Universität Duisburg-Essen Dr.

Siddiqi
Fakultät für Ingenieurwissenschaften
Abteilung Maschinenbau
Institut für Verbrennung und Gasdynamik
Thermodynamik

ISE-Bachelor

CONCENTRATION MEASUREMENT

(THERE IS A SMALL PART IN GERMAN LANGUAGE)

1
Concentration Measurement

1 Introduction

2 Important gas analysis methods

2.1 Orsat-Apparatus

2.2 Infra red spectroscopy

2.3 Paramagnetic oxygen analysis

2.4 Mass spectrometry

2.5 Gas chromatography

2.6 Thermal conductivity detector (TCD)

2.7 Flame ionization detector (FID)

3 Experiments for concentration measurements

3.1 Measurement of the concentration of Propane, Isobutane and n-Butane
in gas mixture using a gas chromatograph

3.1.1 Basic principles

3.1.2 Experimental set up

3.1.3 Experimental procedure

3.1.4 Evaluation

3.2 Bestimmung der Raumanteile von CO2 und CO in einem Gasgemisch

mit den Prüfröhrchen

3.2.1 Kurzbeschreibung

3.2.2 MAK Wert

3.2.3 Chemische Grundlagen

3.2.4 Versuchsaufbau

3.2.5 Versuchsablauf

2
1 Introduction
The general purpose of gas analysis is to measure the concentration of each
component in a gas mixture. Both physical and chemical methods are applied in gas analysis.
Each gas component is measured on the basis of different chemical/physical or physical
principles of measurements. Such principles include:

a. Chemical reactions (e.g. Orsat Apparatus, Dräger test tubes)

b. Absorption of radiation (e.g. infrared)
c. Paramagnetism (this method measures oxygen concentration)
d. Mass spectrometry
e. Gas chromatography
f. Thermal conductivity (requires separation using chromatography)
g. Flame ionization (requires separation using chromatography)

2. Important gas analysis methods

2.1 ORSAT apparatus:

The Orsat apparatus, illustrated in Fig. 1, is generally used for analyzing gas mixtures (e.g.
flue gases). The burette 4 is graduated in cubic centimeters up to 100, and is surrounded by a
water jacket to prevent any change in temperature from affecting the density of the gas being
analyzed.

It uses three pipettes (some use four pipettes for more accuracy), (1+1a),(2+2a),(3+3a), the
first containing a solution of caustic potash (KOH) for the absorption of carbon dioxide, the
second an alkaline solution of pyrogallol (1,2,3-trihydroxybenzene) for the absorption of
oxygen, and the third an acid solution of cuprous chloride (Cu2Cl2) for absorbing the carbon
monoxide. Each pipette contains a number of glass tubes, to which some of the solution
clings, thus facilitating the absorption of the gas. In the pipette 3, copper wire is placed to re-
energize the solution as it becomes weakened. The rear half of each pipette is fitted with a
rubber bag, one of which is shown at 15, to protect the solution from the action of the air. The
solution in each pipette should be drawn up to the mark on the capillary tube.

The gas is drawn into the burette through the valve 11. To discharge any air or gas in the
apparatus, the valve is opened to the air and the bottle 9 is raised until the water in the burette
reaches the 100 cubic centimeters mark. The valve 11 is then turned so as to close the air
opening and allow gas to be drawn through, the bottle 9 being lowered for this purpose. The
gas is drawn into the burette to a point below the zero mark, the valve 11 then being opened to
the air and the excess gas expelled until the level of the water in 9 and in 4 are at the zero
mark. This operation is necessary in order to obtain the zero reading at atmospheric pressure.

The apparatus should be carefully tested for leakage as well as all connections leading thereto.

3
Figure1 : Orsat apparatus.

Before taking a final sample for analysis, the burette 4 should be filled with gas and emptied
once or twice, to make sure that all the apparatus is filled with the new gas. The valve 11 is
then closed and the valve 14 in the pipette 1a is opened and the gas driven over into 1a by
raising the bottle 9. The gas is drawn back into 4 by lowering 9 and when the solution in 1a
4
has reached the mark in the capillary tube, the valve 14 is closed and a reading is taken on the
burette, the level of the water in the bottle 9 being brought to the same level as the water in 4.
The operation is repeated until a constant reading is obtained, the number of cubic centimeters
being the percentage of CO2 in the gas mixture.

The gas is then driven over into the pipette 2a and a similar operation is carried out. The
difference between the resulting reading and the first reading gives the percentage of oxygen
in the gas mixture.

The next operation is to drive the gas into the pipette 3a.

The process must be carried out in the order named, as the pyrogallol solution will also absorb
carbon dioxide, while the cuprous chloride solution will also absorb oxygen.

The analysis made by the Orsat apparatus is volumetric; if the analysis by weight is required,
further calculations are to be done.

2.2 Absorption of radiation (Infra red spectroscopy)

The basis for the quantitative measurements using optical spectroscopy is provided by the
Lambert-Beer law which relates the spectral response (absorbance) to the concentration.
The absorbance of a measured absorption band is a function of the measurement wavelength,
the thickness of the sample and the concentration of the absorbing species being measured.
This is expressed as follows:
A1λ = ε1λ c1d
where A1λ is the absorbance of species 1 at wavelength λ , ε1λ is the absorptivity of species 1
at wavelength λ , c1 is the concentration of the absorbing species 1, and d is the optical
thickness of the sample or path length of the measurement cell. So from the absorbance
measurements the concentration c of a particular component may be calculated.

