PROCESS AND DEVICE FOR SAMPLING THE HEADSPACE

Abstract

Process for sampling the headspace, comprising the steps of: (i) preparing a container (1) containing a substance in the liquid phase (2), a substance in the gaseous phase (3), a substance to be analyzed (4) initially at least partially contained in the substance in the liquid phase (2), wherein the substance in the liquid phase (2) has a contact surface (S) contacting the substance in the gaseous phase; (ii) constraining said container (1) to a supporting element (10) rotatable around a rotation axis (A1); (iii) rotating said supporting element (10) at such an angular velocity to tilt said contact surface (S) by an angle (a) of at least 20 degrees with respect to a plane (H) parallel to the bearing surface of the supporting element (10); (iv) stopping the rotation of said supporting element (10); (v) collecting a sample of the substance to be analyzed, in the gaseous phase.

Claims

1) Process for sampling the headspace, comprising the steps of: (i) preparing a container (1) containing a substance in the liquid phase (2), a substance in the gaseous phase (3), a substance to be analyzed (4) initially at least partially contained in the substance in the liquid phase (2), wherein the substance in the liquid phase (2) has a contact surface (S) contacting the substance in the gaseous phase; (ii) constraining said container (1) to a supporting element (10) rotatable around a rotation axis (A1); (iii) rotating said supporting element (10) at an angular velocity such as to tilt said contact surface (S) by an angle (a) of at least 20 degrees with respect to a plane (H) parallel to the bearing surface of the supporting element (10); (iv) stopping the rotation of said supporting element (10); (v) collecting a sample of the substance to be analyzed, in the gaseous phase.

2) Process according to claim 1, wherein, in said step (iii), said supporting element covers at least one complete revolution.

3) Process according to claim 1, wherein, in said step (iii), the rotation is stopped or slowed down and subsequently restarted at least once.

4) Process according to claim 3, wherein, during said step (iii), each of said stops lasts for a time period between 0.5 and 10 seconds.

5) Process according to claim 1, wherein, in said step (iii), the rotation direction is reversed at least once.

6) Process according to claim 1, wherein, in said step (iii), the supporting element (10) is rotated for at least 1 second.

7) Process according to claim 1, wherein, in said step (iii), the angular velocity of said supporting element (10) exceeds 1 revolution per second.

8) Process according to claim 1, wherein, in said step (iii), the contact surface (S) is tilted by at least 30 degrees, or by an angle (a) maximizing the size of the contact surface (S) without allowing the contact between the liquid and the cap (1a) of the container (1).

9) Process according to claim 1, wherein said supporting element (10) is placed inside a heated housing (100) and, at least in said step (iii), the temperature inside said heated element is between 20 and 300 C.

10) Process according to claim 1, wherein, in said step (ii), said container (1) is constrained to said supporting element (10) so that said rotation axis (A1) does not cross said supporting element (1).

11) Process according to claim 1, wherein, in said step (ii), the longitudinal axis (A2) of said container is placed at a distance (r) from the rotation axis (A1) of said supporting element (10) higher than 2 cm.

12) Process according to claim 1, wherein said rotation axis (A1) is substantially vertical.

13) Device for sampling the headspace, comprising a supporting element (10) rotatable around a rotation axis (A1), provided with at least one seat (11) to accommodate a container (1) so that, in use, said rotation axis (A1) does not cross said supporting element (1).

Description

[0028] Hereinafter, referring to the appended figures, exemplary and non-limiting embodiments of the present invention will be described, wherein:

[0029] FIG. 1 is a schematic plan view of a possible supporting element to carry out a sampling of the headspace by means of an embodiment of a process according to the present invention;

[0030] FIG. 2 is a schematic front view of a container or vial for sampling the headspace;

[0031] FIG. 3 is a schematic front view of the container of FIG. 2 constrained to the supporting element of FIG. 1;

[0032] FIG. 4 is a plan view of FIG. 3;

[0033] FIG. 5 is a simplified view of FIG. 3, wherein part of the elements has been omitted in order to highlight the behavior of the liquid inside the container;

[0034] FIG. 6 is a plan view similar to FIG. 4, wherein the supporting element has begun its rotation;

[0035] FIG. 7 is a schematic front view of FIG. 6, wherein part of the elements has been omitted;

[0036] FIG. 7A is an enlarged detail of FIG. 7;

[0037] FIG. 8 is a plan view similar to FIG. 6, wherein the supporting element has been further rotated;

