U.S. patent number 3,782,078 [Application Number 05/225,948] was granted by the patent office on 1974-01-01 for apparatus for chromatographic separations.
Invention is credited to James H. Jerpe.
United States Patent |
3,782,078 |
Jerpe |
January 1, 1974 |
APPARATUS FOR CHROMATOGRAPHIC SEPARATIONS
Abstract
The subject chromatographic column employs certain excitation
means to alter the sorption of a sample passing through a sorbent
contained within the column to better effect separation of the
various components of the sample. These excitation means include a
geometric curvature of the central cavity of the column, or a
voltage gradient established within the cavity between the column
wall which defines the cavity and an electrically isolated wire
extending along the longitudinal axis of the cavity, or a
combination of the two. The columns can be housed in series within
composite blocks and these blocks can be stacked to permit columns
of substantial length within a confined space.
Inventors: |
Jerpe; James H. (Pittsburgh,
PA) |
Family
ID: |
22846936 |
Appl.
No.: |
05/225,948 |
Filed: |
February 14, 1972 |
Current U.S.
Class: |
96/104;
210/198.2 |
Current CPC
Class: |
G01N
30/6065 (20130101); G01N 2030/0035 (20130101); G01N
2030/8881 (20130101); G01N 2030/386 (20130101); G01N
30/02 (20130101) |
Current International
Class: |
G01N
30/00 (20060101); G01N 30/60 (20060101); G01N
30/02 (20060101); G01N 30/38 (20060101); G01N
30/88 (20060101); B01d 015/08 () |
Field of
Search: |
;55/67,197,386
;210/31C,198C |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Adee; John
Attorney, Agent or Firm: Orkin; Russell D.
Claims
I claim:
1. A chromatographic column including a central cavity extending
therethrough to accommodate a sorbent and excitiation means within
the column for cooperating with the sorbent to alter the sorbing
characteristics of the sorbent with respect to a sample passing
therethrough, said excitation means comprising a thin elongated
electrical conducting means extending longitudinally through and
along the longitudinal axis of the central cavity and electrically
isolated from the column, said electrical conducting means adapted
to connect to a potential source to establish a voltage gradient
within the cavity between the column and the conducting means.
2. A chromatographic column including a central cavity extending
therethrough to accommodate a sorbent and excitation means within
the column for cooperating with the sorbent to alter the sorbing
characteristics of the sorbent with respect to a sample passing
therethrough said excitation means comprising a geometric surface
defining the cavity, said surface being curved, symmetrical about
the cavities' longitudinal axis and increasing in cross section
both from the inlet means and outlet means inward to a point
intermediate said inlet and outlet means.
3. A chromatographic column including at least one sorbent
accommodating central cavity extending from inlet means to outlet
means, said cavity defined by a curved surface symmetrical about
the cavities' longitudinal axis and increasing in cross section
both from the inlet means and outlet means inward to a point
intermediate said inlet and outlet means.
4. The chromatographic column of claim 3, the central cavity being
symmetrical about all axes and thusly increasing in cross section
from the inlet and outlet means inward to a point equidistant from
the inlet means and the outlet means.
5. The chromatographic column of claim 4, the central cavity being
defined by the general equation Y = e.sup.-.sup.kx .
6. The chromatographic column of claim 4 wherein a series of said
central cavities are coaxially aligned and connected in series so
that the outlet means of one central cavity cooperates with the
inlet means of an adjacent central cavity.
7. The chromatographic column of claim 3 having a conducting metal
block which houses the central cavity.
8. The chromatographic column of claim 7 wherein the conducting
metal block consists of two separate sections, each recessed to
define one-half of said cavity, said sections connected to form the
chromatographic column.
9. The chromatographic column of claim 7, including thin elongated
electrical conducting means extending along the longitudinal axis
of the cavity and electrically isolated from the metal block, said
conducting means adapted to connect to a potential source to create
a voltage gradient within the cavity between the electrical
conducting means and the conducting block.
10. In a metallic electrical conducting chromatographic column
having a passageway extending therethrough, the improvement
comprising a thin elongated electrical conducting means extending
along the longitudinal axis of the passageway and electrically
isolated from the column, said conducting means adapted to connect
to a potential source to create a voltage gradient within the
cavity between the electrical conducting means and the column.
11. The chromatographic column of claim 9 wherein the elongated
electrical conducting means comprises a copper wire.
12. The chromatographic column of claim 9 wherein the elongated
electrical conducting means comprises a thin carbon rod.
13. The chromatographic column of claim 7 wherein the metal block
is aluminum.
14. A chromatographic column comprised of at least one composite
block, said block including at least two layers joined in assembled
relationship, said layers internally recessed to define a plurality
of separate and spaced elongated cavities joined in series and
having an inlet means and an outlet means through the block and in
communication with the cavities.
