U.S. patent number 3,797,300 [Application Number 05/201,396] was granted by the patent office on 1974-03-19 for automatic base line drift corrector device for use in an integrator for chromatographical analysis.
This patent grant is currently assigned to Shimadzu Seisakusho Ltd.. Invention is credited to Tatsuo Sato.
United States Patent |
3,797,300 |
Sato |
March 19, 1974 |
AUTOMATIC BASE LINE DRIFT CORRECTOR DEVICE FOR USE IN AN INTEGRATOR
FOR CHROMATOGRAPHICAL ANALYSIS
Abstract
An automatic base line drift corrector device for use in an
integrator for chromatographical analysis, essentially including
means for generating an instantaneous correction signal by which a
correcting operation with respect to the base line value of the
signal can be instantaneously carried out and means for generating
a non-instantaneous correction signal by which a correcting
operation with respect to the base line value of the signal can be
carried out with a time lag with respect to the detected signal,
either of said first and second generating means being employed by
a switching means for excluding an interval between the starting
and terminating points of the peak appearing in the signal in
connection with the wave form or time of the signal.
Inventors: |
Sato; Tatsuo (Kyoto City,
JA) |
Assignee: |
Shimadzu Seisakusho Ltd. (Kyoto
City, JA)
|
Family
ID: |
26444508 |
Appl.
No.: |
05/201,396 |
Filed: |
November 23, 1971 |
Foreign Application Priority Data
|
|
|
|
|
Nov 25, 1970 [JA] |
|
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45-103936 |
Nov 25, 1970 [JA] |
|
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45-117157 |
|
Current U.S.
Class: |
73/23.23;
73/23.35; 702/32 |
Current CPC
Class: |
G06G
7/186 (20130101); G01N 30/8603 (20130101) |
Current International
Class: |
G06G
7/00 (20060101); G01N 30/86 (20060101); G01N
30/00 (20060101); G06G 7/186 (20060101); G01n
031/08 () |
Field of
Search: |
;73/23.1
;235/151.35,183 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Queisser; Richard C.
Assistant Examiner: Kreitman; Stephen A.
Attorney, Agent or Firm: Wenderoth, Lind & Ponack
Claims
What is claimed is:
1. An automatic base line drift corrector device for use in an
integrator for chromatographical analysis, comprising:
a. means for receiving a signal from a measuring instrument;
b. peak detecting means coupled to said signal receiving means for
detecting the start and end time points of a peak appearing in said
signal;
c. correction signal generating means coupled to said signal
receiving means and said peak detecting means for generating a
correction signal by which the base line value of the signal can be
carried out;
d. first switching means coupled to said correction signal
generating means and said peak detecting means for switching said
correction signal generating means off between the start and end
time points of a peak in said signal;
e. instantaneous correction signal means coupled to said correction
signal generating means for causing instantaneous generation of a
correction signal;
f. time delay correction signal means coupled to said correction
signal generating means for causing generation of a correction
signal after a predetermined time delay;
g. further switching means coupled to said instantaneous correction
on signal means and said time delay correction signal means for
switching from one to the other for causing said correction signal
generating means to generate a correction signal instantaneously or
with a time delay at the end time point of a peak appearing in said
signal; and
h. integrating means coupled to said correction signal generating
means and said peak detecting means for integrating the area under
a peak in the wave form of the signal.
2. An automatic base line drift corrector device as claimed in
claim 1, in which said further switching means includes delay means
for delaying the operation of said further switching means for a
certain period and after said certain period, said further
switching means switches said instantaneous correction signal means
when the start time point has been detected by said peak detecting
means and switches said time delay correction signal means when no
start time point has been detected.
3. An automatic base line drift corrector device as claimed in
claim 2 wherein said delaying means is operable to vary the certain
period.
4. An automatic base line drift corrector device as claimed in
claim 1 wherein said further switching means comprises
discriminating means for detecting the polarity of the wave form of
the signal and for switching said instantaneous correction signal
means when the discriminating means detects a negative polarity and
for switching said time delay correction signal means when the
discriminating means detects a positive polarity.