Infrared spectroscopy includes the methods that are based on the absorption (or reflection) of
electromagnetic radiation with wavelengths in the range of 0.8 to 1000 μm. This spectral
range has been divided into three groups: near infrared (NIR) (0.8 – 2.5 μm), mid infrared
(MIR)(2.5 – 25 μ) and far infrared (FIR) (25 – 1000 μm). Of these three ranges the MIR
region is the most accessible and the richest in providing structural information (molecular
fingerprint). Infrared analyses are performed on dispersive (conventional) and Fourier-
transform spectrometers.

Besides the dispersive spectrophotometers many spectrometers have been designed for
routine analysis (in laboratory as well as for on-site control) to quantify one or many
compounds. Almost one hundred gases or volatile compounds can be quantified with the help
of such photometers. The optical lay outs for two typical models are shown in Figure 2. The
most widely used photometers are for the measurement of carbon monoxide (CO)
[absorbance measurement at 2170 cm-1] and carbon dioxide (CO2) [absorbance measurement
at 2350 cm-1] from car exhausts.

In Figure 2a the light coming from the source S passes through an interface filter F depending
on the wavelength to be measured. Cell C contains the sample while the reference cell R
5
contains a known concentration of the same type of gas to be quantified. Another cell A is
filled with a non absorbing gas (N2). The cells A and R are placed in the optical path
alternatively. By a comparison of the absorbance measured by the detector with and without
the sample cell in the path the concentration of the concerned gas in the sample can be
determined.

In the other model (Figure 2b) the light beam from the source 1 travels through the
measurement cell 2 before reaching the cells V1 and V2 which contains the gas component to
be measured (e.g. CO or CO2). In this arrangement the sample absorbs a part of the radiation
before the radiation reaches V1. The chambers V1 and V2 are so constructed that in the
absence of any absorbance in the measurement cell (e.g. when the inert gas flows through it)
the absorption in V1 and V2 are same and no pressure difference is observed by the pressure
transducer. The beam chopper M is necessary to obtain a repetitive pulsed signal. This is the
zero point adjustment. The intensity of the beam reaching V1 will be attenuated if the same
gas is present in cell (as is the case it is the case when the sample flows through V) and this
will be proportional to the concentration of the gas component to be measured.

Figure 2: Layout of some typical gas analysers.

2.3 Paramagnetic Oxygen Analyser

Oxygen has a relatively high magnetic susceptibility as compared to other gases such as
nitrogen, helium, argon, etc. and displays a paramagnetic behaviour. The paramagnetic
oxygen sensor consists of a cylindrical shaped container inside of which is placed a small
glass dumbbell. The dumbbell is filled with an inert gas such as nitrogen and suspended on a
taut platinum wire within a non-uniform magnetic field. The dumbbell is designed to move
freely as it is suspended from the wire. When a sample gas containing oxygen is processed
through the sensor, the oxygen molecules are attracted to the stronger of the two magnetic
fields. This causes a displacement of the dumbbell which results in the dumbbell rotating. A
precision optical system consisting of a light source, photodiode, and amplifier circuit is used
to measure the degree of rotation of the dumbbell. In some paramagnetic oxygen sensor
designs, an opposing current is applied to restore the dumbbell to its normal position. The
6
current required to maintain the dumbbell in it normal state is directly proportional to the
partial pressure of oxygen and is represented electronically in percent oxygen. There are
design variations associated with the various manufacturers of magnetodynamic paramagnetic
oxygen sensors. Also, other types of sensors have been developed that use the susceptibility
of oxygen to a magnetic field which include the thermomagnetic or `magnetic wind' type and
the magnetopneumatic sensor. In general, paramagnetic oxygen sensors offer very good
response time characteristics and use no consumable parts, making sensor life, under normal
conditions, quite good. It also offers excellent precision over a range of 1% to 100% oxygen.
The magnetodynamic sensor is quite delicate and is sensitive to vibration and/or position. Due
to the loss in measurement sensitivity, in general, the paramagnetic oxygen sensor is not
recommended for trace oxygen measurements.

Figure 3: Layout of a paramagnetic analyser.

2.4 Mass spectrometry

Mass spectrometry (MS) is an analytical technique for the determination of the elemental
composition of a sample. The MS principle consists of ionizing chemical compounds to
generate charged molecules or molecule fragments and measurement of their mass to charge
ratios. In a typical MS procedure:

1. a sample is loaded onto the MS instrument, and undergoes vaporization.

2. the components of the sample are ionized by one of a variety of methods (e.g., by
impacting them with an electron beam), which results in the formation of positively
charged particles (ions)
3. the positive ions are then accelerated by a magnetic field
4. computation of the mass to charge ratio of the particles based on the details of motion
of the ions as they transit through electromagnetic fields, and
5. detection of the ions, which in step 4 were sorted according to m/z.

7
MS instruments consist of three modules: an ion source, which can convert gas phase sample
molecules into ions; a mass analyser, which sorts the ions by their masses by applying
electromagnetic fields; and a detector, which measures the value of an indicator quantity and
thus provides data for calculating the abundances of each ion present. The technique has both
qualitative and quantitative uses. These include identifying unknown compounds, determining
the isotopic composition of elements in a molecule, and determining the structure of a
compound by observing its fragmentation. Other uses include quantifying the amount of a
compound in a sample or studying the fundamentals of gas phase ion chemistry (the
chemistry of ions and neutrals in a vacuum). MS is now in very common use in analytical
laboratories that study physical, chemical, or biological properties of a great variety of
compounds.

Figure 4: Schematic diagram of a mass spectrometer.

