Title of Invention

"AN ISOTOPE GAS ANAL YZING AND MEASURING APPARTUS"

Abstract The present invention is related to an isotope gas analyzing and measuring apparatus in which a gas to be measured containing, as gas components, carbon dioxide 13CO2 and carbon dioxide 12CO2, is introduced into a cell, and the intensities of transmitted lights having wavelengths suitable for measurement of the respective gas components, are measured and data-processed to measure the concentration of the carbon dioxide 13CO2, the isotope gas analyzing and measuring apparatus.
Full Text DESCRIPTION
GAS INJECTION AMOUNT DETERMINING METHOD IN ISOTOPE GAS
ANALYSIS, AND, ISOTOPE GAS ANALYZING AND MEASURING METHOD
AND APPARATUS
BACKGROUND OF THE INVENTION
Field of the Invention
After a medicine containing isotopes has been administered
to a living body, the metabolic rate of the living
body can be measured by measuring changes in concentration
re:io of the isotopes. Accordingly, isotope analysis is
utilized for disease diagnosis in the medical field.
The present invention is achieved with attention
focused on the difference in light absorption characteristics
of isotopes, and relates to a gas injection amount
determining method in isotope gas analysis for measuring
the concentration ratio of isotope gases, and also relates
to isotope gas analyzing and measuring method and apparatus
Description of Related Art
It is generally known that bacteria called
Helicobacter pylori (HP) are present in the stomach as the
cause of gastric ulcer and gastritis.
When HP is present in the patient's stomach, it is
required to conduct a bacteria elimination treatment by
administering a:i antibiotic substance. Accordingly it is
important whether or not HP is present in the patient. HP
presents a strong urease activity and therefore dissolves
urea into carbon dioxide and ammonia.
On the other hand, carbon includes isotopes of which
mass number is 13 and 14, in addition to 12. Out of these
isotopes, the isotope 13C having the mass number of 13 is
not radioactive and is sable, thus causing the same to be
readily handled.
In this connection, when urea marked with the isotope
13C is administered to a living body (patient), and t \e 1JC
concentration, more specifically the concentration ratio
between 13CO2 and 12CO2, in the expired breath of the patient
which is the final metabolic product, is measures, the
presence/absence of HP can be made sure.
However, the concentration ratio between 13C02 and 12C02
in the natural world, is as high as 1:100. It is therefore
difficult to precisely measure the concentration ratio in
the expired breath of the patient.
Conventionally, it is known a method using infrared
spectral diffraction as a method of obtaining the concentration
ratio between 13C02 and 12C02 or the concentration
of 13C02 (See Japanese Patent Publication Mo.
61(1986)-42220(B)}.
According to the method of Japanese Patent Publication
No. 61 (1986) -42220 (B) , there are prepared two, long and short,
cells having lengths such that the 12C02 absorption in one
cell is equal to the UCO2 absorption in the other cell, and
lights having wavelengths suitable for respective analyses
are irradiated to the respective cells, and the intensities
of the transmitted lights are measured. According to this
method, the light absorption ratio at the concentration ratio
in the natural field can be made 1, and if the concentration
ratio undergoes a change, the light absorption ratio varies
according to this change. Thus, the change in concentration
ratio can be known.
Even though there is adopted the method using infrared
spectral diffraction above-mentioned, it is difficult to
detect a slight change in concentration ratio.
According to the isotope gas analyzing and measuring
method above-mentioned, the concentration of carbon dioxide
"CQz is obtained with the use of a calibration curve which
determines the relationship between absorbance and concentration
of 13C02. However, if the atmospheric pressure
at which the calibration curve has been prepared, is different
from the atmospheric pressure at which the absorbance of
carbon dioxide 13C02 is measured, such difference may cause
an error of measurement of 13C02 concentration.
Table 1 shows the results of measurement of C02
concentration obtained in the following manner. That is,
a predetermined volume of air having a predetermined C02
concentration, was collected by a gas injection device at
each of a plurality of atmospheric pressures, and was then
injected into a cell. Each cell inside pressure was measured
Then, each absorbance was measured to measure the C02
concentration. The calibration curve used at this time was
prepared at an atmospheric pressure of 1005hPa.
(Table Removed)
According to Table 1, the cell inside pressures are
naturally proportional to the atmospheric pressures, and
the COs concentrations which must originally be constant,
are lowered according to the reduction in atmospheric
pressure. Thus, the concentration varies with the
variations of the atmospheric pressure.
In measurement in which gas to be measured containing,
as gas components, carbon dioxide 13CO2 and carbon dioxide