5. An automatic base line drift corrector device as claimed in
claim 4 wherein said discriminating means is operable when
fluctuations in the signal are much larger than a predetermined
value of drift.
Description
The present invention relates to an automatic base line drift
corrector device for use in an integrator for chromatographical
analysis adapted to automatically detect the starting point and
terminating point of the peak in a chromatograph to integrate the
area under the peak so that correction of the base line drift can
be effected without altering the wave shape or amplitude of the
analytical signals detected. In the art of chemical analysis,
chromatographs are used to analyze the chemical contents of samples
and are designed so as to provide output analytical fluctuations
indicative of the occurrence and concentration of the chemical
constituents. Nevertheless a proper technique for this purpose
includes the use of actual onset analysis which results in a higher
or lower base line value. Obviously, it is sometimes desirable or
even necessary to alter the base line value to accomplish various
chromatographic analyses in which the analytical signals provided
by various sensors, detectors, voltage sources or other transducers
may normally integrate the areas under respective peaks with
respect to the base line thereof. Because of the importance of
obtaining analytical signals having a base line which is
essentially drift-free, and for many reasons, it has been found
desirable to provide a device for correcting base line drift.
The correction of the base line for the chromatograph constitutes,
in principle, instantaneously correcting to zero a point on the
curve which is above the zero point of the base line before
detecting the peak. However, according to such a method, a part of
the curve of the peak is corrected to zero by a drift of the base
line, when the detection of the start of the positive slope of the
peak has been delayed as shown in FIG. 1(a). The vertical axis of
FIG. 1(a) and the horizontal axis thereof show the height of the
peak and the time interval thereof, respectively. If the peak is
wide with a gentle slope when the peak starts at the time point A,
there will be a considerable amount of time elaspe until the slope
reaches a fixed value or more. Accordingly, the detection of the
peak is often delayed. If the peak is detected, for example,
starting at time point B, the base line is instantaneously
corrected so that the peak starts at zero at the time point B,
whereby the portion of the peak prior to the time point B is
corrected to zero by a drift of the base line. Therefore, only the
lined area of the peak between B and C is calculated by means of an
integrator. Since the peak actually ends at D a considerable error
is caused with respect to the actual area under the peak because
the area under the line B C and between A and D is not
calculated.
Thus, a fixed time lag is generally used for the correction of the
base line and the part of the curve of the peak before the start of
the calculation of the area under the peak is not cancelled, and
the area of the hatched portion defined by B, E, F and C in FIG.
1(b) is calculated.
However, in such a method of correcting the base line a
considerable error is likely to be caused with respect to a peak
which is difficult to separate. This is described hereinafter with
reference to FIGS. 2 and 3.
The vertical axis of FIGS. 2 and 3 shows the peak and the base
line, respectively, while the horizontal axis thereof, shows the
time. The start of the positive slope of the first peak is detected
at point A, the end thereof being detected at point B, the start of
the next peak being detected at point C and the end thereof being
detected at point D. At first, in FIG. 2(a), it is assumed that the
base line has drifted from the height designated at point A to the
height designated at point C when the end of the first peak has
been detected at point B. In this case, as for the second peak, the
area covered with oblique lines between C and D has to be
calculated.
However, in the conventional system, the base line correcting
device is actuated after the end of the first peak has been
detected at point B. If there is a lag in the correcting operations
of the correcting device, the base line can not be shifted
completely between points B and C when the time interval from the
point B to the start point C of the next peak is short. As shown in
FIG. 2(b), the base line can drift as far as point F. Accordingly,
the area under the second peak calculated by the integrating device
becomes the portion covered with the oblique lines between C, F, G
and D of FIG. 2(b), which is a considerably bigger size than the
actual area, that is, the area of the portion covered with the
oblique lines between C and D of FIG. 2(a).
In order to prevent the errors, as shown in FIG. 2(b), from being
caused, the area of the portion covered with the oblique lines
between C and D of FIG. 2(a) must be calculated as if the
instantaneous correction were carried out without a time lag in the
correcting action for the base line. However, in this case, a
considerable error is caused with respect to the type of peak shown
in FIG. 3.