[0038] FIG. 9 is a schematic front view of FIG. 8, wherein part of the elements has been omitted;

[0039] FIG. 10 is a schematic view similar to FIG. 8, wherein the supporting element has been stopped after a further rotation;

[0040] FIG. 11 is a schematic front view of FIG. 10, wherein part of the elements has been omitted;

[0041] FIG. 12 is a schematic view similar to FIG. 10, wherein the supporting element has been rotated in the direction opposite to the rotation direction of FIGS. 6-9;

[0042] FIG. 13 is a schematic front view of FIG. 10, wherein part of the elements has been omitted;

[0043] FIG. 14 is a schematic view of the collection of a sample from the headspace of a container at the end of the rotation of FIGS. 5-13;

[0044] FIG. 15 is a schematic view of a rotating container containing liquid.

[0045] Referring to the figures, a device 200 comprises a supporting element 10 configured to accommodate one or more containers (or vials) 1 for sampling the headspace.

[0046] The container 1 is configured in a known way to contain a substance to be analyzed by a special instrument, typically a gas chromatograph, not shown in detail. Briefly, according to the known art, the container 1 is provided with a substance in liquid phase (hereinafter also liquid) 2 that only partially fills container 1. Above the liquid 2 there is a substance in the gaseous phase (hereinafter also gas) 3, so that the liquid 2 and the gas 3 are in contact with one another at a contact surface S, which corresponds to the free surface of the liquid 2. At least initially, the liquid 2 contains a substance to be analyzed (hereinafter also referred to as sample) 4. Various options, known in the art, are possible. The liquid 2 may be composed entirely of the sample 4, or the liquid 2 may be a solution containing the sample 4. Similarly, the gas 3 may be the gaseous phase of the liquid 2, but generally contains additional gases, such as for example inert gases. Once the sample 4 has been at least partially volatilized, the gaseous phase of the sample 4 will become part of the gas 3 located above the liquid 2.

[0047] In general, the liquid 2 comprises (or consists of) the sample to be analyzed, which must be volatilized before being able to be collected from container 1. In fact, when sampling the headspace, only the content of the gas 3 is analyzed, which is collected by special means, for example a syringe passing through the cap 1a of the container 1. The higher the concentration of the sample 4 in the gas 3, the better the results of the subsequent analyses.

[0048] The supporting element 10 has at least one seat 11 to accommodate a container 1. The seat 11 is typically configured as a cavity, and the container 1 can be partially inserted therein, preferably with limited clearance. According to a possible aspect, the seat 11 is at least partially closed at the bottom, so that, in use, the container 1 is supported by the seat 11 and partially inserted therein. The shape of the supporting element 10 can vary between different embodiments. In the embodiment shown, the supporting element 10 has circular section and limited height, i.e. it is shaped as a rotating drum.

[0049] The supporting element 10 can be rotated around a rotation axis A1. This solution is obtained in a manner known in the art, for example by an electric motor M suitably connected to the supporting element 10. The supporting element is preferably rotated at angular velocities exceeding 2 revolutions per second.

[0050] The device 200 is typically configured so that, in use, the rotation axis A1 is substantially vertical.

[0051] The seat 11 is placed at a distance from the rotation axis A1, i.e. the rotation axis A1 does not cross the seat 11. In other words, when the container 1, in use, is inserted into the seat 11, the axis A1 does not cross the container 1.

[0052] Preferably, considering the longitudinal axis A2 of the container 1, in use, the distance r between the two axes A1, A2 is higher than 2 cm, more preferably higher than 3 cm, even more preferably higher than 4 cm.

[0053] Typically, when the container 1 is received by the seat 11, the two axes A1, A2 are substantially parallel to one another. In general, these axes A1, A2 are substantially perpendicular to a plane H parallel to the surface on which, in use, the supporting element is arranged, or parallel to the horizontal line.

[0054] At the seat 11, there may be protrusions 12 adapted to prevent or limit the tilt of the container during the rotation of the supporting element 10. These protrusions 12 are typically arranged around the seat 11, and their main extension direction is substantially parallel to the rotation axis A1. In the embodiment shown, the protrusions 12 have circular section; preferably the diameter of the protrusions is smaller (at most equal) than the diameter of the seat 11, while the height of the protrusions 12 is greater than the diameter of the section of the protrusions 12. Typically the height of the protrusions 12 is greater than the height of a standard container for sampling the headspace.

