooled
and then transported to absorbing liquid-injecting mechanism 30 to
receive injection of absorbing liquid.
[0075] FIG. 12 is a schematic diagram of the inventive pretreatment
device. In FIG. 12, numeral 15 is the inventive appliance and, by
multijoint type motor robot 19 and mechanical hand 17, the
inventive appliance 15 is transported from appliance-installing
section 18 to circular electric furnace 12. Thereafter, the heated
inventive appliance 15 is transported to air shower 31 to be cooled
and then transported to absorbing liquid-injecting mechanism 30 to
receive injection of absorbing liquid.
[0076] FIG. 13 is a schematic diagram of the inventive pretreatment
device. In FIG. 13, numeral 15 is the inventive appliance and, by
air cylinder 21 and mechanical hand 17, the inventive appliance 15
is transported from appliance-installing section 18 to circular
electric furnace 12. Thereafter, the heated inventive appliance 15
is transported to air shower 31 to be cooled and then transported
to absorbing liquid-injecting mechanism 30 to receive injection of
absorbing liquid.
[0077] FIG. 14 is a schematic diagram of the inventive analytical
device. In FIG. 14, numeral 15 is the inventive appliance and, by
cross type multiaxial motor robot 34 and mechanical hand 17, the
inventive appliance 15 is transported from appliance-installing
section 18 to circular electric furnace 12. Thereafter, the heated
inventive appliance 15 is transported to air shower 31 to be cooled
and then transported to absorbing liquid-injecting mechanism 30 to
receive injection of absorbing liquid. And, after sufficiently
stirred the inventive appliance 15 by cross type multiaxial motor
robot 34 and mechanical hand 17, port or all of absorbed liquid in
the inventive appliance 15 are sampled with autosampler 32 and
injected into ion chromatographic deice 33 to analyze the testing
components.
[0078] FIG. 15 is a schematic diagram of the inventive analytical
device. In FIG. 15, numeral 15 is the inventive appliance and, by
cross type multiaxial motor robot 34 and mechanical hand 17, the
inventive appliance 15 is transported from appliance-installing
section 18 to circular electric furnace 12. Thereafter, the heated
inventive appliance 15 is transported to fan 29 to be cooled and
then transported to absorbing liquid-injecting mechanism 30 to
receive injection of absorbing liquid. And, after sufficiently
stirred the inventive appliance 15 with stirring absorbing
mechanism comprising uniaxial motor robot 35 and mechanical hand
17, port or all of absorbed liquid are sampled with autosamnler 32
and injected into ion chromatographic device 33 to analyze the
testing components. Besides, as for the stirring absorbing
mechanism, a stirring absorbing mechanism comprising air cylinder
or belt conveyer and mechanical hand may be used.
[0079] By appropriately disposing each means to be used in the
inventive device as above, the inventive pretreatment device or the
inventive analytical device is constituted.
[0080] Moreover, on the actual pretreatment or analysis, each
section in these inventive devices may be operated separately by
each section, but can be operated under control by information
processing means such as computer so as to become the routine
aforementioned.
[0081] The inventive appliance, inventive method and inventive
device as described above are used suitably for the quality control
of organics to be manufactured or used, identification of
compounds, grasp of elemental compositions, and the like in all
industries such as petroleum, chemicals, medicines, foods,
semiconductor and papermaking.
[0082] In following, the invention will be illustrated in detail
based on the examples, but the invention is not confined only to
these examples.
[0083] Besides, the results etc. obtained in following examples 1
through 20 are collectively shown, respectively; type of sample,
quantity of sample, theoretical amount of oxygen, amount of oxygen
at heating section of the inventive appliance and ratio of amount
of oxygen at heating section to theoretical amount of oxygen in
Table 1; material of heating section, inner diameter of heating
section, length on injection of sample into furnace, heating
temperature, heating time, material of sample boat, type of
absorbing liquid used and angle on slanting sample in Table 2;
contents of halogen and sulfur derived theoretically from sample
(theoretical value), contents of halogen and sulfur obtained as a
result (observed value) and recovery rate being a ratio
therebetween (observed value/theoretical value) in Table 3.