2.5 Gas chromatography

Chromatography is the collective term for a family of laboratory techniques for the separation
of mixtures. It involves passing a mixture dissolved in a "mobile phase" through a stationary
phase, which separates the component to be measured from other molecules in the mixture
and allows it to be isolated. Chromatography is a physical method of separation in which the
components to be separated are distributed between two phases, one which is the stationary
(stationary phase) while the other (the mobile phase) moves in a definite direction. In
chromatographic methods, separations results from differences in the distribution constants of
the individual sample components between the two phases.

8
In gas chromatography (GC) separations are achieved by distribution of a solute between an
immobile solid or liquid stationary phase and a gas phase that percolates over the stationary
phase. Sample molecules spend part of the time in the mobile phase and the other part in the
stationary phase during the passage through the column. The time for an unretained solute to
reach the detector from the point of injection is called the column dead time or the hold -up
time(tM). The solute retention time (tR) is the time difference between sample injection and
the detector sensing the maximum of the retained peak. The amount of time solute molecules
spend in the stationary phase is called the adjusted retention time (tR’).
tR= tR’+ tM

Retention factor (or capacity factor) is more fundamentally important than the absolute
retention time. This represents the ratio of the time spent by solute in the stationary phase to
the time it spends in the mobile phase. k= tR’/ tM = (tR - tM)/ tM In gas chromatography it is
usually more convenient to measure the retention factor, k, than the gas-liquid partition
coefficient, K, which requires exact knowledge of the column phase ratio. The gas-liquid
partition coefficient is the relevant free energy parameter for modeling retention but this is of
no great consequence since the partition coefficient is related to the retention factor by the
relationship K = bk where b is the column phase ratio (volume of gas phase/volume of
stationary phase).

The main parts of a basic GC system are shown in Figure 5. One or more high purity gases
are supplied to the GC. One of the gases (called the carrier gas) flows into the injector,
through the column and then into the detector. A sample is introduced into the injector usually
with a syringe or an exterior sampling device. The injector is usually heated to 150-250 °C
which causes the volatile sample solutes to vaporize. The vaporized solutes are transported
into the column by the carrier gas. The column is maintained in a temperature controlled
oven. The solutes travel through the column at a rate primarily determined by their physical
properties, and the temperature and composition of the column. The various solutes travel
through the column at different rates. The fastest moving solute exits (elutes) the column first
then is followed by the remaining solutes in corresponding order. As each solute elutes from
the column, it enters the heated detector. An electronic signal is generated upon interaction of
the solute with the detector. The size of the signal is recorded by a data system and is plotted
against elapsed time to produce a chromatogram.

Figure 5: A GC system.
9
The ideal chromatogram has closely spaced peaks with no overlap of the peaks. Any peaks
that overlap are called co-eluting. The time and size of a peak are important in that they are
used to identify and measure the amount of the compound in the sample. The size of the
resulting peak corresponds to the amount of the compound in the sample. A larger peak is
obtained as the concentration of the corresponding compound increases. If the column and all
of operating conditions are kept the same, a given compound always travels through the
column at the same rate. Thus, a compound can be identified by the time required for it to
travel through the column (called the retention time). The identity of a compound cannot be
determined solely by its retention time. A known amount of an authentic, pure sample of the
compound has to be analyzed and its retention time and peak size determined. This value can
be compared to the results from an unknown sample to determine whether the target
compound is present (by comparing retention times) and its amount (by comparing peak
sizes). If any of the peaks overlap, accurate measurement of these peaks is not possible. If two
peaks have the same retention time, accurate identification is not possible. Thus, it is desirable
to have no peak overlap or co-elution.

2.6 Thermal conductivity detector (TCD)

The TCD consists of an electrically heated filament in a temperature-controlled cell. Under

normal conditions there is a stable heat flow from the filament to the detector body. When a
component (analyte) elutes and the thermal conductivity of the column effluent is reduced, the
filament heats up and changes resistance. This resistance change is often sensed by a
Wheatstone bridge circuit which produces a measurable voltage change. The column effluent
flows over one of the resistors while the reference flow is over a second resistor in the four-
resistor circuit.

Figure 6: Schematic diagram of a TCD.

A schematic of a classic thermal conductivity detector design utilizing a wheatstone bridge

circuit. The reference flow across resistor 3,4 (Luft,air) of the circuit compensates for drift

10
due to flow or temperature fluctuations. Changes in the thermal conductivity of the column
effluent flow across resistor 1,2 will result in a temperature change of the resistor and
therefore a resistance change which can be measured as a signal.

Since all compounds, organic and inorganic, have a thermal conductivity different from
helium, all compounds can be detected by this detector. The TCD is often called a universal
detector because it responds to all compounds. Also, since the thermal conductivity of organic
compounds are similar and very different from helium, a TCD will respond similarly to
similar concentrations of analyte. Therefore the TCD can be used without calibration and the
concentration of a sample component can be estimated by the ratio of the analyte peak area to
all components (peaks) in the sample.

The TCD is a good general purpose detector for initial investigations with an unknown
sample. Since the TCD is less sensitive than the flame ionization detector and has a larger
dead volume it will not provide as good resolution as the FID. However, in combination with
thick film columns and correspondingly larger sample volumes, the overall detection limit can
be similar to that of an FID. In conclusion the TCD is not as sensitive as other detectors but it
is non-specific and non-destructive.

The TCD is also used in the analysis of permanent gases (argon, oxygen, nitrogen, carbon
dioxide) because it responds to all these pure substances unlike the FID which cannot detect
compounds which do not contain carbon-hydrogen bonds.