[0055] The supporting element 10 is preferably housed in an incubator or oven 100, or in any case a heated housing known in the art and schematically shown in FIG. 3, so that, in use, the container housed inside the supporting element can be heated to an appropriate temperature between 20 and 300 degrees, selected according to the type of sample to be analyzed.

[0056] In use, a container 1 is constrained (even by simple leaning) to the supporting element 10. Then, as shown in FIGS. 6-9, the supporting element 10 is rotated. The rotation speed (due to centrifugal force) pushes the liquid 2 towards the side surface of the container 1, so as to tilt the contact surface S.

[0057] The contact surface S, with respect to the plane H (i.e. a plane parallel to the bearing surface of the support 10or the device 200or else parallel to the horizontal line, or in any case parallel to a plane tangent to the contact surface S in the rest condition of the supporting element 10), has a tilt a higher than 30 degrees, more preferably higher than 45 degrees, even more preferably higher than 60 degrees, or in any case an angle that maximizes the size of the liquid-gas contact surface S, i. e. typically without the contact surface S touching either the cap or a container narrowing, or the bottom of the container 1.

[0058] By touching the bottom of the container 1, drops of liquid phase may be generated which, when projected onto the cap 1a, may contaminate the needle at the time of collection. By touching the cap 1a, the cap material may contaminate the liquid, and thus the results of subsequent sample analysis may be corrupted.

[0059] A possible method to determine the rotation speed of the supporting element 1 that allows the maximum angle (i.e. the maximum tilt of the contact surface S, without the latter touching the cap 1a or the bottom of container 1) is as follows.

[0060] Referring to FIG. 15, having established the size of the container 1 and the amount of the liquid phase 2 inserted therein, it is possible to obtain the angle taken by the contact surface S with respect to the horizontal line when the container 1 rotates at a certain speed and, as a result, the extent of the contact surface S between the liquid phase 2 and the gas phase 3.

[0061] Data: [0062] g, gravity acceleration [0063] r, distance of the axis A2 of the container 1 from the rotation axis A1 of the supporting element 10 [0064] v, tangential velocity of the container 1 along its trajectory around the rotation axis A1 of the supporting element 10

[0065] The apparent centrifugal acceleration ac acting on the container 1 is:

[00001]$\mathrm{ac}=\frac{v^2}{r}$

[0066] The apparent gravity force ag acting on the container is the vector composition of g and ac, having modulus equal to

ag={square root over (g.sup.2+ac.sup.2)}

[0067] As a result, the angle taken by the contact surface S with respect to the horizontal is:

[00002]$=\arcsin \left(\frac{\mathrm{ac}}{\mathrm{ag}}\right)$

[0068] It is now possible to calculate the extent of the contact surface S between the liquid phase 2 and the gaseous phase 3 as a function of the angle taken by the contact surface S, the amount of liquid 2 contained in the container 1 and the size of the container 1 itself.

[0069] Data: [0070] dc, the diameter of the container 1 [0071] hc, the height of the container 1 [0072] ql, the amount of liquid 2 in the container 1

[0073] The height hl of the liquid 2 in the container 1 at rest is:

[00003]$\mathrm{hl}=\frac{\mathrm{ql}}{\left(\frac{*{\mathrm{dc}}^2}{4}\right)}$

[0074] Accordingly, the height hs of the headspace in the container at rest is:

hs=hchl

[0075] Therefore, the distance d on the wall between the free surface of the liquid when horizontal, with the vial at rest, and when inclined, with the vial rotating, can be calculated:

[00004]$d=\frac{\mathrm{dc}}{2}.Math.\tan \left(\right)$

[0076] Thus, the smallest distance hf on the wall between the liquid 1 and the bottom of the container 1 is:

hf=hld

Similarly, the smallest distance ht on the wall between the liquid 2 and the cap 1a of the container is:

ht=hc(hl+d)

[0077] In order to calculate the surface Spl of the liquid's free-surface (i.e. the area of the contact surface) when the container 1 is rotating, the greater radius rm of the ellipse formed by the contact surface S must be calculated:

[00005]$\mathrm{rm}=\sqrt{\left({\left(\frac{\mathrm{dc}}{2}\right)}^2+d^2\right)}$

[0078] Thus, when the container 1 is rotating, the free surface Spl of the liquid 2 is:

[00006]$\mathrm{Spl}=*\frac{\mathrm{df}}{2}*\mathrm{rm}$

[0079] These equations allow the rotation speed rm to be optimized, according to the amount of liquid 2 contained in the container 1 and the type of container 1, so as to maximize the size of the contact surface S, that is to say to calculate the greatest angle that allows the liquid 2 not to touch the cap 1a or the bottom of the container 1.