FIGS. 3(a) and 3(b) show the case where the second peak is produced
on the negative slope of the first big peak, in which condition, as
shown in FIG. 3(a), the respective areas of the portions, defined
by A, E and B and C, F and D have to be calculated. However, if the
correction of the base line is carried out instantaneously after
the slope of the first peak has become a fixed value or less at
point B and the end of the first peak has been detected, in the
second peak the area of the portion covered with the oblique lines
between C and D of FIG. 3(b) is calculated, which area is
considerably smaller than the actual area CFD in FIG. 3(a).
The conventional method of calculating the area of the portion
covered with the oblique lines in FIG. 3(a) has been carried out by
the interposition of a delay circuit wherein the base line
correcting device is not operated at all during a predetermined
time period which is longer than the time interval between B and C
of FIG. 3(a), and is actuated after the lapse of the predetermined
time.
However, the area can not be calculated correctly by any
conventional method for the curves of both FIG. 2(a) and FIG. 3(a).
Either the area of FIG. 2(a) or that of FIG. 3(a) can be calculated
correctly, but not both.
However, the delay circuit means for correction of the base line
for a gentle curve as shown in FIG. 3 can not keep up with
variations of the base line when the area of the peak on the
negative slope as shown in FIG. 4 is calculated, whereby the error
becomes considerable. FIG. 4 shows changes of the peak and the base
line with respect to the time elapsed, in which the waveforms vary
in the direction of the arrow as time passes. When the first peak
is finished at time point B, the point B of the figure becomes a
base line. But the slope of the curve to the start time point C of
the second peak is so relatively steep that the correction of the
base line can not catch up with the slope. At the start time point
C of the second peak, the base line is corrected to a value before
the time point C, for example, a value in the time point E, whereby
the area of the second peak becomes the area between E and F
covered with the oblique lines, and is considerably smaller than
the actual peak area between the time point C and the time point D
where the second peak actually begins and ends. Moreover, in
practical gas chromatography which employs gas as the mobile phase,
the base line of the detected signals is normally shifted all of a
sudden from the high value X of the carrier gas to the low value Y
of the sample gas, as shown in FIG. 5. Therefore, when the
correcting operation for the base line delayed by means of a delay
control circuit is subjected to the detected signals of the carrier
gas in gas chromatography, the first peak of the detected signals
appearing adjacent to the turning point A at which the sample gas
is mixed with the carrier gas may be integrated on a false base
line, i.e., the line D-E in FIG. 5, which is much higher than the
real base line, i.e., the line B-C in FIG. 5, thereby reducing the
detected area and giving misleading information as to contents of
the sample gas. Accordingly, it is necessary to carry out an
instantaneous correcting operation for the base line to follow the
detected signals at once when the output of the base line
correcting device is detected to have negative polarity at the
turning point.
An object of the present invention is to provide a base line
correcting device wherein a exact correction of the base line can
be carried out with respect to any peak which is insufficiently
separated from adjacent peaks.
Another object of the present invention is to provide a base line
correcting device for an integrator for chromatographical analysis,
which is adapted to delay the start of the correcting operations
for the base line by means of a delay control circuit, which can
select the delay time after the end of the peak has been detected,
to carry out a correcting operation instantaneously for a very
short time, unless the start of the next peak is detected, after
the delay time has elapsed, and to carry out the correcting
operation for the base line with an ordinary time lag after the
very short time has been elapsed.
A further object of the present invention is to provide a system
wherein the slope is instantaneously corrected even when the slope
of the negative slope of the peak is steep, whereby the peak area
on the negative slope can be calculated more correctly. The
instantaneous correction of the base line is carried out when the
base line falls steeply, while the correction of the base line is
carried out with time lag, as before, on the other occasions.
A still further object of the present invention is to provide a
base line correcting system for an integrator for chromatographical
analysis wherein the polarity of the output of the base line
correcting device is discriminated, the correcting operation of the
base line correcting device being carried out with a time lag when
the polarity of the output is positive or zero while the correcting
operations of the base line correcting device are instantaneously
carried out when the polarity of the output is negative.