1TABLE 1 (Sample) Theoretical Amount of Amt. of oxygen at Quantity
amount of oxygen at heating section/ Example of sample oxygen
heating section theoretical amt. of No. Type of Sample (mg) (ml)
(ml) oxygen Example 1 S-benzylthiuronium chloride Ca.5 8.15 40.2
4.93 Example 2 Fire-resistant ABS Ca.5 9.60 40.2 4.19 Example 3
S-benzylthiuronium chloride 4.790 7.82 40.2 5.14 Example 4
S-benzylthiuronium chloride 2.902 4.74 15.7 3.31 Example 5
S-benzylthiuronium chloride 3.601 5.88 15.7 2.67 Example 6
S-benzylthiuronium chloride 7.712 12.6 40.2 3.19 Example 7
S-benzylthiuronium chloride 2.282 3.72 11.8 3.17 Example 8
S-benzylthiuronium chloride 4.885 7.97 40.2 5.04 Example 9
S-benzylthiuronium chloride 4.915 8.02 40.2 5.01 Example 10
S-benzylthiuronium chloride 2.486 4.06 15.7 3.87 Example 11
S-benzylthiuronium chloride 5.302 8.65 57.2 6.61 Example 12
S-benzylthiuronium chloride 5.118 8.35 40.2 4.81 Example 13
S-benzylthiuronium chloride 4.457 7.27 40.2 5.53 Example 14
S-benzylthiuronium chloride 5.339 8.71 40.2 4.62 Example 15
S-benzylthiuronium chloride 4.754 7.76 40.2 5.18 Example 16
Fire-resistant ABS 5.080 9.74 40.2 4.13 Example 17 p-chlorobenzoic
acid 4.804 5.26 40.2 7.64 Example 18 S-benzylthiuronium chloride
1.573 2.57 15.7 6.11 Example 19 S-benzylthiuronium chloride 4.900
8.00 40.2 5.03 Example 20 o-iodobenzoic acid 5.370 3.71 40.2
10.8
[0084]
2TABLE 2 (Appliance plus conditions) Inner diameter Inserting
Material of of heating length into Heating Heating Type of Slanting
Example heating section furnace temperature time Material of
absorbing angle No. section (mm) (cm) (.degree. C.) (min) sample
boat liquid (deg.) Example 1 Quartz 16 20 1000 5 Platinum NaOH +
H.sub.2O.sub.2 0 Example 2 Quartz 16 20 1000 5 Platinum NaOH +
H.sub.2O.sub.2 0 Example 3 Quartz 16 20 800 3 Platinum NaOH +
H.sub.2O.sub.2 0 Example 4 Quartz 10 20 1000 5 Platinum NaOH +
H.sub.2O.sub.2 0 Example 5 Quartz 10 20 1000 5 Platinum NaOH +
H.sub.2O.sub.2 0 Example 6 Quartz 16 20 1000 5 Platinum NaOH +
H.sub.2O.sub.2 0 Example 7 Quartz 10 15 1000 5 Platinum NaOH +
H.sub.2O.sub.2 0 Example 8 Quartz 16 20 1000 5 Quartz NaOH +
H.sub.2O.sub.2 0 Example 9 Quartz 16 20 1000 5 Ceramic NaOH +
H.sub.2O.sub.2 0 Example 10 Quartz 10 20 1000 5 Direct set up NaOH
+ H.sub.2O.sub.2 0 Example 11 Quartz 27 10 1000 5 Quartz NaOH +
H.sub.2O.sub.2 0 Example 12 Quartz 16 20 1000 5 Platinum NaOH +
H.sub.2O.sub.2 0 Example 13 Quartz 16 20 1000 5 Platinum NaOH +
H.sub.2O.sub.2 0 Example 14 Quartz 16 20 1000 5 Platinum NaOH +
H.sub.2O.sub.2 0 Example 15 Quartz 16 20 1000 5 Platinum NaOH +
H.sub.2O.sub.2 30 Example 16 Quartz 16 20 1000 5 Platinum NaOH +
NH.sub.2NH.sub.2 0 Example 17 Quartz 16 20 1000 5 Quartz H.sub.2O 0
Example 18 Hard glass 10 20 600 30 Hard glass NaOH + H.sub.2O.sub.2
0 Example 19 Ceramic 16 20 1000 5 Platinum NaOH + H.sub.2O.sub.2 0
Example 20 Quartz 16 20 1000 5 Platinum NaOH + NH.sub.2NH.sub.2 +
H.sub.2O.sub.2 0
[0085]
3TABLE 3 (Results) Theoretical Observed Example value value
Recovery No. (%) (%) rate (%) Example 1 Cl: 17.49 Cl: 17.46 Cl:
99.83 S: 15.82 S: 15.67 S: 99.05 Example 2 Br: 9.73 Br: 9.62 Br:
