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after some thought, your analyzer system can run on positive pressure but you should have a "vaporizing regulator" in the system that drops the pressure. It may be heated to minimize mist formation, downstream you should have a coalescing filter to remove any mist or solids.
The soln valves you are using have very tight pressure limits. 65kPa may be to much for them to operate against. Most gas analyzers work great on a few kPa as long as they have adequate flow (a few cc/min inside the cabinet).
If the spent sample is vented to a 0 kPa system, then you need to install a needle valve in the heated cabinet to reduce the pressure and set the flow.
There may be one there already. If so adjust it. It may be located on a sample flow rotameter. Set it. You may also have a sample back-pressure regulator down stream of the analyzer: check it's setting.
If the max. sample pressure to the analyzer is below the pressure of the sample return point in the process, then you need to re-compress it.
Your analyzer reading will depend on the pressure of the gases being tested and those being used for calibration. So pay careful attention to the pressure balance.