These and other objects and features of the present invention will
become apparent from the following full description of the present
invention taken in conjunction with preferred embodiments thereof
with reference to the accompanying drawings, in which:
FIGS. 1(a) and 1(b) are schematic diagrams each showing examples
wave forms of the signal for chromatographical analysis, this
diagram being shown only for the purpose of illustration,
FIGS. 2(a) and 2(b) are schematic diagrams each showing another
example like that of FIG. 1,
FIGS. 3(a) and 3(b) are schematic diagrams each showing a further
example like that of FIG. 1,
FIGS. 4(a) and 4(b) are schematic diagrams each showings a still
further example like that of FIG. 1,
FIG. 5 is a schematic diagram showing a still further example like
that of FIG. 1,
FIG. 6 is a circuit block diagram showing a preferred embodiment of
the present invention,
FIG. 7 is a circuit block diagram showing the details of part of
FIG. 6,
FIG. 8 is a circuit block diagram showing another embodiment of
FIG. 7,
FIG. 9 is a schematic diagram of a wave form shown only for the
purpose of illustration, and
FIG. 10 is a schematic diagram of another wave form shown only for
purpose of illustration.
Considering the invention broadly, attention is directed to FIG. 6
which illustrates a Gas Chromatography detector 10 in schematic
block form for providing an input signal to the device 11 of the
present invention which is the base line corrector. The signal from
the detector 10 is amplified by a DC amplifier 12 which provides an
input for two branches of the circuit, i.e., to a peak detector 13
and the base line corrector 11. The peak detector 13 indicates the
existence of a peak in the signal from the detector 10 and
maintains the peak indicating signal for an interval of time
beginning from the occurrence of the onset of the analytical
voltage fluctuation and ending at the termination of the analytical
fluctuation. The signal in the peak detector 13 serves as one means
for informing the base line corrector 11 of the occurrence of the
peak so that the base line corrector 11 can withhold correction
during the analytical fluctuation. The base line corrector 11 is
adapted to co-operate with the input signal to correct the base
line drift as will be more throughly described hereinafter.
The output of the base line corrector 11 is supplied to digital
integrator including a voltage-to-frequency converter 14, a gate 15
and a counter 16. The base line corrector 11 provides an input
current to the converter 14 to effect a drift correction in
accordance with the present invention. The V-F converter 14
provides to the gate 15, an output in the form of pulses having a
repetition rate proportional to the amplitude of the input voltage.
The gate 15 can be switched on to transfer the pulses from the
converter 14 to the counter 16 when the peak detector 13 detects
the existence of a peak. The output of the counter 16 for counting
the number of the pulses is then fed to a printer 17 which
indicates the measured size of the peak. The base line corrector 11
in the gas chromatograph is usually operated in the range of the
low level signal the value of which is lower than that of a
threshold level provided selectively in accordance with the
sampling gas. The operation of the base line corrector 11 is
illustrated more in detail in FIG. 7.
FIG. 7 is a block diagram showing one embodiment of the base line
correcting device in accordance with the present invention.
Referring to FIG. 7, 21 is a base line correcting device input to
which signals from the chromatograph are provided, 22 being an
amplifier, 23 being a base line correcting device output, 24 and 25
being normally closed and normally open contact points,
respectively, for a relay which is described later, and 26 being an
amplifier or an integrator which consists of, for example, a
resistor 27 with the resistance value of R and a capacitor 28 with
the capacity of C. The output signal of the amplifier 22 is
supplied to the integrator 26 through the contact point 24, and the
input of the integrator 26 is fed back to the input side of the
output of the amplifier 26. The contact point 25 is disposed in
parallel with the resistor 27. 29 is a detector for the peak start,
30 being a detector for the peak end, 31 being a flip-flop circuit
which is set or reset by means of detectors 29 and 30, and 32 and
33 being relays each of which is operated by means of the flip-flop
31 for closing the contact points 24 and 25, respectively.
The amplifier 22 is provided with a signal from the chromatograph
at the input 21 thereof. When the contact point 24 is closed and
the contact point 25 is open, the output 23 of the amplifier 22 is
supplied to the integrator 26 and the output of the integrator 26
is fed back to the input side of the amplifier 22, whereby the
output 23 is reduced zero. This is the correcting operation for the
base line, which, as long as contact 24 is closed is continuously
carried out with a time lag determined by the time constant of the
resistance R and capacitance C of the integrator 26. It is well
known that the correcting operation for the base line is carried
out with a time lag by negative feedback of the integrator output
to the input side of the amplifier 22.