12C02, is introduced into a cell, and in which the intensities
of transmitted lights having wavelengths suitable for
measurement of the respective gas components, are measured
and then data-processed to measure the concentrations of
the gas components, it is an object of the present invention
to provide a gas injection amount determining method in
isotope gas analysis, and isotope gas analyzing/measuring
method and apparatus, each of which can correct concentration
variations resulting from the atmospheric pressure
variations, thus improving the measuring precision.
SUMMARY OF THE INVENTION
According to the present invention, a gas injection
amount determining method in isotope gas analysis comprises
the steps of: filling a cell with the air at an atmospheric
pressure; operating a gas injection device so as to suck
the air of a predetermined volume Va, the gas injection device
being arranged to inject the gas to be measured into the
cell; transferring the air stored in the gas injection device
into the cell to pressurize the cell inside, and measuring
the cell inside pressure P; and subtracting the cell volume
Vc from the product obtained by multiplying the sum VO of
the volume Va and the cell volume Vc, by the ratio PO/P in
which PO is the target pressure of the gas to be measured
in isotope gas analysis measurement, thus determining the
one-time gas injection amount of the gas injection device.
According to the method above-mentioned, when an
isotope gas analysis measurement is conducted with the use
of the one-time gas injection amount determined by multiplying
the ratio PO/P with the standard volume or sum VO
of the volume Va and the cell volume Vc, the gas to be measured
can be measured at the target pressure PO of the gas to be
measured. In other words, the cell inside pressure influenced
by variations of the atmospheric pressure can be
corrected.
Accordingly, the measuring precision and the reproducibility
are improved. Further, the measuring apparatus
is not required to be made in large sizes.
It is preferable that the cell volume Vc includes not
only net volume of the cell, but also inner volumes of pipes,
valves and pressure sensor which are in connection through
the cell. With use of the above volume Vc, more precise
measurement can be attained.
The target pressure PO of the gas to be measured is
preferably equal to the gas pressure at which a calibration
curve for determining the relationship between absorbance
and concentration of carbon dioxide 13C02, has been prepared.
According to an isotope gas analyzing and measuring
method of the present invention, gas to be measured having
the volume determined by the gas inj ection amount determining
method above-mentioned, is collected by a gas injection
device, the gas thus collected is transferred into the cell
to pressurize the cell inside, and the concentration of the
carbon dioxide 13CO2 or the concentration ratio 13C02/12C02
is measured.
An isotope gas analyzing and measuring apparatus of
the present invention is arranged to embody the isotope gas
analyzing and measuring method above-mentioned, and
comprises: a gas injection device for injecting gas into
acell/ gas transferringmeans for transferring the gas stored
in the gas injection device into the cell; a pressure sensor
for measuring the pressure of the gas housed in the cell;
and gas injection amount determining means arranged such
that the air having a predetermined volume Va is sucked by
the gas injection device, that the air stored in the gas
injection device is transferred to the cell filled with the
air at an atmospheric pressure , thereby to pressurize the
cell inside, that the cell inside pressure P is measured,
and that the cell volume Vc is subtracted from the product
obtained by multiplying the sum VO of the volume Va and the
cell volume Vc, by the ratio PO/P in which PO is the target
pressure of the gas to be measured in isotope gas analysis
measurement/ thus determining the one-time gas injection
amount of the gas inj ection device; whereby gas to be measured
having the volume determined by the gas injection amount
determining means, is collected by the gas injection device,
the. gas thus collected is transferred into the cell filled
with gas to be measured at an atmospheric pressure, and the
concentration of carbon dioxide 13C02 or the concentration
ratio 13C02/12C02 is measured.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a block diagram illustrating the general
arrangement of an isotope gas spectroscopic measurement
apparatus;
Fig. 2 (a) is a plan view of a gas injection device
21 for quantitatively injecting gas to be measured, and Fig.
2(b) is a front view of the gas injection device 21;
Fig. 3(a) and Fig. 3(b) are views illustrating gas
flow passages at the time when a one-time gas injection amount
is determined;
Fig. 4 (a) and Fig. 4(b) are views illustrating gas
flow passages at the time when a reference gas light amount
measurement is conducted;
Fig. 5 (a) and Fig. 5(b) are view illustrating gas flow
passages at the time when a base gas light amount measurement
is conducted; and
Fig. 6(a) and Fig. 6(b) are view illustrating gas flow
