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Sample introduction · No. 23The Ideal Gas Law

Sample introduction — the physics of getting in

The ideal gas law at the instrument

PV = nRT runs through every gas chromatograph: how much sample a gas loop delivers, whether a liquid injection fits its liner, and how the carrier flows.

By Medrado Analytical Innovations · Foundations, No. 23 · for the working analyst

In this piece · 6 min read
  1. The law in one line
  2. The gas sample loop
  3. Liquefied gases
  4. The liquid injection
  5. The carrier gas
  6. When gases stop being ideal
  7. The judgement

Most analysts last met the ideal gas law in a first-year chemistry exam: PV = nRT, pressure times volume equals the amount of gas times a constant times the temperature. It seems to belong to the textbook, not the lab. But a gas chromatograph runs on it. It describes how much sample a gas loop delivers, how much room a liquid injection needs in the inlet, and how the carrier gas flows. And for a gas loop filled to the room's atmosphere, it is one reason a QC chart can follow the barometer.

The law in one line

Pressure, volume, temperature and the amount of gas are tied together:

P × V = n × R × T n = amount of gas (moles), R = 8.314 J/(mol·K), T in kelvin, P absolute for a fixed volume filled to a set pressure: n is proportional to P / T

Read the second line in plain words. A container of fixed size, filled until it reaches a given pressure, holds more gas when that pressure is higher, and less gas when it is warmer. (This is different from the classroom picture of a sealed flask, where the amount is fixed and the pressure rises when you heat it.) Two things to keep straight: P must be the absolute pressure, not the gauge reading, and T must be in kelvin.

Check yourself

Answer in your head first, then open the answer. Any question can go into your Quiz me.

  1. A gas loop is filled to the room's pressure. The barometer rises. What happens to the sample delivered?

    Show the answer
    “A gas sample loop holds a fixed volume, so the amount of sample it holds rises and falls with the pressure and temperature of the gas inside it.”

    See it in the article ·

  2. Why can one microlitre of liquid overfill an inlet liner?

    Show the answer
    “One microlitre of liquid becomes hundreds to about a thousand microlitres of vapour in a hot inlet, and the liner has to hold it.”

    See it in the article ·

  3. What happens when the vapour cloud is larger than the liner?

    Show the answer
    “If the vapour cloud is larger than the liner, sample escapes where it should not, and the results stop repeating.”

    See it in the article ·

Glossary

Absolute pressure
The gauge reading plus the atmosphere; the pressure the ideal gas law needs.
Sample loop
A short tube of known volume that fills with a gas sample and is then switched into the carrier stream.
Liner
The glass sleeve in a GC inlet where a liquid injection vaporises.
Compressibility factor
The correction that describes how far a real gas departs from PV = nRT; close to 1 near atmospheric pressure.

Sources

  1. P. Atkins, J. de Paula and J. Keeler, Atkins' Physical Chemistry, 11th ed. (Oxford University Press, 2018): the perfect gas equation; real gases and the compressibility factor.
  2. Agilent Technologies, "Tips on Making your GC System and Analysis more Robust" (e-seminar, 2016; solvent vapour volumes at 250 °C and 20 psig, liner volumes), agilent.com/cs/library/eseminars/public/Tips_on_Making_your_GC_System_and_Analysis_more_Robust_10112016.pdf; and the Agilent GC Vapor Volume Calculator (OpenLab GC help).
  3. H. M. McNair, J. M. Miller and N. H. Snow, Basic Gas Chromatography, 3rd ed. (Wiley, 2019): carrier gas, viscosity and flow control.