A problem from thermodynamics -- Freezing of water at 273 K and 1 atm

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Discussion Overview

The discussion revolves around the thermodynamic process of freezing water at 273 K and 1 atm, specifically examining various thermodynamic properties and equations related to this phase change.

Discussion Character

  • Homework-related
  • Technical explanation
  • Conceptual clarification

Main Points Raised

  • Some participants propose that since the freezing occurs at constant temperature, the internal energy remains constant, leading to claims about ΔU being zero.
  • Others argue that the process is isobaric, and since the volume changes due to the phase change, work done is not zero, suggesting heat must be exchanged according to the first law of thermodynamics.
  • One participant notes that randomness decreases during the freezing process, leading to the assertion that ΔSsys is less than zero.
  • It is mentioned that the process is exothermic, with heat flowing out of the water to form ice, which implies that ΔQ is negative.
  • There is a discussion about the relationship between ΔG, ΔQ, and ΔS, with some participants stating that ΔG equals zero under constant pressure and temperature conditions.
  • One participant expresses uncertainty regarding whether work done (w) is zero, highlighting that ice occupies more volume than liquid water, suggesting some work is done on the surroundings.
  • Clarifications are made regarding the average kinetic and potential energy of water molecules during the freezing process, with emphasis on the loss of rotational kinetic energy.

Areas of Agreement / Disagreement

Participants express differing views on the work done during the freezing process and the implications for internal energy and entropy. There is no consensus on whether work done is zero, and the discussion remains unresolved regarding some of the thermodynamic properties involved.

Contextual Notes

Participants mention various assumptions about the nature of the phase change, including the effects on kinetic and potential energy, as well as the implications of constant pressure and temperature. The discussion does not resolve the mathematical steps involved in the thermodynamic equations.

vijayramakrishnan
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Homework Statement


Freezing of water at 273 K and 1 atm

which of the following is true for the above thermodynamics process
p) q=0
q)w=0
r)ΔSsys<0
s)ΔU=0
t)ΔG=0

Homework Equations


none[/B]

The Attempt at a Solution


[/B]
i got r, s ,t

since the reaction happens at constant temperature,internal energy is constant
since the reaction is open so it is isobaric in nature and since the volume changes due to phase change,so work done is not zero,so heat must be exchanged(first law of thermodynamics).
randomness decreases so ΔSsys<0

but answer given is r t q

i couldn't understand please help.
 
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vijayramakrishnan said:

Homework Statement


i got r, s ,t

since the reaction happens at constant temperature,internal energy is constant
since the reaction is open so it is isobaric in nature and since the volume changes due to phase change,so work done is not zero,so heat must be exchanged(first law of thermodynamics).
randomness decreases so ΔSsys<0

but answer given is r t q

i couldn't understand please help.
##\Delta U## includes potential energy. In order to form ice, the water molecules lose potential energy and rotational kinetic energy. Average translational kinetic energy does not change (i.e. temperature) but average potential energy per molecule decreases and there is loss of rotational kinetic energy. The process is exothermic (heat flows out of the water to form ice).

Since ##\Delta Q < 0##, ##\Delta S = \int dQ/T = \Delta Q/T < 0##.

Since P and T are constant, ##\Delta G = \Delta Q - T\Delta S = T\Delta S - T\Delta S = 0##

I am not sure about w = 0, however. Ice takes up more volume than liquid water (which is why ice floats). So there is a small amount of work done on the surroundings.

[later edits are in italics]

AM
 
Last edited:
Andrew Mason said:
##\Delta U## includes potential energy. In order to form ice, the water molecules lose potential energy. Average kinetic energy does not change (i.e. temperature) but average potential energy per molecule decreases. The process is exothermic (heat flows out of the water to form ice).

Since ##\Delta Q < 0##, ##\Delta S = \int dQ/T = \Delta Q/T < 0##.

Since P and T are constant, ##\Delta G = \Delta Q - T\Delta S = T\Delta S - T\Delta S = 0##

I am not sure about w = 0, however. Ice takes up more volume than liquid water (which is why ice floats). So there is a small amount of work done on the surroundings.

AM
thank you very much sir,understood it.
 
With respect to the internal energy, I should have said that the average translational kinetic energy does not change. The specific heat of water is greater than the specific heat of ice. This is because H2O molecules lose rotational kinetic energy when they freeze to form ice because they lose the rotational degree of freedom.

AM
 

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