passages at the time when a sample gas light amount measurement
is conducted.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to the attached drawings, the following
description will discuss in detail an embodiment of the
present invention in which after a urea diagnostic medicine
marked with an isotope 13C has been administered to a living
body, the 13C02 concentration of an expired breath of the
living body is spectroscopically measured.
I. Expired Breath Test
First, an expired breath of a patient before a urea
diagnostic medicine is administered, is collected in an
expired breath bag. Then, a urea diagnostic medicine is
orally administered to the patient. After the passage of
about 20 minutes, an expired breath is collected in an expired
breath bag in a manner similar to that before administration.
The expired breath bags before and after administration
are respectively set to predetermined nozzles of
an isotope gas spectroscopic measurement apparatus. Then,
the following, automatic measurement is conducted.
II. Isotope Gas Spectroscopic Measurement Apparatus
Fig. 1 is a block diagram illustrating the general
arrangement of an isotope gas spectroscopic measurement
apparatus.
The expired breath bag containing the expired breath
after administration (hereinafter referred to as "sample
gas")f and the expired breath bag containing the expired
breath before administration (hereinafter referred to as
"base gas"), are respectively set to nozzles Nl andN2. The
nozzle Nl is connected to an electromagnetic valve
(hereinafter simply referred to as "valve") V4 through a
metallic pipe (hereinafter simply referred to as "pipe") .
The nozzle N2 is connected to a valve V3 through a pipe.
A valve V5 is connected to a pipe for taking in the air through
a dust-proof filter 15.
On the other hand, a reference gas (In this embodiment,
the air with C02 removed is used) supplied from a reference
gas supply unit 30 (to be discussed later), is supplied to
a valve V1.
The valves V1, V3, V4 and V5 are connected to the gas
inj ection device 21 for quantitatively inj ecting a reference
gas, a sample gas or a base gas. The gas injection device
21 has a syringe shape having a piston and a cylinder. The
piston is driven by a feed screw 21e connected to a pulse
motor 21f in association with a nut 21d fixed to the piston
(to be discussed later) . The maximum gas injection amount
of the gas injection device 21 is 40 ml.
The gas injection device 21 is connected, through a
valve V2, to a first sample cell lla and a second sample
cell lib.
As shown in Fig. 1, the cell chamber 11 has the short
first sample cell lla for measuring the 12C02 absorption,
the long second sample cell 11b for measuring the 13C02
absorption, and a dummy cell 11c containing gas which is
not absorbed in the CO2 absorbing range. Provision is made
such that the first sample cell lla and the second sample
cell 11b communicate with each other, and that gas introduced
into the first sample cell lla enters, as it is, the second
sample cell 11b, and is then discharged through an exhaust
valve V6.
Disposed upstream of the exhaust valve V6 is a pressure
sensor 16 for measuring the gas pressure in the first sample
cell lla and the second sample cell 11b. No restrictions
are imposed on the detection method of this pressure sensor
16, but there may be used for example a pressure sensor of
the type in which the movement of a diaphragm is detected
by a piezoelectric element.
The first sample cell lla has a capacity of about 0 085
ml, while the second sample cell 11b has a capacity of about
3.96 ml. More specifically, the first sample cell lla has
a length of 3 mm, the second sample cell 11b has a length
of 140 mm, and the dummy cell 11c has a length of 135 mm.
The cell chamber 11 is surrounded by an insulating material
(not shown).
There is also disposed an infrared light source device
L having two light sources for irradiating infrared rays.
Infrared rays may be generated by an optional method. For
example, there may be used a ceramics heater (surface
temperature of 700°C) or the like. There is further disposed
a chopper 22 for interrupting and passing infrared rays at
predetermined intervals. The chopper 22 is rotated by a
pulse motor 23.
Out of the infrared rays irradiated from the infrared
light source device L, the light path formed by infrared
rays passing through the first sample cell lla and the dummy
cell 11c, is called a first light path L1, and the light
path f ormedby infrared rays passing through the second sample
cell 11b, is called a second light path L2 (See Fig. 1) .
An infrared rays detector device for detecting the
infrared rays having passed through the cells comprises:
a first wavelength filter 24a and a first sensor element
25a disposed in the first light path; and a second wavelength
filter 24b and a second sensor element 25b disposed in the
second light path.
For measuring the absorption of 12CO2, the first
wavelength f ilter 24a is designed to pass infrared ray shaving
a wavelength of about 4280 nm which is the 12C02 absorption
wavelength range. For measuring the absorption of 13C02,
the second wavelength filter 24b is designed to pass infrared