15. The chromatographic column of claim 14 wherein said cavities
are defined by a curved geometric surface symmetrical about each
cavities' longitudinal axis and increasing in cross section from
each end of each cavity inward to a point intermediate said
ends.
16. The chromatographic column of claim 15 wherein each cavity is
defined by the general equation Y = e.sup.-.sup.kx .
17. The chromatographic column of claim 14 comprising a plurality
of said composite blocks, said blocks being joined in stacked
relationship so that an outlet means of a first block cooperates
with the inlet means of an adjacent block in the stack.
18. The chromatographic column of claim 14 including a
nonconducting, heat resistant layer intermediate the two layers,
said nonconducting, heat resistant layer including the series of
separate and spaced elongated cavities extending clear through the
thickness of said layer and at least one of said two layers
defining recessed connecting means to join the cavities in
continuous series.
19. A chromatographic column comprised of at least one composite
block, said block including a plurality of layers joined in
assembled relationship, said plurality of layers including a heat
resistant top and bottom layer, a nonconducting layer adjacent each
heat resistant layer, a conducting metal layer adjacent each
non-conducting layer, a central template nonconducting layer means
defining a series of separate and spaced elongated cavities
extending throughout the thickness of said layer means, at least
one of said conducting metal layers defining recessed connecting
means to join the cavities in continuous series, an inlet and an
outlet means cooperating with said connecting means and said
cavities and an elongated conducting wire extending along the
longitudinal axis of the cavities and through the layer means, said
conducting metal layer adapted to connect to a potential source to
create a voltage gradient within each cavity between the conducting
wire and the conducting metal layers.
20. The chromatographic column of claim 19 wherein at least certain
of said cavities are defined by a curved geometric surface
symmetrical about each cavities' longitudinal axis and increasing
in cross section from each end of each cavity inward to a point
intermediate said ends.
21. The chromatographic column of claim 20 wherein each cavity is
defined by the general equation Y = e.sup.-.sup.kx .
22. The chromatographic column of claim 19 wherein the central
template layer means comprises two sheets in stacked relationship,
said wire extending between the two sheets.
23. The chromatographic column of claim 19 comprising a plurality
of said composite blocks, said blocks being joined in stacked
relationship so that an outlet means of a first block cooperates
with the inlet means of an adjacent block in the stack.
Description
This invention relates to chromatography and, more particularly, to
the chromatographic column.
Basically, chromatography consists in passing a sample mixture
through a sorbent contained within the chromatographic column, thus
providing a two-phase system. In gas chromatography, a liquid
sample is vaporized and sent through the column as a gas. Advantage
is taken of the different equilibria which exist between the two
phases to separate the components of the sample as a result of the
different equilibrium constants thereof. The sample mixture is
normally passed through the column with the aid of a carrier gas.
The various components of the sample form separate bands in the
carrier and as these separate bands leave the column, they are
recorded as a function of time by a suitable detector.
A number of drawbacks exist with present chromatographic systems.
Strongly retained components travel very slowly or, in some cases,
do not move at all within the column. This problem is combated by
using temperature programming, but many samples are heat labile and
are adversely affected as a result thereof. Conventional
chromatographic processes are generally adaptable only to small
sample separation or analysis and are not suitable for large
volumes of solutions. Existing chromatographic systems include
chromatographic columns of substantial length to affect adequate
separations and, as a result thereof, a substantial space is
necessary to accommodate elongated chromatographic columns.
My invention overcomes the problems of strongly retained compounds,
slow elution, partial resolution of compounds and unsuitable
conditions of flow rate of the carrier fluid. In addition, my
chromatographic column permits normally heat reactive labile
compounds to be chromatographed. My chromatographic column also
permits analysis of large, as well as small, sample mixtures. My
invention is a chromatographic column which enhances the resolution
of fluid mixtures by controlling individually or in combination the
variables of column geometry and voltage gradients within the
column. The geometry can be controlled by using curved symmetrical
surfaces to define the central cavity and which increase in cross
section inwardly from both the inlet and outlet ends thereof. The
voltage gradient is established within the cavity between an
electrically isolated wire extending along the longitudinal axis of
the cavity and the wall of the column which defines the cavity.
In the accompanying drawings, I have shown my presently preferred
embodiments of my invention in which:
FIG. 1 is a section through a geometrically shaped chromatographic
column;
FIG. 2 is a section through a chromatographic column having a
plurality of geometric shapes connected in series;
FIG. 3 is a section through a standard chromatographic column
having a conducting wire extending therethrough;
FIG. 4 is a section through a chromatographic column similar to
that depicted in FIG. 1 but including a conducting wire extending
therethrough;
FIG. 5 is an isometric of a simplified composite chromatographic
block;
FIG. 6 is an exploded view of a modified composite block;
FIG. 7 is a plan view of the central template cavity containing
layer illustrated in FIG. 6; and
FIG. 8 is a plan view of the valve containing metal conducting
layer of FIG. 6.