98.87 Example 3 Cl: 17.49 Cl: 17.52 Cl: 100.17 S: 15.82 S: 15.64 S:
98.86 Example 4 Cl: 17.49 Cl: 17.66 Cl: 100.97 S: 15.82 S: 15.79 S:
99.81 Example 5 Cl: 17.49 Cl: 18.04 Cl: 103.14 S: 15.82 S: 15.96 S:
100.88 Example 6 Cl: 17.49 Cl: 17.32 Cl: 99.03 S: 15.82 S: 15.70 S:
99.24 Example 7 Cl: 17.49 Cl: 17.32 Cl: 99.03 S: 15.82 S: 15.54 S:
98.23 Example 8 Cl: 17.49 Cl: 17.42 Cl: 99.60 S: 15.82 S: 15.74 S:
99.49 Example 9 Cl: 17.49 Cl: 17.31 Cl: 98.97 S: 15.82 S: 15.66 S:
98.99 Example 10 Cl: 17.49 Cl: 17.66 Cl: 100.97 S: 15.82 S: 15.79
S: 99.81 Example 11 Cl: 17.49 Cl: 17.45 Cl: 99.77 S: 15.82 S: 15.55
S: 98.29 Example 12 Cl: 17.49 Cl: 17.56 Cl: 100.40 S: 15.82 S:
15.65 S: 98.93 Example 13 Cl: 17.49 Cl: 17.32 Cl: 99.03 S: 15.82 S:
15.66 S: 98.99 Example 14 Cl: 17.49 Cl: 17.57 Cl: 100.46 S: 15.82
S: 15.79 S: 99.81 Example 15 Cl: 17.49 Cl: 17.28 Cl: 98.80 S: 15.82
S: 15.82 S: 100.00 Example 16 Br: 9.73 Br: 9.55 Br: 98.15 Example
17 Cl: 22.64 Cl: 22.00 Cl: 97.17 Example 18 Cl: 17.49 Cl: 17.90 Cl:
102.34 S: 15.82 S: 15.43 S: 97.53 Example 19 Cl: 17.49 Cl: 17.44
Cl: 99.71 S: 15.82 S: 15.77 S: 99.68 Example 20 I: 15.17 I: 15.09
I: 99.47
[0086] Moreover, the values of detecting lower limit (detecting
sensibility) of IC measurement are 0.05 .mu.g/ml for fluorine
(F.sup.-), 0.05 .mu.g/ml for chlorine (Cl.sup.-), 0.1 .mu.g/ml for
bromine (Br.sup.-), 0.3 .mu.g/ml for iodine (I.sup.-) and 0.1
.mu.g/ml for sulfur (as SO.sub.4.sup.2.sup..sup.-). In following
examples, the contents of halogen and sulfur in sample determined
by the detecting lower limit of IC measurement are 0.05% for
fluorine, 0.05% for chlorine, 0.1% for bromine, 0.3% for iodine and
0.03% for sulfur, and the contents of elements not described in
each example are below those described above. In addition, IC
measurement was made by diluting the absorbed liquid to 50 ml, but,
if diluting to 5 ml being one tenth, the detection limit for the
contents of halogen and sulfur in sample will become one tenth of
those above.
EXAMPLE 1
[0087] About 5 mg of S-benzylthiuronium chloride (from Kishida
Kagaku Co.) were weighed out accurately into a platinum boat with
length of 5 mm, width of 15 mm and height of 4 mm using
microbalance M-3 from Metler Co., and inserted deep in a closed
heat-decomposing appliance (length of tube: 30 cm, inner diameter
of tube: 16 mm, outer diameter of tube: 18 mm) shown in FIG. 1.
After injected oxygen, the appliance was stoppered at the absorbing
liquid-introducing section. This closed heat-decomposing appliance
was inserted horizontally as far as about 20 cm beforehand from the
side of sample into a circular electric furnace (from Isuzu
Seisakusho Co., attached with temperature controller EC5600 from
Okura Electric Co.) heated to 1000.degree. C. and heated for 5
minutes. Then, the closed heat-decomposing appliance was drawn out
from the furnace, cooled, and injected with 2.5 ml of absorbing
liquid comprising an aqueous solution of 0.04 mol/L sodium
hydroxide and 24% by weight of hydrogen peroxide from two-way cock,
followed by shaking, which was allowed to stand for 30 minutes.