2.7 Flame ionization detector (FID)

Flame ionization detector involves the detection of ions. The source of these ions is a small
hydrogen-air flame. Sometimes hydrogen-oxygen flames are used due to an ability to increase
detection sensitivity, however for most analysis, the use of compressed breathable air is
sufficient. The resulting flame burns at such a temperature as to pyrolyse most organic
compounds, producing positively charged ions and electrons.

The design of the Flame Ionization Detector varies from manufacturer but the principles are
the same in any case. Most commonly, the FID is attached to a Gas Chromatography system.

The elute exits the GC column (A) and enters the FID detector’s oven (B). The oven is needed
to make sure that as soon as the elute exits the column, it does not come out of the gaseous
phase and deposit on the interface between the column and FID. This deposition would result
in loss of effluent and errors in detection. As the elute travels up the FID, it is first mixed with
the hydrogen fuel (C) and then with the oxidant (D). The effluent/fuel/oxidant mixture
continues to travel up to the nozzle head where a positive bias voltage exists (E). This positive
bias helps to repel the reduced carbon ions created by the flame (F) pyrolysing the elute. The
ions are repelled up toward the collector plates (G) which are connected to a very sensitive
ammeter, which detects the ions hitting the plates, then feeds that signal to an amplifier,
integrator, and display system. The products of the flame are finally vented out of the detector
through the exhaust port (J).

11
 Figure 7: Schematic diagram of a FID.

The current measured corresponds roughly to the proportion of reduced carbon atoms in the
flame. Specifically how the ions are produced is not necessarily understood, but the response
of the detector is determined by the number of carbon atoms (ions) hitting the detector per
unit time. This makes the detector sensitive to the mass rather than the concentration, which is
useful because the response of the detector is not greatly affected by changes in the carrier gas
flow rate.

FID is detecting oxidized carbon atoms in ion form. So in organic species that already have
oxidized carbons via the presence of oxygen, a weaker signal is given when the sample enters
the detector because the oxidized carbons are not ionized as effectively as compared to
compounds solely of carbon and hydrogen. Functional groups such as carbonyl, alcohol,
halogens, or amines are sources of these oxidized carbons, sometimes causing few if any ions.
This points out one of the main drawbacks of using an FID to detect effluent as it comes off a
gas chromatograph column. Another drawback is the sample is destroyed, making it
impossible to use the sample for other measurements. For this reason the FID is typically the
final detector or stage in a series of instruments.

Some of the benefits of a flame ionization detector are quite useful. FIDs are insensitive to
H2O, CO2, CS2, SO2, CO, NOx, and noble gases because they are not able to be
oxidized/ionized by the flame. This allows samples to be studied even if contaminated or if
some leakage of ambient room gases occurs at the time of the injection. Additionally, it has
the ability to determine when a sample will elute off the column with regards to the solvents
used. Some detectors can be damaged if an effluent too concentrated is analyzed, making it
necessary to turn it off to prevent damage.

12
3 Experiments for concentration measurements
3.1 Mesurement of the concentration of Propane, Isobutane and n-
Butane in a gas mixture using a gas chromatograph

A gas mixture (from a gas lighter) will be separated in its components with the help of a gas
chromatograph and its composition will be determined.

3.1.1 Basic principles

Chromatography is a physical method of separation in which the components to be separated
are distributed between two phases, one which is the stationary (stationary phase) while the
other mobile phase(a gas) moves in a definite direction. In chromatographic methods,
separations results from differences in the distribution constants of the individual sample
components between the two phases. The various solutes (components) travel through the
column at different rates. The fastest moving solute exits (elutes) the column first then is
followed by the remaining solutes in corresponding order. Thus the components are separated.
The concentration of each component is then measured using a suitable detector.

3.1.2 Experimental set up

Components:
- Gas separation column
- Glass jacket
- Measuring probe
- Control unit for gas chromatography

Figure 8: Chromatograph Type 36670.88 of Phywe company.

The gas chromatograph consists of a separation column with a glass jacket. The separation
column is a1.5 m long spiral shaped glass tubing having 4 mm diameter. The tubing end

13
 on a functional head. One end of the tubing serves as inlet for the carrier gas and the
measuring probe is connected via a glass gas inlet tube (7 in Fig. 9)

Figure 9: A TCD detector is used as measuring probe.

The measuring probe model 36670.10 (Fig. 9) is used for the measurements. The details of
this measuring probe and the control unit for gas chromatograph are given at the end
under phywe-36670.99.

Figure 10: Control unit for gas chromatography.

The control unit together with the measuring probe detects the components separated by
gas chromatograph.

14
3.1.3 Experimental procedure
1 ml of gas mixture is sucked in an injection gas syringe (1ml) [from gas lighter ampoule].
The gas is then injected into the apparatus with through the rubber seal via the needle of a
gas syringe. Some pressure is applied to press the needle forward through the rubber seal
up to the separation column inside the glass jacket, the gas is now injected in the
separation column and then the needle is pulled back from the seal and the screw on the
coupling ring. Care is to be taken that during this operation the needle is not separated
from the syringe and falls inside the jacket. After multiple uses (test the tightness of the
seal) the seal is to be replaced by a new one. The PC Program LabView will be started and
it shows the measured data. The elution profile (see Figure 11) is displayed on PC screen.
After all the 4 components are eluted (seen by the profile) and the voltage has dropped to
the initial value the program can be stopped.