It is recognized theory in gas chromatography that specific forces,
electrochemical in nature, are involved in obtaining separation
between different components of a sample. These various
electrochemical forces determine the differential solubilities and,
therefore, the resultant separation of the compounds. The combined
effects of these various electrochemical forces are expressed by a
partition coefficient (index of separation) which is normally fixed
throughout a chromatographic determination. My invention alters
these electrochemical forces by adulterating the environment of the
sorbent and solute and, therefore, changes the sorptive
characteristics of the sample passing through the cavity.
The sample to be analyzed is passed through a sorbent in the
gaseous state by means of a carrier gas. The sorbent, commonly
referred to as "substrate" or "packing material," is a porous
substance which must sorb the components of mixtures selectively
and reversibly.
The chromatographic column illustrated in FIG. 1 utilizes a
geometric curved shape to alter the sorbent environment of a sample
passing therethrough. That column, generally designated 10,
consists of a geometric curved surface 12 which defines a central
cavity 14. Curved surface 12 increases in cross section inwardly
from both the inlet end 16 and the outlet end 18. The cavity 14
defined thereby is symmetrical about all the axes and the
particular curve illustrated is defined by the equation Y =
e.sup.-.sup.kx . It is necessary that the cavity 14 be symmetrical
at least about the longitudinal axis of the cavity.
Because of the curvature of the cavity 14, the affinity of the
sorbent within the cavity for the sample passing through the cavity
is not only a function of two dimensional distance traveled through
the column, but is also a function of discreet three dimensional
volume bands. This differing path length causes an obvious and
discreet change in retention time and can be visualized as
concentric doughnut shapes forming in and passing through the
column. The components having the least affinity for the sorbent
will pass along the longitudinal axes of the cavity 14 and those
components having greater affinities for the sorbent will eddy out
into the increased space provided by the curvature of the cavity 14
to increase the retention time for that particular component within
the cavity and, thus, assist in separation of the components
leaving the exit end 18 of the chromatographic column 10. The
decreasing cross section approaching the outlet end 18 further
accentuates the component separation by exaggerating one volume
band from another.
Not only can the specific curvature be changed for different
systems, but similar columns 10 can be connected in series as
illustrated in FIG. 2. There, two cavities 14 are connected in
series with the outlet end 18 of the first cavity coaxially aligned
and cooperating with the inlet end 16 of the second cavity. This
can be accomplished within a single unit by connecting two or more
separate units in axial alignment.
The electrochemical nature of the sorbent and solute can also be
altered by effecting a voltage gradient within the cavity. The
chromatographic column 10 having a standard cylindrical central
cavity 20 and such a voltage gradient is illustrated in FIG. 3. The
cavity 20 is defined by a conducting metal wall 22 such as aluminum
or copper. A thin copper wire 24 extends along the longitudinal
axis of cavity 20 and is electrically isolated from wall 22 by
standard insulating means (e.g. asbestos or Teflon gaskets) 26. The
copper wire 24 is connected to a heavy duty D.C. potentiometer, not
shown, and the anode of the potententiometer is connected to the
block or wall 22. The wire 24, therefore, is in the geometric
center of the cavity 20 running its entire length and is in contact
solely with the sorbent 28. The voltage gradient is then
established between the wire 24 and the wall 22 within the cavity
20. The wire can also be a thin elongated bar of an electrical
conducting material such as carbon.
The geometric and voltage gradient techniques of altering the
affinity of a sample and a sorbent can be combined as illustrated
in FIG. 4. There, column 10 includes both a geometrically shaped
cavity 14' and an electrically isolated wire 24'. Wire 24' which
extends along the longitudinal axis of cavity 14' is electrically
isolated from wall 12', which defines the cavity 14', by standard
insulating means 26'. In this embodiment not only is there a
combination of the geometrical shape effect and voltage gradient
effect, but the latter is compounded by the former. That is, since
the cavity 14' is increasing in cross section inwardly from both
the inlet end 16' and the outlet end 18', the voltage gradient
within the cavity 14' is not a constant. Since the wire 24' extends
along the geometric center of the cavity 14', the voltage gradient
effect is produced with maximum readings at the column center and
progressively diminishing readings in both directions proportional
to the varying distances between the wall anode defining the cavity
curvature and the wire 24'.