Thereafter, the inside of the closed heat-decomposing appliance
including ground portion was washed with pure water and diluted to
50 ml to submit to IC measurement.
[0088] As for IC, CCPM (specified for resin) from Tosoh Corp. was
used for pump, CM-8010 (electroconductivity detector) from Tosoh
Corp. for detector, CO-8011 from Tosoh Corp. for column oven,
SC-8020 from Tosoh Corp. for integrator, TSK gel IC-Anion-PwPEEK
(4.6 mm I.D..times.50 mm) from Tosoh Corp. for analytical column,
and 1,3 mM potassium gluconate-1.3 mM borax-30 mM boric acid-5%
acetonitrile-0.5% glycerine for mobile layer, and measurement was
made under flow rate of 1.2 ml/min, column temperature of
40.degree. C. and sample injection level of 100 .mu.L. The
calibration curve was prepared by appropriately diluting anion
standard solution from Wako Pure Chemical Industries Ltd. to
measure the absorbed liquid after decomposition of sample.
[0089] To the theoretical contents (% by weight) of 17.49% for Cl
and 15.82% for S in 5-benzylthiuronium chloride, the average and
relative standard deviations (RSD) on ten measurements (three
appliances were use repeatedly four times, four times and two times
for each appliance) were 17.46% (RJD=0.88%) for Cl and 15.67%
(RSD=0.35%) for S.
[0090] Besides, in this example, the ratio of the amount of oxygen
(=40.2 ml) at heating section to the theoretical amount of oxygen
(=8.15 ml) required for complete combustion of S-benzylthiuronium
chloride was 4.93.
EXAMPLE 2
[0091] Except that a fire-resistant ABS kneaded 100 parts of ABS
(trade name JSR ABS10) from Japan Synthetic Rubber Co. with 26
parts of brominated epoxy resin flame retardant (trade name
YDB-408) from Tokyo Kasei Co. and 8.7 parts of flame retardant Sb
203 (trade name Flame Cut 610R) from Tosoh Corp. was used for the
sample, sample was pretreated similarly to Example 1 to implement
the IC measurement. As a result, to the content (% by weight) of
9.73% for Br in this substance determined from the quantity
charged, the average and relative standard deviation on seen
measurements (two appliances were used repeatedly five times and
two times for each appliance) were 9.62% (RSD=1.53%).
EXAMPLE 3
[0092] Except that the temperature of furnace and the heating time
were made to be 800.degree. C. and 3 minutes, respectively, sample
was pretreated similarly to Example 1 to implement the IC
measurement. As a result, to the theoretical contents (% by weight)
of 17.49% for Cl and 15.82% for S in S-benzylthiuronium chloride,
17.52% and 15.64% were obtained for Cl and S. respectively.
EXAMPLE 4
[0093] Except that the shape of the closed heat-decomposing
appliance used in Example 1 was made to be length of tube of 30 cm,
inner diameter of tube of 10 mm and outer diameter of tube of 12 mm
and 2.902 mg of S-benzylthiuronium chloride were used, sample was
pretreated similarly to Example 1 to implement the IC measurement.
As a result, to the theoretical contents (% by weight) of 17.49%
for Cl and 15.82% for S in S-benzylthiuronium chloride, 17.66% and
15.79% were obtained for Cl and S, respectively.
[0094] Besides, in this example, the ratio of the amount of oxygen
(=15.7 ml) at heating section to the theoretical amount of oxygen
(=4.74 ml) required for complete combustion of S-benzylthiuronium
chloride was 3.31.
EXAMPLE 5
[0095] Except that 3.601 mg of S-benzylthiuronium chloride were
used, sample was pretreated similarly to Example 4 to implement the
IC measurement similarly to Example 1. As a result, to the
theoretical contents (% by weight) of 17.49% for Cl and 15.82% for
S in S-benzylthiuronium chloride, 18.04% and 15.96% were obtained
for Cl and S, respectively.
[0096] Besides, in this example, the ratio of the amount of oxygen
(=15.7 ml) at heating section to the theoretical amount of oxygen
(=5.88 ml) required for complete combustion of S-benzylthiuronium
chloride was 2.67.