rays having a wavelength of about 4412 nm which is the 13C02
absorption wavelength range. The first and second sensor
elements 25a, 25b are light-receiving elements for detecting
infrared rays.
The first wavelength filter 24a, the first sensor
element 25a, the second wavelength filter 24b, and the second
sensor element 25b are maintained at a predetermined
temperature by a temperature controlling block 27.
A fan 28 is disposed for discharging, to the outside
of the apparatus, heat radiated from a Peltier element of
the temperature controlling block 27.
Further, the isotope gas spectroscopic measurement
apparatus has a reference gas supply unit 30 for supplying
the air with C02 removed. The reference gas supply unit 30
is connected in series to a dust-proof filter 31 and a carbonic
acid gas absorbing unit 36.
The carbonic acid gas absorbing unit 36 is arranged
to use for example soda lime (a mixture of sodium hydroxide
and calcium hydroxide), as a carbonic acid gas absorbing
agent.
Fig. 2(a) is a plan view of a gas injection device
21 for quantitatively inj ecting gas to be measured, and Fig.
2(b) is a front view of the gas injection device 21.
The gas injection device 21 has a base stand 21a, a
cylinder 21b having a piston 21c disposed on the base stand
21a, a movable nut 2Id coupled to the piston 21c, a feed
screw 21e meshed with the nut 21d, and a pulse motor 21f
for rotating the feed screw 21e, the nut 21d, the feed screw
21e and the pulse motor 21f being disposed under the base
stand 21a.
The pulse motor 21f is driven forwardly/reversely by
a driving circuit (not shown). When the feed screw 21e is
rotated by the rotation of the pulse motor 21f, the nut 21d
is moved back and forth according to the rotation direction.
This causes the piston 21c to be moved back and forth to
an optional position. It is therefore possible to optionally
control both the introduction of gas to be measured, into
the cylinder 21b, and the discharge of the gas to be measured
from the cylinder 21b.
III. Measuring Procedure
The measuring process comprises the steps of determining
a one-time gas injection amount, measuring the
reference gas, measuring the base gas, measuring the
reference gas, measuring the sample gas, and measuring the
reference gas and the like. In Figs. 3 to 5, the arrows
show the gas flowing.
III-l. Determination of the One-Time Gas Injection Amount
This gas injection amount determining step may be
conducted at each measurement of a sample gas or at regular
time intervals (e.g., every one hour).
It is now supposed that the total of the first sample
cell 11a volume and the second sample cell 11b volume is
defined as Vc (a predetermined value). The volume Vc
preferably not only includes the net volume of the sample
cells lla, 11b, but also includes inner volumes of the pipes,
valves and pressure sensor 16 which are connected through
the sample cells lla, lib. It is also supposed that the
volume of the gas injection device 21 at the time when gas
is injectedby the gas injection device 21 to a predetermined
scale thereof, is defined as Va. It is supposed that Vc
+ Va = VO. This volume VO is defined as a standard volume
vo.
The valve V5 is opened, other valves are closed, and
the air is sucked with the use of the gas injection device
21. Then, the valve V5 is closed, and the valve V2 and the
exhaust valve V6 are opened. The air in the gas injection
device 21 is injected into the first sample cell lla and
the second sample cell 11b. Then, the valve V2 is closed
and the exhaust valve V6 is closed. Thus, the air having
the volume Vc at the atmospheric pressure is housed in the
first sample cell lla and the second sample cell 11b.
As shown in Fig. 3 (a) , the valve V5 is opened, other
valves are closed, and the air of volume Va is sucked with
the use of the gas injection device 21.
As shown in Fig. 3 (b) , the valve V5 is closed and the
valve V2 is opened to transfer the air in the gas injection
device 21 into the first sample cell lla and the second sample
cell 11b. Since the exhaust valve V6 remains closed, the
insides of the first sample cell lla and the second sample
cell 11b are pressurized.
With the valve V2 closed to stop the air movement,
the pressure of the first sample cell 11a and the second
sample cell 11b is measured by the pressure sensor 16. This
measured pressure value is defined as P.
It is supposed that each calibration curve for
determining the relationship between absorbance and
concentration of each of carbon dioxide 13C02 and carbon
dioxide 12C02, has been prepared at a predetermined pressure
P0(i.e., 4 atmospheric pressure). The calibration curve
data and the value of the predetermined pressure PO are stored
in an analysis computer of the isotope gas spectroscopic
measurement apparatus.
The analysis computer determines a one-time measuring
gas volume VO(PO/P) with the use of the previously stored
pressure PO, the measured pressure P and the standard volume
VO. As shown by the following equation (1), the gas inj ect ion
amount V of the gas injection device 21 is a value obtained
by subtracting the cell volume Vc from VO(PO/P) . In the
equation (1) , the volume Vc is subtracted because the first
