GeneralChemTutor said:
At this point I believe that your conclusions is neither consistent with an open or closed system. It seems that you are assuming that the system (meaning the pipet and surroundings) equilibriates through a change in the number of moles (and thus your account of "some of the air" leaving as the pipet gets warm). But note that this is clearly an open system. And that there is a constant work input on the system, which makes it a dynamic system. I should review a standard text to clear things up conclusively , however no time right now.
Yes, the system is open until the thumb is pressed to the end of the pipet. But my calculation begins only after this point. It is not essential that the initial temperature of the gas be equal to that of the liquid the pipet is immersed in. Once my thumb is placed over the pipet, the system is closed and n is conserved.
Until this point we have a system that is trying to equilibrate with the surroundings through exchange of mass and energy. However, the time scale for mass exchange is much smaller than that for temperature exchange, since the mass-flow impedance (essentially determined by the diameter of the opening) is tiny compared to the thermal impedance (determined by conductivities of plastic, convective heat transfer coefficient of the air, as well as the mass flow). So, it is possible to sustain a thermal gradient much longer than you can sustain a pressure gradient.
I'll get back to this later, or perhaps you can perform a order of magnitude calculation.
At a depth of 10 cm
P_{hydro} = h \rho g = 0.1 * 10^3 * 10 = 10^3 Pa
1~ atm = 10^5~ Pa, which is 100 times bigger. 1% of 10 cm (roughly 4") is 1 mm. If there's a large, soft bulb (typically the bulb volume is a little more than the stem volume) with twice the stem volume, the rise from hydrostatic pressure is about 3 mm.
As for capillarity, this depends on the material of the pipet and the inside radius. Water has the greatest capillary action with glass, and with most plastics the effect is nearly an order of magnitude smaller. Look at the contact angles http://www.lib.umich.edu/dentlib/Dental_tables/Contangle.html .Let's Assume the pipet is a glass cylinder of 0.25" ID (pretty small) and the contact angle is 0. Then plugging in the surface tension of water, you get a capillary rise of only about 2 mm. (A little less than I'd imagined.)
So, the total rise from hydrostatic and capillary effects is no more than 3 mm (hard) to 5 mm (soft).
On the other hand, if you can get a temperature difference of even 30K, that's a 10% effect on the volume or pressure (depending on the design of the pipet - hard or soft). So, in the hard cylindrical pipet, this makes the water rise by at least 10mm, and in the bulbed pipette, it rises by 30 mm. This number is at least thrice (in the hard case) the height from the other effects and as much as 6 times the height (in the soft case) .
So, it wouldn't be unfair to say that the dominant cause for the water rise is the isochoric/isobaric behavior of the trapped air.
Also, the surface tension of water changes by no more than 10% over a comparable range of temperatures. So, that affects the capillary rise by only a small fraction of a millimeter.