The above principles may be embodied in a variety of different
ways, in addition to the single column or coaxially aligned columns
depicted hereinabove.
FIG. 5 illustrates a simple composite block 30 formed of two layers
32 and 34, respectively. Each layer contains a number of parallel
cavities 36 recessed therein. These cavities 36 are connected in
series by crossovers 38 also recessed within each layer. When the
two layers 32 and 34 are sealably joined in gas tight relationship,
the recessed cavities 36 of each layer align and cooperate to form
the cavities and column for the sorbent. An inlet 40 extends
through the upper layer 32 and connects with the first cavity 36 of
the series and an outlet 42 connects with the end of the last
cavity in the series. These cavities 36 can be standard, or can
incorporate one of both of the geometric and voltage gradient
principles discussed hereinbefore. In addition, these composite
blocks 30 can be stacked to form an even longer resultant column.
To form such a stack of composite blocks, it is necessary to have
inlet and outlet means of composite block 32 positioned in such a
manner that in stacked relationship the outlet of a first composite
block communicates with the inlet of an adjacent composite
block.
The composite block arrangement can be further modified to
facilitate the development of the requisite voltage gradients
within the cavities, FIGS. 6-8.
The composite block 30 disclosed therein includes a plurality of
different layers joined in assembled relationship to form the
chromatographic column. The top and bottom layers 42 and 44,
respectively, are metal blocks such as aluminum. These blocks are
normally placed in a heated environment and it is necessary to have
a somewhat heat resistant material. In addition, the blocks must
withstand substantial torque-bolting to form noncrimped gas tight
seals of the various other layers sandwiched therebetween. An
electrical insulating layer 46 made of a material such as asbestos
is positioned adjacent the lower layer 44. Adjacent the asbestos
layer 46 is a copper plate 48 which forms one of the common poles
for the voltage gradient. Adjacent the copper plate 48 is a Teflon
layer 50 and adjacent layer 50, a second Teflon layer 52. These two
Teflon layers, 50 and 52, form the template for the chromatographic
cavities 54. Each Teflon layer, 50 and 52, includes a plurality of
cavities 54 which extend clear through the thickness of each layer,
FIG. 7. These cavities 54 are in parallel relationship and can be
the cylindrical type cavity or the geometrically shaped curvature
type previously discussed, or a combination of the two. Both types
of cavities are illustrated in FIGS. 6 and 7 for ease of
presentation.
The two Teflon layers 52 and 50, are made separately to facilitate
the accommodation of electrical wires 56 which are inserted between
layers 52 and 54 and which extend along the longitudinal axis of
the cavities 54.
It, of course, will be recognized that the two layers 52 and 50 can
be made as a single cavity containing layer with the electric wire
56 extending therethrough along the longitudinal axis of each
cavity and in sealable relationship with the layer.
Adjacent the upper layer 52 is a copper plate 58 which forms the
valving to join the various cavities 54 in series, FIG. 8. Plate 58
merely has a series of slots 60 which join the adjacent cavities 54
of the template layer, superimposed as dotted lines in FIG. 8. For
ease of manufacture, the slots 60 extend clear through the
thickness of copper plate 58 and, therefore, a second copper plate
62 is placed adjacent thereto to restrict and define the path of
sample travel to within the cavities 54 and the crossovers 60.
Copper plate 58 also forms a common pole with plate 48 to establish
the voltage gradient in the cavities in conjunction with the
electrical wires 56. Adjacent copper plate 62 is another insulating
layer 64 to electrically isolate the copper plate 62 from the top
plate 42.
These various layers are joined and held thereto by connecting
means such as a plurality of torque-bolts, not shown, extending
through all the layers. The layers must be maintained in gas tight
sealable relationship.
Inlet 66 for introducing the sample and the carrier extends through
the copper plate 48 and is directed to the start of the series of
cavities 54. Outlet 68 exits from the end of the cavity series as
per the earlier similar embodiments, FIG. 8. Standard fittings can
be employed to connect the inlet and outlet to the balance of the
chromatographic equipment.
The composite block 30 can also be arranged in stacked relationship
with other similar blocks by merely removing the top aluminum block
42 and connecting outlet 68 with the inlet 66 of a similar
composite block. In this manner a plurality of composite blocks can
be arranged in stacked relationship to maximize the linear path of
travel within a small confined area.
The operation of the various embodiments is quite simple. The
chromatographic columns of the subject invention are merely
inserted in line with the standard chromatographic equipment and
the sample passed therethrough in standard fashion. The use of the
geometrically curved shape and/or the electrically isolated central
wire to establish the voltage gradient will effect the affinity
relationship between the sorbent and the sample to affect accurate
and rapid separation for determination of the various components of
the sample.
* * * * *