Specific Heat
The specific heat of a substance is classically defined as the amount of heat needed to raise one gram of a substance one degree Centigrade. Its importance in chromatography is mostly associated with the response of the thermal conductivity detector. The thermal conductivity detector consists of a filament heated by a small electric current and situated in the exit gas from a gas chromatography column. As vapor from an eluted solute passes the filament the thermal conductivity and the specific heat of the gas changes and the, thus, the heat loss also changes. As a result, the temperature of the filament changes and thus, its electrical resistance also changes. The filament is situated in one arm of a Wheatstone Bridge which becomes unbalanced and the voltage across the bridge is fed to a suitable amplifier and recording device. Originally it was though that the detector responded only to changes in the thermal conductivity of the gas but it is now clear that the major effect is due to the change in specific heat. Specific heat has some minor impact on temperature control of ovens and in temperature programming but its major significance in chromatography is the part it plays in the response of the thermal conductivity detector.
Author: RPW Scott
Book:Plate Theory and Extensions
Section:Plate-Theory Temperature-Changes
, in
terms of the physical properties of the plate and the volume flow of mobile
phase that passes through it must be derived.
Consider the
(n)th theoretical plate in a GC column, as depicted in Figure 21. The
properties of the plate are defined as follows,
vg
is the volume of gas in the plate,
vl
is the volume of liquid (stationary phase) in the plate,
vS
is the volume of support in the plate,
Sl
is the specific heat of the stationary phase,
SS
is the specific heat of the support,
rl
is the density of the stationary phase,
rS
is the density of the support,
Xl(n)
is the concentration of solute in the stationary phase in plate (n),
Xg(n)
is the concentration of solute in the mobile phase (gas) in plate (n),
q
is the excess temperature of the plate above its surroundings
Plate-Theory Temperature-Changes
Author: RPW Scott
Book:Gas Chromatography Detectors
Section:GC-Detectors Classification
property detector measures some bulk physical
property of the eluent (such as dielectric constant or refractive index) and
the solvent property detector, measures some physical or chemical property that
is unique to the solute (such as heat of combustion or fluorescence). Detectors
can also be classified as concentration sensitive devices such as the
katharometer or mass sensitive devices such as the flame ionization
detector (FID). Another method of classification is to define detectors as specific
or non-specific. An example of a specific detector would be the nitrogen
phosphorous detector (NPD), which as its name implies detects only those
substances that contain nitrogen or phosphorous. A non-specific detector would
be the katharometer detector which senses all vapors that have specific heats
or thermal conductivities different from those of the carrier gas. In general
(though not always), non specific detectors have lower sensitivities than the
specific detectors, the reasons
GC-Detectors Classification
Author: RPW Scott
Book:Gas Chromatography Detectors
Section:GC-Detectors Katharometer
A filament carrying a current is situated in
a tubular cavity through which flows the column eluent. Under equilibrium
conditions, the heat generated in the filament is equal to the heat lost and
consequently the filament assumes a constant temperature. The heat lost from
the filament will depend on both the thermal conductivity of the gas and its
specific heat. Both these parameters will change in the presence of a different
gas or solute vapor and as a result the temperature of the filament changes,
causing a change in potential across the filament. This potential change is
amplified and either fed to a suitablerecorder
or passed to an appropriate data acquisition system.As the detector filament is in thermal equilibrium with its
surroundings and the device actually responds to the heat lost from the
filament, the detector is extremely
GC-Detectors Katharometer
Author: RPW Scott
Book:Gas Chromatography
Section:YES Detectors Flame-Ionization
to be specific and sense
specific types of sample (e.g., halogenated substances by the electron
capture detector). Conversely, those detectors with a catholic response,
although highly sensitive compared to LC detectors (e.g. the flame
ionization detector) are significantly less sensitive than the specific
detectors. The detectors with a catholic response are the most popular and the
majority of GC separations are monitored by the flame ionization detector
(FID). The most commonly used specific detectors are the nitrogen phosphorus
detector (NPD) and the electron capture detector (ECD) The katharometer
detector, although having relatively poor sensitivity is widely used in gas
analysis.
The Flame Ionization Detector
The FID,
invented by Harley and Pretorious (7), and separately by McWilliams and Dewer
(8), evolved from the Heat of Combustion Detector developed by Scott (9). The FID detector employs hydrogen as
the combustion gas which is mixed with the
YES Detectors Flame-Ionization
Author: RPW Scott
Book:Gas Chromatography
Section:YES Detectors Katherometer
equilibrium conditions, the
heat generated in the filament is equal to the heat lost by conduction and
convection and consequently the filament assumes a constant temperature. At the
equilibrium temperature, the resistance of the filament and thus the potential
across it is also constant.
Figure 29.
The Katherometer Detector ("In-Line Cell")
The heat lost
from the filament will depend on the thermal conductivity of the gas and its
specific heat and both these parameters will change in the presence of a
foreign gas or solute vapor. The presence of a different gas entering the
detector causes the equilibrium temperature to change, producing a change in
potential across the filament. This potential change is amplified and fed to a
suitable recorder. A diagram of the katherometer is shown in figure 29
YES Detectors Katherometer
Author: RPW Scott
Book:Gas Chromatography
Section:YES Gas-Supplies Flow-Controllers
are placed equidistant up stream and down stream
of the heater. A proprietary set of baffles situated in the main conduit
creates a pressure drop that causes a fixed proportion of the flow to be
diverted through the sensor tube. At zero flow rate both sensors are at the
same temperature. At a finite flow rate, the down stream sensor is heated, producing
a differential temperature across the sensors. The temperature of the gas will
be proportional to the product of mass flowing and its specific heat and so the
differential temperature that will be proportional to the mass flow rate. The
differential voltage from the two sensors is compared to a set voltage and the
difference used to generate a signal that actuates a valve controlling the
flow. Thus, a closed loop control system is formed that maintains the mass flow
rate set by the reference voltage. The device can be made extremely compact, is
highly reliable and affords accurate control of the carrier gas flow rate
YES Gas-Supplies Flow-Controllers