3.1.4 Evaluation

There are 4 maxima in the elution profile. The first belongs to the part of the air which
entered with the gas mixture. The other 3 are the components of the butane gas mixture
(butane gas mixture from the lighter). The gas mixture was separated into 3 components.
The first fraction is the smallest fraction and the third the largest. This is indicated by the
elution profile. The two expected fractions belong to butane (normal butane b.p. -0.5°C,
isobutane b.p. -11,7°C) are seen as fraction 2, (isobutane with lower b.p.) and fraction 3
(Normal butane with higher b.p.). Fraction 1 is an impurity. It is propane (b.p. -42,1 °C).
This can be confirmed if pure propane (from the gas cylinder) is investigated in the
apparatus in the way. The vol-% fractions of each component can be determined from the
area under the concentration curve. The evaluation can be done with the help of a suitable
computer program (e.g. Microsoft Excel).

15
Formula for the calculation of the area:

=ABS((C2-$C$1)*(B2-B1)+0,5*(C2-

Figure 11: Data evalaution with Microsoft Excel

16
3.2 Bestimmung der Raumanteile von CO2 und CO in einem Gasgemisch
mit den Prüfröhrchen

3.2.1 Kurzbeschreibung
Für die Luftuntersuchung am Arbeitsplatz, die Bestimmung kleiner Konzentrationen
giftiger Gase und Dämpfe in der Atemluft (MAK Wert) sowie für die technische
Gasanalyse werden die Prüfröhrchen eingesetzt. Sie gehören heute zu den klassischen
Messverfahren der Gasanalyse. Ein Prüfröhrchen ist ein Glasröhrchen, das eine chemische
Substanz enthält, welche mit dem zu messenden Gas reagiert und eine Farbänderung
herbeiführt. Die Röhrchen sind mit einer Skala versehen. Die Länge der Farbzone stellt
ein Maß für die Konzentration des zu messenden Stoffes dar.

3.2.2 Der MAK Wert

Grenzwerte haben für den praktischen Arbeitsschutz eine zentrale Bedeutung. Die MAK-
Werte (Maximale Arbeitsplatz-Konzentration) sind eine Beurteilungsgrundlage für die
Bedenklichkeit oder Unbedenklichkeit der am Arbeitsplatz auftretenden Konzentrationen
von Schadstoffen. Neben der Giftigkeit der eingeatmeten Stoffe werden bei der
Festlegung der Werte noch andere Faktoren berücksichtigt, u.a. Ätzwirkung,
Hautdurchdringungsvermögen, sensibilisierende und ernsthaft beeinträchtigende
Eigenschaften.

Der MAK-Wert ist die höchstzulässige Konzentration eines Arbeitsstoffes (Gas, Dampf
oder Schwebstoff) in der Luft am Arbeitsplatz, die auch bei wiederholter und
langfristiger, in der Regel achtstündiger Exposition im Allgemeinen die Gesundheit der
Beschäftigten nicht beeinträchtigt und diese nicht unangemessen belästigt.

Der MAK-Wert für Kohlenmonoxid beträgt 33mg/m³. Wir messen in diesem Versuch
eine höhere Konzentration im Probengas. Da sich das Probengas aber im Raum verteilt,
bleibt es im Ganzen unter dem MAK-Wert.

3.2.3 Chemische Grundlagen

Die Grundlage der Prüfröhrchen sind chemische Reaktionen des zu messenden Stoffes
(Gases) mit der chemisch-reagierenden Substanz der Füllschichten. Die Reaktionen sind
mit einer Farbänderung verbunden. Die Farbänderung ist ein Maß für den Massenumsatz
des reagierenden Gases mit dem Präparat (der chemisch-reagierenden Substanz) im
Röhrchen. Meist gelingt es, diesem Stoffumsatz quantitativ in Form einer
Färblängenanzeige darzustellen.

Für Kohlenstoffmonoxid kommt die folgende Reaktion zur Anwendung:

5CO + I2O5 ⎯H⎯ ⎯→ 5CO2 + I2

2 SO4

Die Umsetzung von Iodpentoxid zu Iod wird unter sauren Bedingungen mit
Kohlenstoffmonoxid durchgeführt. Es ist grundsätzlich eine klassenselektive Reaktion zur

17
Messung leicht oxidierbarer Stoffe. Die Selektivität läßt sich durch geeignete
Vorschichten gezielt steigern.

Die Messung von Kohlenstoffdioxid wird durch Oxidation von Hydrazinhydrat bei
Anwesenheit von Kristallviolett als Redoxindikator durchgeführt:

CO2 + N2H4 ⎯
⎯→ NH2-NH-COOH

Da die Konzentration von Kohlenstoffdioxid typischerweise im Vergleich zu anderen

Schadstoffen höher ist, beeinträchtigt die Querempfindlichkeiten die Selektivität nicht.
Unter Querempfindlichkeit versteht man die Eigenschaft eines Stoffes einen anderen im
Messverfahren zu beeinflussen und so das Messergebnis zu verfälschen.

3.2.4 Versuchsaufbau

Das Meßsystem besteht aus einem Dräger-Röhrchen und einer Dräger-Gasspürpumpe.

Jedes Dräger-Röhrchen enthält ein hochempfindliches Reagenzsystem, das immer dann
präzise Messergebnisse ermöglicht, wenn die technischen Eigenschaften der verwendeten
Gasspürpumpe auf die Reaktionskinetik des Reagenzsystems im Röhrchen exakt
abgestimmt wird. Deshalb muss bei einer Gasspürpumpe das Fördervolumen und der
zeitliche Ablauf des Volumenstromes (Saugcharakteristik), innerhalb geringer
Toleranzen auf das Röhrchen abgestimmt sein. Diese Anforderungen sind in
internationalen Prüfröhrchen-Standards (Normen) festgelegt, wonach die Verwendung
von Prüfröhrchen mit einer dazu passenden Pumpe des gleichen Herstellers gefordert
wird.