Next, the operations of the relay contacts 24 and 25 will be
described. When the start of the peak is detected by means of the
detector 29, the flip-flop circuit 31 is set by the output thereof.
At the setting by the output of the flip-flop circuit 31, the relay
32 is operated to open the contact point 24. At this time, the
relay 33 is not operated so that the contact point 25 is maintained
open. When the end of the peak is detected by means of the detector
30, the flip-flop circuit 31 is reset whereby the output
disappears. At this time, the relay 32 holds the contact point 24
for a fixed time which is a time lag, while the relay 33 closes the
contact point 25 for a very short time with the same time lag as in
the relay 32.
FIG. 9 is a wave form of a chromatograph for illustrating the
operation of the device shown in FIG. 7. Before the positive slope
of the peak is detected at point A, the contact point 24 in FIG. 7
is closed while the contact point 25 is open, and the correcting
operation for the base line is carried out with a fixed time lag.
When the start of the positive slope of the peak has been detected
at the point A, an output of the detector 29 is provided to set the
flip-flop circuit 31, and the relay 32 opens the contact point 24
by the setting output of the flip-flop circuit. Therefore, since
the output of the amplifier 22 is not provided to the integrator
26, the correcting operation for the base line is not carried out,
whereby the value at the point A is retained. When the end of the
peak is detected at point B, the flip-flop circuit 31 is reset by
the output of the detector 30. At this time, the relay 32 closes
the contact point 24 after a fixed time lag, which is the time
interval corresponding to the time between B and C of FIG. 9, and
also, the relay 33 closes the contact point 25 for a very short
time after the same delay time. The contact point 24 remains open
for a fixed time after the end of the peak has been detected,
whereby the correcting operation for the base line is not carried
out during this period. At the time C, the contact point 24 is
closed and the contact point 25 closes for a very short time.
Accordingly, the contact point 24 remains closed during the very
short time, and the resistor 27 is short-circuited by the contact
point 25, whereby the correcting operation for the output 23 is
carried out instantaneously. If the output 23 has diverged from the
zero point, the output 23 is corrected to zero instantaneously.
After the correcting operation is completed, the contact point 25
opens while the contact point 24 remains closed. Accordingly, the
correcting operation for the base line is carried out again with
the usual time lag until the point D at the start of the positive
slope of the next peak.
When the start of the next peak has been detected by the detector
29 between B and C, of FIG. 9, or during the delay time when the
correcting operation for the base line is not carried out after the
end of one peak has been detected, the contact point 24 is opened
immediately by the output of the detector 29, whereby the
instantaneous correcting operation for the base line and the
following ordinary correcting operation are not carried out. The
area of the second peak is integrated with the same base line as
that of the first peak.
The relay 33 comprising, for example, a delay circuit, a not
circuit and a series circuit for a monostable multi-vibrator, can
close the contact point 25 for a short time after a fixed delay
time when the setting output from the flip-flop disappears.
The present invention is designed as described hereinbefore, so as
to delay the start of the correcting operation for the base line
during a fixed time upon detection of the peak end, to carry out
the instantaneous correcting operation for the base line during a
very short time, unless the start of the next peak is detected
during a fixed delay time, to instantaneously correct the
divergence of the base line during the detection of the first peak
and thereafter, to carry out the correcting operation for the base
line with the ordinary time lag. Therefore, if the time interval,
i.e., delay time, or the time between B and C of FIG. 9 during
which the correcting operation for the base line, after the end of
the peak has been detected for peak as in FIG. 2(a), is not carried
out, is selected to be shorter than the time interval between B and
C of FIG. 2(a), the instantaneous correcting operation for the base
line can be carried out at the point C of FIG. 2, whereby a correct
calculation of peak area can be carried out, as in FIG. 2(a), with
respect to the second peak. If the second peak is wide and gentle,
and the detection of the start of the peak is delayed (if the peak
of FIG. 1(b) is the second peak, and the first peak has ended prior
thereto) as shown in FIG. 1(b), the instantaneous correcting
operation for the base line is completed by point B, and the
correcting operation for the base line is carried out with the
ordinary time lag at the point B. Thus, the shaded area of FIG.