EXAMPLE 6
[0097] Except that 7.712 mg of S-benzylthiuronium chloride were
used, sample was pretreated similarly to Example 1 to implement the
IC measurement. As a result, to the theoretical contents (% by
weight) of 17.49% for Cl and 15.82% for S in S-benzylthiuronium
chloride, 17.32% and 15.70% were obtained for Cl and S,
respectively.
[0098] Besides, in this example, the ratio of the amount of oxygen
(=40.2 ml) at heating section to the theoretical amount of oxygen
(=12.6 ml) required for complete combustion of S-benzylthiuronium
chloride was 3.19.
EXAMPLE 7
[0099] Except that 2.282 mg of S-benzylthiuronium chloride were
inserted into the closed heat-decomposing appliance used in Example
4 and the closed heat-decomposing appliance was inserted as far as
15 cm into circular electric furnace from the side of sample,
sample was pretreated similarly to Example 1 to implement the IC
measurement. As a result, to the theoretical contents (by weight)
of 17.49% for Cl and 15.82% for S in S-benzylthiuronium chloride,
17.32% and 15.54% were obtained for Cl and S, respectively.
[0100] Besides, in this example, the ratio of the amount of oxygen
(=11.8 ml) at heating section to the theoretical amount of oxygen
(=3.72 ml) required for complete combustion of S-benzylthiuronium
chloride was 3.17.
EXAMPLE 8
[0101] Except that S-benzylthiuronium chloride was placed in a
quartz boat (length: 5 mm, width: 15 mm, height: 3 mm), sample was
pretreated similarly Example 1 to implement the IC measurement. As
a result, to the theoretical contents (% by weight) of 17.49% for
Cl and 15.82% for S in S-benzylthiuronium chloride, 17.42% and
15.74% was obtained for Cl and S, respectively.
EXAMPLE 9
[0102] Except that S-benzylthiuronium chloride was placed in a
alumina ceramic boat (length: 5 mm, width: 15 mm, height: 4 mm),
sample was pretreated similarly Example 1 to implement the IC
measurement. As a result, to the theoretical contents (% by weight)
of 17.49% for Cl and 15.82% for S in S-benzylthiuronium chloride,
17.31% and 15.66% was obtained for Cl and S, respectively.
EXAMPLE 10
[0103] Except that S-benzylthiuronium chloride was accommodated in
a sampling vessel and weighed accurately, and, after dropped sample
alone in the closed heat-decomposing appliance, the sampling vessel
was weighed accurately to determine the quantity of sample, sample
was treated similarly to Example 4 to implement the IC measurement
similarly to Example 1. As a result, to the theoretical contents (%
by weight) of 17.49% for Cl and 15.82% for S in S-benzylthiuronium
chloride, 17.66% and 15.79% were obtained for Cl and S,
respectively.
EXAMPLE 11
[0104] Except that the shape of the closed heat-decomposing
appliance used in Example 1 was made to be length of tube of 18 cm,
inner diameter of tube of 27 mm and outer diameter of tube of 30
mm, S-benzylthiuronium chloride was inserted thereinto and the
closed heat-decomposing appliance was inserted as far as 10 cm into
circular electric furnace from the side of sample, sample was
pretreated similarly to Example 8 to implement the IC measurement
similarly to Example 1. As a result, to the theoretical contents (%
by weight) of 17.49% for Cl and 15.82% for S in S-benzylthiuronium
chloride, 17.45% and 15.55% were obtained for Cl and S,
respectively.
EXAMPLE 12
[0105] Except that S-benzylthiuronium chloride was inserted into
the closed heat-decomposing appliance (length of tube: 30 cm, inner
diameter of tube: 16 mm, outer diameter of tube: 18 mm) shown in
FIG. 2, sample was pretreated similarly Example 1 to implement the
IC measurement. As a result, to the theoretical contents (% by
weight) of 17.49% for Cl and 15.82% for S in S-benzylthiuronium
chloride, 17.56% and 15.65% were obtained for Cl and S,
respectively.
EXAMPLE 13
[0106] Except that S-benzylthiuronium chloride was inserted into
the closed heat-decomposing appliance (length of tube: 30 cm, inner
diameter of tube: 16 mm, outer diameter of tube: 18 mm) shown in
FIG. 3, sample was pretreated similarly Example 1 to implement the
IC measurement. As a result, to the theoretical contents (% by
weight) of 17.49% for Cl and 15.82% for S in S-benzylthiuronium
chloride, 17.32% and 15.66% were obtained for Cl and S,
respectively.