Für die Messung von Momentankonzentrationen wird Dräger-Gaspürpumpe Modell 31

eingesetzt. Dräger-Gasspürpumpe Modell 31 ist eine handbetätigte Balgpumpe mit ca.
100 cm³ Hubvolumen, d.h. die Pumpe saugt pro Hub 100 cm³ an. Den Aufbau eines
solchen Gerätes zeigt Abb. 20.

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Abb. 20: Die Balgpumpe und das Prüfrohrchen

3.2.5 Versuchsablauf
1. Das Gasgemisch aus der Prüfgasflasche mit einer Entnahmevorrichtung in einen
Meßbeutel von 1 Liter Inhalt geblasen.
2. Die Gasspürpumpe auf Funktionsfähigkeit prüfen.
Dichtigkeitsprüfung:
• Pumpe mit ungeöffneten Röhrchen zusammen drücken.
• Nach Freigabe der Pumpe darf sich die Position des Balges eine Minute lang nicht
ändern.
Saugleistungsprüfung:
• Nach Zusammendrücken der Pumpe muß sich der Balg schlagartig öffnen.
3. Beide Spitzen des Dräger-Röhrchens in der Abbrechöse (Abb21(a)) der Pumpe oder
in der Abbrechhülse (Abb. 21(b)) abbrechen.
4. Dräger-Röhrchen in den Pumpenkopf dicht einsetzen, so daß der Pfeil zur Pumpe
zeigt (Abb. 21(c)).
5. Pumpe in die Hand nehmen, wie Abb. 21(d) zeigt.
6. Die andere Seite des Röhrchens in den Meßbeutel einsetzen.
7. Balg bis zum Anschlag zusammendrücken (Abb. 21(e)).
8. Finger strecken. Saugvorgang läuft selbsttätig ab und ist beendet, wenn die Kette
gespannt ist. (Abb.21(f)).
9. Saugvorgang so oft wiederholen, wie es die Gebrauchsanweisung des Dräger-
Röhrchens vorschreibt. (Auf den Röhrchen ist ein n-Wert aufgedruckt. Dabei gibt n
die Anzahl der notwendigen Pumpenhübe an. In unserem Fall ist n meist 1.)
10. Anzeige auswerten. Bei der Auswertung soll nach drei Fällen unterschieden werden:
- die Farbanzeige endet rechtwinklig zur Röhrchen-Längsachse (Abb. 22(a)),
- die Farbanzeige ist schräg zur Röhrchen-Längsachse (Abb. 22(b)),
- die Farbanzeige verläuft nicht gleichmäßig (Abb22(c)).

19
Abb. 21: Versuchsablauf

Abb. 22: Drei unterschiedliche Fälle der Farbanzeige

Wenn die Farbanzeige rechtwinklig zur Röhrchen-Längsachse verläuft, kann die

Konzentration direkt an der Skala abgelesen werden. Ist die Farbanzeige verzerrt
(verläuft schräg zur Röhrchen-Längsachse), so ist eine lange und eine kurze
Verfärbung zu erkennen. In diesem Fall wird aus den beiden Anzeigen der
Mittelwert gebildet. Bei einer nicht einheitlich Verfärbung ist der Endpunkt dort
abzulesen, wo eine noch schwache Verfärbung gerade sichtbar ist.

20
 R

Control unit for gas chromatography 36670.99

Measuring probe for gas chromatography 36670.10

PHYWE SYSTEME GMBH

Robert-Bosch-Breite 10
D-37079 Göttingen

Telefon (0551) 604-0

Telefax (0551) 604-107

The instrument complies

with the corresponding
EC guidelines.

Operating Instructions
Fig. 1

Contents 1 PURPOSE AND CHARACTERISTIC FEATURES

The control unit for gas chromatography (article no.:
1 PURPOSE AND CHARACTERISTIC FEATURES 36670.99) serves, together with the measuring probe for gas
chromatography (article no.: 36670.10), for the detection of
2 HANDLING separated substances in the emergent flow of carrier gas
2.1 Functional and operating elements of the from a gas chromatograph by means of the thermal conduc-
control unit tivity principle. The control unit not only supplies power to the
2.2 Functional and operating elements of the measuring probe, but also contains a measuring system with
measuring probe which the change in the resistance of the measuring probe
2.3 Putting into operation can be detected.
2.3.1 Electrical connection The most important part of the measuring probe is an NTC
2.3.2 Connection of the measuring probe to the control unit element, which has a highest permissible temperature limit of
2.3.3 Connection of a display instrument to the control unit approximately 110°C. To avoid exposure to mechanical
2.3.4 Zero balancing the measuring bridge stress, the semiconductor and its fine lead wires are fused in
2.4 Notes on operation a thin walled glass capillary tube, which is fitted in a glass
tube with attached side tube. Power is supplied to the semi-
3 RECORDING A CHROMATOGRAM conductor through a coaxial cable with BNC plug, with which
the measuring probe is connected to the control unit.
4 CHANGING THE FUSE The measuring system in the control unit is based on the
principle of a voltage compensated measuring amplifier. With
5 SPECIFICATIONS the measuring probe connected, and after zero balancing,
there is a voltage of 0 mV on the recorder output of the con-
6 NOTE ON THE GUARANTEE trol unit (see 2.3.4). Subsequent changes in the detector resi-
stance effect a change in the measured value, which is pas-
7 RECOMMENDED ACCESSORIES sed to the output of the control unit as a proportional voltage
7.1 Chromatograph signal.
7.2 Display instruments Zero balancing and measurement signals can be displayed
7.2.1 Analogue demonstration multimeters by a measurement instrument connected to the recorder out-
7.2.2 Recorders put of the control unit. Suitable instruments for this are a mul-
7.2.3 Interface systems timeter (e.g. analogue demonstration multimeter ADM 2,
7.3 Literature article no. 13820.00), a Yt recorder (e.g. Yt Recorder, 1 chan-
nel, article no.: 11414.95), or an interface in connection with
a PC (e.g. Cobra3 CHEM-UNIT, article no.: 12153.00).