1(b) can be calculated correctly.
On the other hand, if the time between B and C of FIG. 9 is
selected to be longer than the time between B and C of FIG. 3(a)
for a peak as shown in FIG. 3(a), the correcting operation for the
base line is not carried out at all between B and C of FIG. 3(a),
whereby the area covered with oblique lines in FIG. 3(a) can be
calculated correctly. The time between B and C of FIG. 9 can be
changed at will by a change of the delay time of the relays 32 and
33. Therefore, according to the present invention, the correct
calculation of peak area can be carried out with respect to any
chromatograph.
The start of the correcting operation for the base line after
detection of the end of the peak can be delayed by means of the
flip-flop circuit 31, and the relays 32 and 33. Since the delay
time is variable, the circuit comprising these elements 31, 32 and
33 has been called a delay control circuit in view of the fact that
the relay 32 opens the contact point 24 without the delay time upon
detection of the peak start, but operates with the delay time when
the contact point 24 is closed.
FIG. 8 is a block diagram showing another example of the device in
accordance with the present invention, wherein 41 is an input
terminal to which the signal from the chromatograph is provided, 42
being an amplifier, 43 being a feedback circuit for correcting the
base line, 44 being a polarity discriminating means, 45 being a
relay having two contacts 46 and 47, 48 being a switch, and 49
being an output terminal.
The circuit including the amplifier 42 and the feedback circuit 43,
for carrying out the correcting operation for the base line with
the time lag, is known to those skilled in the art. In this case,
the feedback circuit 43 is, for example, an integration circuit,
the signal of output side P of the amplifier 42 being fed back to
the amplifier 42 as a negative feedback signal by the feedback
circuit 43, whereby the signal at point P is controlled to be zero.
The signal supplied from the chromatograph through the terminal 41
appears at point P through the amplifier 42. It is well known that
the signal of point P is controlled to zero with a fixed time lag
to carry out the correcting operation for the base line.
Also, a circuit for carrying out the correcting operation for the
base line by feeding the signal at P back to the amplifier 42 is
also known.
Referring to FIG. 8, the signal at point P is fed through the
feed-back circuit 43 to the input side of the amplifier 42 with a
fixed time lag when the contact point 46 of the relay 45 is closed,
whereby the signal at point P is controlled to zero with a fixed
time lag. On the other hand, when the contact point 47 of the relay
45 is closed, the signal at point P is instantaneously controlled
to zero. The switch 48 opens when a peak has been detected. The
correcting operation for the base line is not carried out during a
period in which the switch 48 is open, with the result that the
feedback from the feedback circuit to the amplifier is maintained
at a constant value.
The polarity discriminating device 44 detects the polarity of the
signal at point P. The polarity of the signal which is applied to
the input terminal 41 negative slope, is negative, and the polarity
of the signal at point P when the signal at point P has been
shifted from zero by such a signal is negative. The polarity
discriminating device 44 closes the contact point 46 of the relay
45 when the signal at the point P is positive or zero, while the
contact point 47 of the relay 45 closes when the signal at the
point P is negative.