sample cell lla and the second sample cell lib already contain
the gas to be measured having the volume Vc.
V = VO(PO/P) - Vc (1)
The following description will discuss the equation
(1) . When the measured pressure P is equal to pO, the gas
injection amount V is equal to Va. If the atmospheric
pressure is high, the measured pressure P is higher than
PO. At this time, the gas injection amount V may be set
to a value smaller than Va. If the atmospheric pressure
is low, the measured pressure P is lower than PO. At this
time, the gas injection amount V may be set to a value higher
than Va. With such an operation, the COz concentration can
always be measured under conditions identical to those under
which the calibration curve has been prepared.
111-2. _Ref erence Measurement
A clean reference gas is flowed into the gas flow
passages and the cell chamber 11 of the isotope gas
spectroscopic measurement apparatus to wash the gas flow
passages and the cell chamber 11. At this time, the piston
21c is moved back and forth to wash the inside of the cylinder
2lb. A reference gas at an atmospheric pressure is housed
in the first sample cell 11a and the second sample cell 11b.
In the reference measurement, the valve V1 is opened,
other valves are closed, and a reference gas is sucked with
the use of the gas injection device 21, as shown in Fig.
4(a) .
Then, as shown in Fig. 4 (b), the valve VI is closed,
and the valve V2 and the exhaust valve V6 are opened. While
the reference gas in the gas injection device 21 is slowly
flowed into the first sample cell lla and the second sample
cell 11b by controlling the gas injection device 21, the
light amount measurement is conducted by the sensor elements
25a, 25b.
The light amount thus obtained by the first sensor
element 25a is recorded as 12R1, and the light amount thus
obtained by the second sensor element 25b is recorded as
13R1.
III-3. Base Gas Measurement
The valve V3 is opened, other valves are closed and
the base gas is sucked with the use of the gas injection
device .21. Then, the valve V3 is closed, the valve V2 and
the exhaust valve V6 are opened, and the base gas in the
gas injection device 21 is injected into the first sample
cell 11a and the second sample cell 11b. Thereafter, the
exhaust valve V6 is closed. Thus, the base gas at an
atmospheric pressure is housed in the first sample cell lla
and the second sample cell 11b.
Then, the valve V3 is opened, other valves are closed
and the base gas having the volume V calculated according
to the equation (1) is sucked from the expired breath bag
by the gas injection device 21, as shown in Fig. 5(a).
After the base gas has been sucked, the valve V3 is
closed, and the valve V2 is opened as shown in Fig. 5(b) .
The base gas is mechanically pushed out with the use of the
gas injection device 21 to pressurize the first sample cell
lla and the second sample cell 11b. This increases the
pressure of the base gas in the first sample cell lla and
the second sample cell 11b, to a value equal to the pressure
PO.
At this state, the valve V2 is closed and the light
amount is measured by the sensor elements 25a, 25b.
The light amount thus obtained by the first sensor
element 25a is recorded as 12B, and the light amount thus
obtained by the second sensor element 25b is recorded as
13B.
III-4 Reference Measurement
Again, the gas flow passages and the cells are washed/
and the reference gas light amount measurement is conducted
(See Figs. 4 (a), (b) ) . The light amount thus obtained by
the first sensor element 25a is recorded as 12R2, and the
light amount thus obtained by the second sensor element 25b
is recorded as 13R2.
III-5 Sample Gas Measurement
The valve V4 is opened, other valves are-closed and
the sample gas is sucked with the use of the gas injection
device 21. Then, the valve V4 is closed, the valve V2 and
the exhaust valve V6 are opened, and the sample gas in the
gas injection device 21 is injected into the first sample
cell lla and the second sample cell 11b. Thereafter, the
exhaust valve V6 is closed. Thus, the sample gas at an
atmospheric pressure is housed in the first sample cell lla
and the second sample cell 11b.
Then, the valve V4 is opened, other valves are closed
and the sample gas having the volume V calculated according
to the equation (1) is sucked from the expired breath bag
by the gas injection device 21, as shown in Fig. 6(a).
After the sample gas has been sucked, the valve V4
is closed, and the valve V2 is opened, as shown in Fig. 6 (b) .
The sample gas is mechanically pushed out with the use of
the gas injection device 21 to pressurize the first sample
cell lla and the second sample cell lib. This increases
the pressure of the sample gas in the first sample cell lla
and the secondsample cell lib, to a value equal to thepressure
PO.
At this state, the valve V2 is closed and the light
amount is measured by the sensor elements 25a, 25b.
The light amount thus obtained by the first sensor
element 25a is recorded as 12S, and the light amount thus
obtained by the second sensor element 25b is recorded as
13S.
III-6. Reference Measurement
Again, the gas flow passages and the cells are washed,