36670.99/4902 1
 1 6

2 3

Fig. 2

2 HANDLING
2.1 Functional and operating elements of the control 10
unit
With the exception of the on/off switch 1, all functional and
operating elements are on the front of the control unit

1 On/off switch
The on/off switch and the connecting socket for the
supply of power are to be found at the back of the
instrument.
7 9
2 Coarse balancing button 8
Press button ("COARSE") for coarse balancing of the
measuring bridge. Fig. 3

3 Rotary knob for fine balancing
Rotary knob ("FINE") for fine balancing of the measu-
ring bridge.
4 BNC socket for connection of the measuring probe
Input ("IN") for connection of the measuring probe
(article no.: 36670.10) for gas chromatography to the
control unit (see 2.2).
2.2 Functional and operating elements of the
measuring probe
7 Gas inlet tube
Connection of the measuring probe to the gas outlet of
a gas chromatograph is made via this glass gas inlet
tube. It has an outer diameter of 8 mm and the measu-
ring probe is held inside of it.

5 Recorder output 8 Gas outlet tube

Two 4 mm safety sockets with colour coding for The gas which flows into the measuring probe exits it
connection to a recorder, multimeter or interface via this glass gas outlet tube, which also has an outsi-
system for displaying measured values. de diameter of 8 mm.

6 Control lamp 9 BNC plug

The measuring probe is connected to the control unit
Green light-emitting diode shows when the instrument
via this BNC plug (see 2.1).
is switched on.
10 Handle
A handle is fixed to the sensor for handling and holding
the measuring probe.