Referring to FIG. 10, the vertical axis shows the level of the
signal at the input terminal 41 and the signal at point P, while
the horizontal axis shows time. Assuming now that the signal (a) at
the input terminal 41 has been changed to the negative direction
after the time point t.sub.O, the signal (b) at the point P, which
has been corrected with a fixed time lag, also changes to the
negative direction, whereby the contact point 47 of the relay 45
closes, and the contact point 46 thereof is opened by the output of
the polarity discriminating device 44. When the contact point of
the relay 45 is switched to 47, the signal at the point P is
instantaneously fed back to the amplifier 42 through the feed-back
circuit 43 to instantaneously set the signal at the point P to
zero. At the time point t.sub.1, the correction for the base line
is instantaneously carried out to set the signal at the point P to
zero, whereupon the relay 45 is switched to complete the circuit
through the contact point 46 by the output of the discrimination
circuit 44. At this time, the signal at point P is fed back to the
amplifier 42 with a fixed time lag through the feed-back circuit
43. If the signal (a) at the input 41 still remains in the negative
direction, the signal at point P is changed to negative again with
the fixed time lag. At the time point t.sub.2, the relay 45 is
again switched to complete the circuit through the contact point 47
by the discriminating circuit 44, whereby the signal at the point P
is instantaneously fed back to the amplifier 42 to again set the
signal at point P to zero. Such operation is repeated so long as
the signal (a) at the input 41 is in the negative direction. Each
time the signal at point P is instantaneously set to zero, the
instantaneous correcting operation for the base line is carried
out. The waveforms (b) of FIG. 10 show the signals at the point P
which have been corrected as described hereinbefore.
The advantages obtainable by the present invention as described
with reference to FIG. 8 are described hereinafter with reference
to FIG. 4(b). FIG. 4(b) shows the changes of the base line for the
peaks as in FIG. 4(a) with respect to the time elapsed. At the
point B, the output of the amplifier 42 is zero, corresponding to
t.sub.0 of FIG. 10. As the slope, corresponding to (a) of FIG. 10,
of the negative slope from point B of FIG. 4(b) to point C thereof,
is corrected such as shown by (b) in FIG. 10, the detection point C
of the start of the second peak becomes the base line for the
second peak, whereby the area of the portion defined by C, E, F and
D covered with the oblique lines in FIG. 4(b) can be calculated. It
will be found that the error is greatly reduced as compared with
the shaded portion defined by E and F in FIG. 4(a).
As described hereinbefore, in the present invention, the output the
signal, signal at point P of the amplifier 42 which receives the
signal from the chromatograph, is fed back through a feed-back
circuit 43. The output signal of the amplifier 42 is set to zero to
carry out the correcting operation for the base line of the
integrator for the chromatograph, and the amplifier 42 and
feed-back circuit 43 carry out the correcting operation for the
base line as described hereinbefore. Therefore, they are
hereinafter refered to as a base line correcting device. However,
the output signal of the base line correcting device produces an
output signal of the amplifier 42 or the signal at the point P. In
this case, a circuit 44, which detects the polarity of the output
of the base line correcting device, decides whether the polarity of
the output signal of the base line correcting device is negative or
positive or zero. When the polarity of the output signal of the
base line correcting device is detected as being positive or zero
by the the polarity discriminating circuit, the correcting
operation for the base line is carried out with a fixed time lag,
while, when the polarity of the output signal of the base line
correcting device is negative, the correcting operation for the
base line is instantaneously carried out. Accordingly, when the
base line is shifted in the positive direction, the correcting
operation for the base line is carried out by a conventional
fixed-time-lag-system as described with reference to FIG. 1(b). The
correcting operation for the base line is instantaneously carried
out on the negative slope or when the base line suddenly shifts in
the negative direction due to a pressure change or the like. Thus,
the area under the peak can be calculated more correctly, even on
the negative slope or when the base line suddenly shifts in the
negative direction. Although the present invention has been fully
described by way of example, various changes and modifications will
be apparent to those skilled in the art. For example, the
correcting operations for the base line hereinbefore described in
connection with FIG. 8 are applied to the initial state of a
gas-chromatographical measurement in which the base line is
normally shifted all of a sudden from the high value of the carrier
gas to the low value of the sample gas beyond the small value of
the usual shifts thereof. In addition, both means described as a
first embodiment shown in FIG. 7 and a second embodiment shown in
FIG. 8 can be employed together so as to use properly either of the
above two means in accordance with the detected peak of the wave
form, for example, in such a manner that, when the wave form of
signal has a plurality of integrated small peaks on the negative
slope thereof, the first means are employed with respect to the
first small peak while the second means are employed with respect
to the other small peak. Also, the detailed construction of means
44 and 47 described in the second embodiment shown in FIG. 8 is the
same as the construction of means 25, 26, 27 and 28 described in
the first embodiment shown in FIG. 7 as a unit.
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