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Does analyte signal from GC-TCD depend on the matrix?

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BROe:
I'm trying to calibrate a GC-TCD with CO in order to measure the amount generated by CO2 reduction in a sealed electrochemical cell. Currently I am injecting volumes of the calibration gas (CO) into the sealed cell before sending a sample of its headspace through the GC. Would my calibration be equally as accurate if I instead injected known volumes of the calibration gas into the GC? I'm thinking that it should be despite not having the same matrix (CO2) in my calibrators as I would when sampling the sealed cell headspace.

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