36670.99/4902 2
2.3 Putting into operation
2.3.1 Electrical connection
Plug the connecting cable supplied with the control unit into
the socket in the back of the instrument and connect the
other end to the AC mains. Check that the AC mains voltage
is in accordance with the permissible voltage stated on the
type plate on the back of the instrument! The on/off switch is
also situated on the back of the instrument.
2.3.2 Connection of the measuring probe to the control unit
With the control unit still switched off, insert the BNC plug 9
of the measuring probe into the BNC socket 4 of the control
unit and lock it in position by turning it.
Important! It is imperative that you do not switch the con-
trol unit on until carrier gas flows around the sensor of the
measuring probe. Should you do so, and so put the mea-
suring probe into operation without a flow of carrier gas,
heat conduction away from the sensor could be insuffi-
cient with resulting damage to the NTC element.
Further to this, the temperature of the carrier gas flowing
into the measuring probe must not exceed 100°C, again
to avoid damage to the sensor by overheating.
2.3.3 Connection of a display instrument to the control unit
Various display instruments for recording chromatograms
can be connected via the two 4 mm sockets of recorder out-
put 5. Connect the selected instrument to the control unit by
using two 4 mm connecting cables. When doing this, ensure
correct polarity, as otherwise the signals will be falsely orien-
ted. The yellow socket designates the positive terminal of
recorder output 5 and the white one the earth connection.
The following display instruments can be connected to recor-
der output 5 for the presentation of measurement results:
• An analogue or digital multimeter (setting: voltage mea-
surement): The peaks of the chromatogram are indicated
by the swing of the pointer or a change in the displayed
digital value.
• A Yt recorder: The signals for the chromatogram are
recorded over time by the vertical deflection of a pen
which writes on a horizontally moving sheet of paper.
When one considers that, under some circumstances,
the time interval between individual signals is very short,
then a continuously self-recording Yt recorder is always
to be preferred. A further advantage over a multimeter is
the fact that the chromatogram printed by the recorder
can be directly archived after the measurement, and so
be easily compared with other chromatograms.
• An interface system combined with a PC: The plotting of
the chromatogram with such a system is analogous to
that with a Yt recorder. The difference is only that the sig-
nals are not printed on paper, but are stored in digital
form and displayed on a PC screen. The advantage is
that the measurements are stored on a data carrier. They
can be called up again at any time and, when appropria-
te, be easily subjected to further evaluation.
2.3.4 Zero balancing the measuring bridge
The sensor of the measuring probe for a gas chromatograph
is part of a circuit which works on the principle of a voltage
compensated measurement amplifier (see 1). As the resi-
stance of the sensor varies greatly according to the ambient
conditions (temperature and flow rate of the carrier gas; ...),
the zero balance must as a rule be reset prior to the start of
each new measurement.
When the instrument is switched on, there is a voltage of
36670.99/4902
approx. ±13 V at the recorder output. Carry out zero balan-
cing in two steps. As first step, press the coarse balancing
button 2 on the control unit. This effects an automatic elec-
tronic coarse balancing which reduces the signal on the
recorder output to a few millivolts, as can be seen on a
connected display instrument. As second step, compensate
this signal to reduce it to 0 mV by turning the fine balancing
potentiometer 3 in the one or other direction until around 0
mV is actually displayed. Signals subsequently received
during the measurement will then be given out as difference
to this compensation at the recorder output.
2.4 Notes on operation
The high quality instrument which you have been supplied
with fulfills all of the technical requirements which are sum-
marized in the current European Community Guidelines. It
therefore carries the CE mark.
When operating the instrument, please pay attention to the
following points:
• Refer to the type plate for the fuse rating.
• Refer to the type plate for the mains voltage: permissible
voltage/current values (+ 6-10%).
• The length of individual cables that are connected to the
control unit must not be longer than three meters.
• Electrostatic discharges and other electromagnetic phe-
nomena can exert such an influence on the instrument,
that it no longer operates within specifications:
The following measures hinder or prevent disturbing
influences:
- Avoid fitted carpets.
- Balance potentials.
- Carry out experiments on a conductive, earthed
underlay.
- Use screened cables.
- Do not operate high frequency emitters
(radios, mobile phones) in the immediate vicinity.
- After a blackout failure, carry out a "reset" with the
on/off switch.
• This instrument is only to be used under trained supervi-
sion in housing, business or industrial areas (schools,
universities, laboratories etc.).
3 RECORDING A CHROMATOGRAM
To record a chromatogram, connect the gas inlet tube of the
measuring probe for gas chromatography 7 to the gas outlet
opening of the gas chromatograph used (e.g. a Gas separa-
tion column, article no.: 36670.00). If appropriate, connect a
flow meter (e.g. a Soap bubble flow meter, article no.:
36675.00) to the gas outlet tube of the measuring probe 8, to
quantitatively determine the flow rate of the carrier gas. The
connections of the measuring probe to the gas chromato-
graph and to the flow meter must be gas-tight to ensure that
the carrier gas from the chromatograph flows quantitatively
through the probe. Leaks would result in measurement
errors. These connections are best made with so-called glass
threaded connectors of size GL 18/8 or with tight-fitting
tubing. Connect the measuring probe to the control unit (see
2.3.2) and connect a suitable display instrument to recorder
output 5 (see 2.3.3). After arranging a continuous flow of car-
rier gas, switch on the control unit.
The control unit is generally ready to operate when switched
on. As the heat generated by the transformer it contains affec-
ts the electronics, however, it should be switched on about
half an hour before the first measurement for optimal results.
The conditions (temperature, flow rate of the carrier gas,
separating material, ...) under which the mixture to be exami-
3
ned is to be gas chromatographically separated depend on 7 RECOMMENDED ACCESSORIES
the properties of the mixture and the selected separating 7.1 Chromatograph
column. It is naturally not possible to go into details on these Gas separation column Order no.: 36670.00
parameters here. As a rule, the conditions under which sepa- Glass jacket Order no.: 02615.00
rations are to be carried out are described in the appropriate Kieselguhr, 50 g Order no.: 31501.05
literature or in information provided by manufacturers of Dinonyl phthalate, 100 ml Order no.: 31276.10
separating columns. Soap bubble flow meter Order no.: 36675.00
Immersion thermostat A 100 Order no.: 46994.93
Accessories set immersion
4 CHANGING THE FUSE thermostat A 100 Order no.: 46994.02
Bath for thermostat, 6 l Order no.: 08487.02
Pressure cylinder, helium, 2 l Order no.: 41776.00
Caution! Do not change the fuse until the control unit has Pressure reducing valve, helium Order no.: 33481.00
been separated from the source of electricity by unplug- Table stand for 2 l gas cylinder Order no.: 41774.00
ging it from the AC mains connection!
7.2 Display instruments
To change the fuse, first switch off the control unit, then unp- 7.2.1 Multimeters
lug it from the alternating current mains connection. Only Analogue demonstration multimeter
after having done this, remove the rectangular fuse holder ADM 1 Order no.: 13810.00
that is integrated above the connecting plug of the instru- Analogue demonstration multimeter
ment. Use a screwdriver or similar to open it, with the mains ADM 2 Order no.: 13820.00
connecting cable removed from the instrument. Remove the Multi range meter, analogue Order no.: 07028.01
old fuse, replace it with a new one and push the fuse holder Digital multimeter Order no.: 07134.00
completely back in again.
7.2.2 Recorders
Yt recorder, 1 channel Order no.: 11414.95
Caution! The fuse used as replacement must be of exac- Yt recorder, 2 channels Order no.: 11415.95
tly the same rating as that given on the type plate of the
instrument. It is not permissible to use any other type of 7.2.3 Interface systems
fuse! Cobra3 CHEM-UNIT Order no.: 12153.00
Cobra3 power supply Order no.: 12151.99
Software Cobra3 CHEM-UNIT Order no.: 14520.61
5 SPECIFICATIONS alternatively:
Input Cobra3 BASIC-UNIT Order no.: 12150.00
BNC socket for connection to the measuring probe for Cobra3 power supply Order no.: 12151.99
the gas chromatograph (article no.: 36670.10) Software Cobra3 universal recorder Order no.: 14504.61

Output 7.3 Literature

Recorder output 4 mm sockets, Umax = ±13 V Handbook, glass jacket system Order no.: 01196.12

Power supply
Mains voltage 110 - 240 V~ / 50 - 60 Hz
Power consumption approx. 7 VA
Fuse (5 x 20) See the label on the instrument
for the fuse rating

Dimensions of the casing 194 mm x 130 mm x 140 mm

(W x H x D)

Weight 900 g

6 NOTE ON THE GUARANTEE

We guarantee the instrument supplied by us for a period of
twenty four months. This guarantee does not cover natural
wear nor damage resulting from improper handling.
The manufacturer can only be held responsible for the func-
tion and safety characteristics of the instrument, when main-
tenance, repairs and changes to the instrument are only car-
ried out by the manufacturer or by personnel who have been
explicitly authorized by him to do so.

36670.99/4902 4