and the reference gas light amount measurement is conducted
(See Figs. 4 (a), (b)) .
The light amount thus obtained by the first sensor
element 25a is recorded as 12R3, and the light amount thus
obtained by the second sensor element 25b is recorded as
13R3.
IV Data Processing
IV-1. Calculation of the Base Gas Absorbance Data
First, both the absorbance 12Abs (B) of 12C02 and the
absorbance 13Abs (B) of 13C02 in the base gas, are obtained
with the use of (i) the transmitted light amounts 12R1, 13R1
of the reference gas, (ii) the transmitted light amounts 12B,
13B of the base gas, and (iii) the transmitted light amounts
12R2, 13R2 of the reference gas.
Here, the absorbance 12Abs (B) of 12C02 is obtained by
the following equation:
12Abs(B) = -log [212B/(12R1 + 12R2)]
The absorbance 13Abs (B) of 13C02 is obtained by the
following equation:
13Abs(B) = -log [213B/(13R1 + 13R2)]
Thus, when calculating each absorbance, there is
calculated the average value (Rl + R2) 12 of the light amounts
of reference measurements conducted before and after the
absorbance calculation, and the absorbance is then calculated
with the use of the average value thus obtained and
the light amount obtained by the base gas measurement.
Accordingly, the influence of drift (influence exerted to
measurement by the passage of time) can be cancelled each
other. Accordingly, the measurement can quickly be
initiated without the need of waiting until the apparatus
is brought into perfect thermal equilibrium after the
apparatus has been stared (generally, several hours are
required).
IV-2. Calculation of Sample Gas Absorbance Data
Then, both the absorbance uAbs(S) of 12C02 and the
absorbance 13Abs(S) of 13C02 in the sample gas are obtained
with the use of (i) the transmitted light amounts 12R2, 13R2
of the reference gas, (ii) the transmitted light amounts 12S,
13S of the sample gas, and (iii) the transmitted light amounts
12R3, 13R3 of the reference gas.
Here/ the absorbance 12Abs(S) of 12C02 is obtained by
the following equation:
12Abs(S) = -log [212S/(12R2 + 12R3}]
The absorbance 13Abs (S) of 13C02 is obtained by the
following equation:
13Abs(S) = -log [213S/(13R2 + 13R3)]
Thus, when calculating an absorbance, there is
calculated the average value of the light amounts of reference
measurements conducted before and after the absorbance
calculation, and the absorbance is then calculated with the
use of the average value thus obtained and the light amount
obtained by the sample gas measurement. Accordingly, the
influence of drift can be cancelled each other.
IV-3 Concentration Calculation
12C02 concentration and 13C02 concentration are obtained
with the use of calibration curves.
As mentioned earlier, the concentration curves are
prepared with the use of gas to be measured of which 12C02
concentration is known and gas to be measured of which 13C02
concentration is known.
To obtain the calibration curve for 12C02 concentration,
12CO: absorbance data are measured with the 12C02 concentration
changed in the range of 0% to about 8%, and the data thus
measured are plotted on a graph in which the axis of abscissas
represents the 12C02 concentration and the axis of ordinates
represents the i2CO? absorbance. Then, the curve is determined
by the method of least squares.
To obtain the calibration curve for 13CC>2 concentration,
13CO2 absorbance data are measuredwith the I3COa concentration
changed in the range of 0% to about 0.08%, and the data thus
measured are plotted on a graph in which the axis of abscissas
represents the 13C02 concentration and the axis of ordinates
represents the 13COa absorbance. Then, the curve is determined
by the method of least squares.
The curves approximated by quadratic equations are
relatively less in error. Accordingly, the calibration
curves approximated by quadratic equations are adopted in
this embodiment.
There are recorded the 12C02 concentration of the base
gas as 12Conc(B) , the 13C02 concentration of the base gas as
13Conc(B), the 12C02 concentration of the sample gas as
i:Conc(S) , and the 13C02 concentration of the sample gas as
13Conc (S) , these concentration data being obtained with the
use of the calibration curves above-mentioned.
IV-4 Calculation of the Concentration Ratios
Then, each concentration ratio between 13C02 and 12C02
is obtained. That is, the concentration ratio between 13CC>2
and 12C02 of the base gas is obtained by 13Conc (B) / 12Conc (B) ,
and the concentration ratio between 13C02 and 12COz of the
sample gas is obtained by 13Conc(S)/ 12Conc(S).
The concentration ratios may also be defined as
13Conc(B)/(12Conc(B) +13Conc(B)) and as 13Conc (S) / (12Conc (S)
+ 13Conc (S) ) . Since the 12CC>2 concentrations are much greater
than the 13C02 concentrations, the concentration ratios
obtained by these different calculation methods are
substantially equal to each other.
IV-5 Determination of 13C Changed Portion
The 13C changed portion in comparison of the sample
gas data with the base gas data, is calculated by the following
equation:
A13C = [Sample Gas Concentration Ratio - Base Gas
Concentration Ratio] x 103/[Base Gas Concentration Ratio]
(Unit: permil).





