Posted 16 March 2005 - 07:11 PM
Guest:
Your statement: “A liquid will boil if saturated vapour pressure equals atmospheric pressure” is not a correct statement because it is taken “out of context”. This is a common failing when strict and detailed definitions are not followed precisely as they were intended. This is typically a situation that causes engineering students a lot of grief.
The true statement would be: “A liquid will boil when its vapour pressure is such that it is equal to the system pressure in which it finds itself”. In other words, your definition only works when the system pressure is the atmosphere. My definition is the general definition that works for all cases – where the system pressure is the atmosphere or not.
Boiling involves a change of phase – the liquid molecules are converted to vapor molecules by the addition of the latent heat of vaporization of the parent liquid. If the system that the parent liquid finds itself in is a contained one – i.e., consider a conventional steam boiler – the liquid molecules start to vaporize, exerting their vapor pressure once the liquid achieves its corresponding boiling point. However, if the boiler is blocked-in – i.e., there is no vapor (“steam”) being withdrawn – then the vapor pressure inside the boiler continues to increase if additional heat input is continued. If the heat input is stopped upon reaching a very high pressure level (and the boiler remains blocked-in) the parent liquid water inside the boiler does not “boil”. It remains as water – except that it is categorized as “saturated water”, existing at its corresponding saturated pressure. It is, for practical purposes, in equilibrium with its saturated vapor. This condition is defined very clearly in your Mollier Diagram for steam, on the saturated vapor liquid line. I like the T-S diagram better, because the temperature is a horizontal “tie-line” that communicates the saturated liquid side of the “dome” with the saturated vapor side. If the boiler is maintained in an adiabatic condition (there is no heat loss or gain) while it is blocked-in, there is no “boiling” effect taking place inside. The saturated water level is static and the vapor molecules leaving the surface are equal to the vapor molecules returning to the liquid. This equilibrium can be achieved at any conventional level of pressure (below the Critical Point), and once you open the steam block valve, you will allow the boiler’s vapor pressure to seek a lower level (the effect of a driving force). When this action occurs you will witness “boiling” and, should you continue this while adding the required latent heat of vaporization through the burning of fuel inside the boiler, you will cause continuous boiling and production of steam. In this case the system pressure will be the pressure that you control at by throttling the outlet steam valve. And since the fluid inside the boiler is, for all essential purposes, pure water, then the system pressure is equal to the vapor pressure of water at the saturated temperature.
You can follow the conventional steam cycle through all its circuit on the Mollier Diagram and I highly recommend that you do this with dedicated concentration and study. If you succeed in doing this while identifying all the fluid Thermodynamic paths, you will find a similar, important Thermodynamic process in the mechanical refrigeration cycle using Ammonia – which is also rewarding and a key learning experience for any engineer-to-be.
I hope I explained the answer to your presumed simple question in a manner that allows you not only to understand the “boiling” of water, but the thermodynamic principles and their important applications.
As you can now appreciate, your simple question opens the door to the highly important and rewarding world of Thermodynamics – a subject that is very important to all Chemical Engineers. Welcome to that area of engineering where engineers are made – or broken.
Art Montemayor