EXAMPLE 14
[0107] Except that S-benzylthiuronium chloride was inserted into
the closed heat-decomposing appliance (length of tube: 30 cm, inner
diameter of tube: 16 mm, outer diameter of tube: 18 mm) shown in
FIG. 4, sample was pretreated similarly Example 1 to implement the
IC measurement. As a result, to the theoretical contents (% by
weight) of 17.49% for Cl and 15.82% for S in S-benzylthiuronium
chloride, 17.57% and 15.79% were obtained for Cl and S,
respectively.
EXAMPLE 15
[0108] Except that the closed heat-decomposing appliance was
inserted by slanting 30.degree. to horizontal, making the closed
introducing section down, sample was pretreated similarly Example 1
to implement the IC measurement. As a result, to the theoretical
contents (% by weight) of 17.49% for Cl and 15.82% for S in
S-benzylthiuronium chloride, 17.28% and 15.82% were obtained for Cl
and S, respectively.
EXAMPLE 16
[0109] Except that an aqueous solution of 0.04 mol/L sodium
hydroxide and 10% by weight of hydrazine were used for the
absorbing liquid, sample was pretreated similarly Example 2 to
implement the IC measurement similarly to Example 1. As a result,
to the content (% by weight) of 9.73% for Br in this substance,
9.55% was obtained for Br.
EXAMPLE 17
[0110] Except that p-chlorobenzoic acid was used for the sample and
pure water was used for the absorbing liquid, sample was pretreated
similarly Example 4 to implement the IC measurement similarly to
Example 1. As a result, to the theoretical content (% by weight) of
22.64% for Cl in this substance, 22.00% was obtained for Cl.
EXAMPLE 18
[0111] Except that the same closed heat-decomposing appliance as
that in Example 4, excluding use of hard glass tube with one side
closed as a material, and hard glass boat were used, and the
temperature of furnace and heating time were made to be 600.degree.
C. and 30 minutes, respectively, sample was treated similarly to
Example 4 to implement the IC measurement similarly to Example 1.
As a result, the theoretical contents (% by weight) of 17.49% for
Cl and 15.82% for S in S-benzylthiuronium chloride, 17.90% and
15.43% were obtained for Cl and S, respectively.
EXAMPLE 19
[0112] Except that the same closed heat-decomposing appliance as
that in Example 1, excluding use of alumina ceramic tube with one
side closed as a material, was used, sample was pretreated
similarly to Example 1 to implement the IC measurement. As a
result, to the theoretical contents (% by weight) of 17.49% for Cl
and 15.82% for S in S-benzylthiuronium chloride, 17.44% and 15.77%
were obtained for Cl and S, respectively.
EXAMPLE 20
[0113] Except that o-iodobenzoic acid was used for the sample and
absorbing liquid comprising an aqueous solution of 0.04 mol/L
sodium hydroxide, 24% by weight of hydrogen peroxide and 10% by
weight of hydrazine was used, sample was pretreated similarly to
Example 1 to implement the IC measurement. As a result, to the
theoretical content (% by weight) of 15.17% for I in this
substance, 15.09% was obtained for I.
[0114] From the examples as above, it was seen that, by pretreating
the organic compounds containing various halogens and sulfur using
the inventive appliance and measuring the contents of halogen and
sulfur in the pretreatment liquids obtained, they are determined
accurately as shown by low RSD, and further almost 100% recovery
rates lead to accurate measurement results.
[0115] As having described above, according to the invention,
following advantages can be achieved,
[0116] 1) There is little contamination due to no combustion
assistant used.
[0117] 2) There are no complicated dangerous procedures, comparing
with conventional methods implementing firing of sample and
combustion in flask, sealing tube operation, insertion of sample
into heating area and rotation of heat-decomposing tube together
with furnace.
[0118] 3) Since the absorbing liquid is injected after heating,
there are no anxieties of increased inner pressure due to
evaporation on heating and evaporation of absorbing liquid.
[0119] 4) There is no obstruction due to ash present in the sample,
thereby the testing components can be quantitatively analyzed
accurately.
[0120] 5) The inventive appliance can be used repeatedly.
[0121] In addition, the pretreatment device and analytical device
using the inventive appliance are useful industrially, since their
procedures can be automated while making the best use of such
advantages.
* * * * *