We Claim:
1. An isotope gas analyzing and measuring apparatus in which a gas to be measured containing, as gas components, carbon dioxide 13CO2 and carbon dioxide 12CO2, is introduced into a cell, and the intensities of transmitted lights having wavelengths suitable for measurement of the respective gas components, are measured and data-processed to measure the concentration of the carbon dioxide 13CO2, the isotope gas analyzing and measuring apparatus comprising:
means for filling an atmospheric air into the cell of an volume Vc;
a gas injection device for sucking and storing another atmospheric air of a predetermined volume Va therein;
gas transferring means for transferring the air stored in the gas injection device into the cell, when an exhaust valve of the cell is stopped;
a pressure sensor for measuring the pressure of the air housed in the cell; and
gas injection amount determining means arranged such that the air sucked and stored by the gas injection device is transferred to the cell, thereby to pressurize the cell inside, such that the cell inside pressure P is measured, and such that the cell volume Vc is subtracted from the product obtained by multiplying the sum VOof the volume Va and the cell volume Vc, by the ratio PO/P in which PO is the target pressure of the gas to be measured in isotope gas analysis measurement, by the following formulae,
(Formula Removed)
thus determining the one-time gas injection amount V of the gas injection device,
whereby gas to be measured having the volume V determined by the gas injection amount determining means, is collected by the gas injection device, the gas thus collected is transferred into the cell filled with gas to be measured at an atmospheric pressure, and the concentration of carbon dioxide 13CO2 or the concentration ratio 13CO2/12CO2 is measured.
2. An isotope gas analyzing and measuring apparatus as claimed in Claim 1, wherein the cell volume Vc includes a net volume of the cell and volumes of pipes, valves and the pressure sensor which are in connection through the cell.