[0080] Considering the containers 1 spaced 46.5 mm from the rotation axis A1 of the supporting element 10, the following table lists some examples of calculation of the highest rotation speed rm, and the respective size of the contact surface S:

TABLE-US-00001 Amount of Angle the Liquid-gas liquid Rotation speed liquid takes surface 20 ml vial 5 ml 2.9 revolutions per 57.6 585.7 mm.sup.2 second 20 ml vial 10 ml 3.8 revolutions per 69.7 905.1 mm.sup.2 second 10 ml vial 5 ml 2.7 revolutions per 53.8 531.3 mm.sup.2 second

[0081] It should be noted that for convenience's sake, in the figures, the container height hc has been considered up to the cap 1a. When using a container with a bottleneck top, if the contact between the liquid 2 and the cap of the container 1 is to be prevented, the height hc of the container can be considered as the distance hc between the bottom of the container and the lower portion of the bottleneck. It can be observed that by keeping the liquid 2 at a height lower than the lower portion of the bottleneck, the contact between the liquid 2 and the cap 1a of the container 1 is prevented.

[0082] In general, thanks to the tilt of the contact surface S, the latter is larger with respect to its size in the rest state, thereby favoring the exchange between the liquid 2 and the gas 4, and in particular the transition of the sample 3 from the liquid 2 to the gas 4.

[0083] The angular velocity of the supporting element 10 is preferably higher than 1 revolution per second, more preferably higher than 2 revolutions per second, even more preferably it is calculated according to the above-described equations in order to maximize the liquid-gas contact surface.

[0084] According to an aspect, the supporting element 10 is kept rotating for at least 1 second. Preferably, moreover, during its rotation, the supporting element 10 rotates for at least one complete revolution, i.e. at least 360, more preferably for at least two complete revolutions, i.e. at least 720, even more preferably for at least five complete revolutions, i.e. at least 1800.

[0085] According to a preferred aspect, the rotation is not continuous but is preferably stopped (or slowed down), as schematically shown in FIGS. 10 and 11, for a time period preferably exceeding 0.5 seconds, more preferably ranging between 0.5 and 10 seconds. Slowed down means an angular velocity much lower (at least 5 times, preferably at least 10 times lower) than the previous rotation step.

[0086] Moreover, according to a particular aspect, at least one rotation cycle (i.e. one rotation step between two slowdowns or stops) causes the supporting element 10 to rotate by at least 360, or at least 720, or at least 1800.

[0087] In the embodiment shown, the supporting element 10 changes its rotation direction at least once. In other words, the supporting element performs a first rotation step in a direction (e.g. clockwise, as shown in FIG. 8), and then performs a second rotation step in the direction opposite to the previous direction (e.g. counterclockwise, as shown in FIG. 12), typically by alternating them with the aforementioned stopping or slowing down steps.

[0088] The rotation speed of the first and second steps is preferably the same, although embodiments in which the rotation speed varies between the first and second rotation steps are not excluded.

[0089] In the embodiment shown in figures, a single change in the direction (i.e. the way) of rotation of the supporting element 10 is shown. Actually, the rotation direction is preferably changed several times, i.e. the rotation direction preferably varies at least twice, more preferably at least three times, even more preferably at least five times.

[0090] As described above, the supporting element is arranged in a heated housing 100, typically an oven or incubator, so that the temperature inside the housing is between 20 and 300 C. at least during the rotation of the supporting element.

[0091] At the end of the rotation of the supporting element 10, a sample is collected from the headspace of the container 1 in a known manner, for example by means of a needle or a similar sampling element 201, as shown in FIG. 14. For example, a lift 203 can be used so as to move the container 1 towards the sampling element 201.

[0092] The collected sample is typically sent to a gas chromatograph or similar analysis instrument. As discussed above, thanks to the equilibrium reached by shaking the container 1 (and preferably also by heating it), at least part of the substance to be analyzed has been volatilized (i.e. has become gaseous) and has been transferred to the headspace.

[0093] Typically, the device 200 is further equipped with a control unit 202 configured to control the operations of the device 200, including the rotation of the supporting element.