Ipho 1987, thermodynamics problem: Moist air ascending over a mountain range

  • #51
I'm still not confident about it's temperature. So when the temperature of all components is equal then the process is reversible, so only the assumption of reversibility has given us this argument of equal temperatures? What about condensation and freezing are these also reversible?
 
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  • #52
Jacob White said:
I'm still not confident about it's temperature. So when the temperature of all components is equal then the process is reversible, so only the assumption of reversibility has given us this argument of equal temperatures?
Yes. In a reversible process, the system passes through a continuous sequence of thermodynamic equilibrium states.
What about condensation and freezing are these also reversible?
Sure. Have you ever heard of an ice bath, with ice and liquid water, both at 0 C? All the ice doesn't suddenly change to liquid water and all the liquid water doesn't suddenly change to ice. And you can obviously have steam and water both in contact at 100 C and 1 atm pressure, and all the steam doesn't suddenly change to water and all the water suddenly doesn't all change to steam.
 
  • #53
But it's strictly the assumption of reversibility that ensure us that moist air will stay at the temperature of ice and liquid water, because otherwise it would be irreversible?
 
  • #54
Jacob White said:
But it's strictly the assumption of reversibility that ensure us that moist air will stay at the temperature of ice and liquid water, because otherwise it would be irreversible?
Sure. Then otherwise there would be a finite rate of heat transfer between the moist air and the ice and liquid water.
 
  • #55
Thank you for explanation, so I think now we can go further.
 
  • #56
The variation of the parcel enthalpy with pressure during the interval of declining pressures over which the temperature remains constant at 0 C is still given by: $$dH=VdP\tag{1}$$Since the temperature of the bone dry air does not change, its contribution to dH is zero. Only the relative changes in the amounts of water vapor, liquid water, and ice determine dH. Let ##\omega_S##, ##\omega_L##, and ##\omega_V## represent the number of moles of ice, liquid water, and water vapor present in our parcel at any pressure P in the interval. Then, from a mass balance on the water, we have: $$\omega_S+\omega_L+\omega_V=\omega_{total}$$where ##\omega_{total}=\frac{p_s(279)}{84.5}## is the total number of moles of water in the parcel initially, a constant. From this it follows that the changes in the relative molar amounts are given by:
$$d\omega_S+d\omega_L+d\omega_V=0\tag{2}$$

The change in enthalpy of the overall parcel in the pressure interval over which the temperature remains constant at 0 C is then given by: $$dH=h_Sd\omega_S+h_Ld\omega_L+h_Vd\omega_V\tag{3}$$
where ##h_S##, ##h_L##, and ##h_V## are the molar enthalpies of saturated ice, saturated liquid water, and water vapor relative to an arbitrary reference state. If we eliminate ##d\omega_S## between Eqns. 2 and 3, we obtain: $$dH=(h_L-h_S)d\omega_L+(h_V-h_S)d\omega_V$$where ##(h_l-h_S)=L_F=6200\ J/mole## is the heat of fusion and ##(h_V-h_S)=L_S=(L+L_F)=45000 + 6200 = 51200\ J/mole## is the heat of sublimation. So we have: $$dH=L_Fd\omega_L+L_Sd\omega_V\tag{4}$$During the pressure interval where the temperature is constant, the mole fraction of water vapor in the parcel is given by $$\omega_V=\frac{p_s(273)}{P}$$So $$d\omega_V=-\frac{p_s(273)}{P^2}dP$$and thus our equation for the enthalpy change becomes:
$$L_Fd\omega_L=L_S\frac{p_s(273)}{P^2}dP+\frac{273R}{P}dP\tag{5}$$Because this equation is not a function of temperature, it can be integrated analytically to get the change in the moles of liquid water as a function of the decreasing pressure. It should be integrated from the pressure at which the temperature first hits 0C to the pressure at which the moles of liquid water has dropped to zero.

From your numerical solution, what is the pressure at which the temperature first hits 273 K? How many moles of liquid water are present in the parcel at this pressure?
 
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  • #57
So I get the pressure 74.108kPa and 0.008 moles of vapour. I have integrated equation(5) and get:
$$\omega_L = \frac {-L_s p_s} {L_f P}, + \frac {273R lnP} {L_f} + c$$
Putting numbers c is approximately -4.029.
Then I solve for 0 moles in wolfram but I got some nonsense value(85kPa)
 
  • #58
Jacob White said:
So I get the pressure 74.108kPa and 0.008 moles of vapour. I have integrated equation(5) and get:
$$\omega_L = \frac {-L_s p_s} {L_f P}, + \frac {273R lnP} {L_f} + c$$
Putting numbers c is approximately -4.029.
Then I solve for 0 moles in wolfram but I got some nonsense value(85kPa)
At 74.1, I get 0.0082 moles water in the vapor, and in the initial moist air I get 0.0110 moles water in the vapor. So the amount of liquid water at 74.1 kPa is 0.0028 moles. So, integrating, I get:
$$-0.0028L_F=-L_S(0.606)\left(\frac{1}{P}-\frac{1}{74.1}\right)+273R\ln{(P/74.1)}$$or, equivalently,
$$L_S(0.606)\left(\frac{1}{P}-\frac{1}{74.1}\right)+273R\ln{(74.1/P)}=0.0028L_F$$The solution to this for P must be less than 74.1
 
  • #59
So at 73.535kPa there would be no water molecules left. So from this pressure we could just go back to our first numerical solution and simply change the condensation heat to sublimation heat?
 
  • #60
Jacob White said:
So at 73.535kPa there would be no water molecules left. So from this pressure we could just go back to our first numerical solution and simply change the condensation heat to sublimation heat?
Yes, and also use this heat of sublimation in calculation of subsequent values for the vapor pressure (of ice), starting at 0.606 kPa at 273 K.
 
  • #61
So now after these corrections the final temperature I get is 270.89K which is about 0.6K higher than without considering ice. And that makes sense since we get some additional energy from freezing water.
 
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  • #62
Jacob White said:
So now after these corrections the final temperature I get is 270.89K which is about 0.6K higher than without considering ice. And that makes sense since we get some additional energy from freezing water.
Very nice Jacob. Using the vapor pressure of ice at the final temperature, what do you now predict for the amount rained per kg?
 
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  • #63
Much more - about 3.737g.
 
  • #64
Jacob White said:
Much more - about 3.737g.
It doesn't seem possible. What vapor pressure did you estimate at the final temperature?
 
  • #65
0.5084 kPa
 
  • #66
Jacob White said:
0.5084 kPa
That sounds right, but it implies 2.32 grams/kg
 
  • #67
Sorry again, I forgot about molar masses. 3.737*18/29=2.32
 
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