Documents:

2317-DELNP-2006-Abstract-(09-05-2011).pdf

2317-delnp-2006-abstract.pdf

2317-delnp-2006-assignments.pdf

2317-DELNP-2006-Claims-(09-05-2011).pdf

2317-delnp-2006-claims.pdf

2317-DELNP-2006-Correspondence Others-(01-09-2011).pdf

2317-DELNP-2006-Correspondence Others-(02-05-2011).pdf

2317-DELNP-2006-Correspondence Others-(09-05-2011)..pdf

2317-delnp-2006-Correspondence Others-(09-05-2011).pdf

2317-DELNP-2006-Correspondence-Others (03-11-2009).pdf

2317-delnp-2006-Correspondence-Others-(02-11-2010).pdf

2317-DELNP-2006-Correspondence-Others-(14-05-2010).pdf

2317-delnp-2006-correspondence-others-1.pdf

2317-delnp-2006-correspondence-others.pdf

2317-delnp-2006-description(complete).pdf

2317-DELNP-2006-Drawings-(02-05-2011).pdf

2317-delnp-2006-Drawings-(09-05-2011).pdf

2317-delnp-2006-drawings.pdf

2317-DELNP-2006-Form-1-(09-05-2011).pdf

2317-delnp-2006-form-1.pdf

2317-delnp-2006-form-18.pdf

2317-DELNP-2006-Form-2-(09-05-2011).pdf

2317-delnp-2006-form-2.pdf

2317-DELNP-2006-Form-3 (03-11-2009).pdf

2317-DELNP-2006-Form-3-(01-09-2011).pdf

2317-delnp-2006-Form-3-(02-11-2010).pdf

2317-DELNP-2006-Form-3-(09-05-2011).pdf

2317-DELNP-2006-Form-3-(14-05-2010).pdf

2317-delnp-2006-form-3.pdf

2317-delnp-2006-form-5.pdf

2317-DELNP-2006-GPA-(09-05-2011).pdf

2317-delnp-2006-pct-101.pdf

2317-delnp-2006-pct-202.pdf

2317-delnp-2006-pct-210.pdf

2317-delnp-2006-pct-220.pdf

2317-delnp-2006-pct-237.pdf

2317-delnp-2006-pct-301.pdf

2317-delnp-2006-pct-304.pdf

2317-delnp-2006-pct-308.pdf

2317-delnp-2006-pct-311.pdf

2317-delnp-2006-pct-326.pdf

2317-delnp-2006-pct-373.pdf

2317-delnp-2006-Petition-137-(09-05-2011).pdf


Patent Number 257483
Indian Patent Application Number 2317/DELNP/2006
PG Journal Number 41/2013
Publication Date 11-Oct-2013
Grant Date 08-Oct-2013
Date of Filing 27-Apr-2006
Name of Patentee OTSUKA PHARMACEUTICAL CO., LTD.
Applicant Address 9, KANDATSUKASA-CHO 2-CHOME, CHIYODA-KU,TOKYO 101-8535,JAPAN.
Inventors:
# Inventor's Name Inventor's Address
1 KUBO YASUHIRO 2093-211, BODAIJI, KONAN-SHI, SHIGA 520-3242, JAPAN,
2 ZASU YASUSHI 7-1, SEIKADAI 3-CHOME, SEIKA-CHO, SORAKU-GUN, KYOTO 619-0238.JAPAN.
3 TANI MASAYUKI 61-22, NAGAONISHIMACHI 2-CHOME, HIRAKATA-SHI, OSAKA 573-0162 JAPAN.
4 HAMAO TAMOTSU 162-22 MUKAIJIMATSUDA-CHO, FUSHIMI-KU, KYOTO-SHI, 612-8154, JAPAN.
5 MORI MASAAKI 20-18,SUGIYAMATE 1-CHOME, HIRAKATA-SHI, OSAKA 573-0118,JAPAN,
6 MORI MASAAKI 20-18
PCT International Classification Number A61B 5/083
PCT International Application Number PCT/JP2004/016451
PCT International Filing date 2004-10-29
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2003-373093 2003-10-31 Japan