First law of thermodynamics situation

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Discussion Overview

The discussion revolves around the application of the first law of thermodynamics in a scenario involving an insulated tank filled with hydrogen and oxygen undergoing a chemical reaction to form water. Participants explore the implications of temperature changes and internal energy in the context of thermodynamic principles, particularly focusing on the assumptions underlying the first law.

Discussion Character

  • Exploratory
  • Technical explanation
  • Debate/contested

Main Points Raised

  • One participant questions the application of the first law of thermodynamics, noting that in their scenario, both heat exchange (Q) and work done (W) are zero, leading to a contradiction with the expected increase in internal energy due to temperature rise.
  • Another participant suggests using a more generalized form of the first law that includes the chemical potential and the number of particles, indicating that the initial assumptions may not hold in this case.
  • Some participants argue that the internal energy of a gas is typically considered to be temperature-dependent, but this perspective may not account for changes due to chemical reactions, which could alter internal energy without a corresponding change in temperature.
  • There is a discussion about the limitations of the kinetic theory of gases, which assumes minimal interactions between particles and may not be applicable when chemical reactions occur, thus complicating the analysis of energy changes.

Areas of Agreement / Disagreement

Participants express differing views on the applicability of the first law of thermodynamics in the context of chemical reactions, with no consensus reached on how to reconcile the apparent contradictions presented.

Contextual Notes

Participants highlight the limitations of the first law when applied to systems undergoing chemical reactions, suggesting that assumptions about constant particle numbers and interactions may not be valid in this scenario.

fluidistic
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Hi,
My mind has been blown up recently when I came across this thread: https://www.physicsforums.com/showthread.php?t=372533.

I'd like some explanations about something.

Imagine an insulated tank filled with hydrogen and oxygen at 100°C (or greater if possible) and 1 atm.
Now a spark starts on.
Imagine that all the gas transformed into H_20. The temperature must increase as I've been told, so that the water is under the gas form (despite the fact that at higher pressure water needs to be put at more than 100°C).

From the first law of thermodynamics, I know that \Delta U = Q-W. In this case, Q and W are worth 0 J because no heat is exchanged within the surroundings of the system and the volume remains constant. So still according to the first law, \Delta U=0 J.
However, in Resnick-Halliday, it is clearly stated that the internal energy of a gas is directly proportional to its temperature and is only temperature dependent. Hence an increase of temperature means an increase of internal energy.
Hence according to this book, I'm tempted to say that the system has gained energy.
It is in contradiction with the first law.
What's going on?

Thanks a lot in advance, I really need to know!
 
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I think, in this case, you must use a more generalized form of the first law.

N changes in this reaction, so your first law must include the mu*dN term (where mu is the chemical potential, N is the number of particles). I'm not sure what else, but the form of the first law that you used makes a few assumptions on what parameters are changeable in your system (e.g. it assumes N stays constant, and perhaps some other stuff).
 
Last edited:
fluidistic said:
However, in Resnick-Halliday, it is clearly stated that the internal energy of a gas is directly proportional to its temperature and is only temperature dependent.

That's based on the assumption that internal energy is the sum of the kinetic energy of all particles. How could they claim such a thing? It's allowed because internal energy is never defined in an absolute sense, because chemical and nuclear energy would have to be included, and they are omitted. So we are talking only about a change in internal energy during a process, not the absolute amount of internal energy. If an exothermic or endothermic chemical reaction occurs, the assumption that makes the first law possible would no longer be valid.

delta U = Q-W is like saying the increase in a bank account balance equals deposits minus withdrawals. If you have a chemical reaction that releases heat, that's like earning some interest on the money, so the balance sheet no longer adds up.
 
mikelepore said:
That's based on the assumption that internal energy is the sum of the kinetic energy of all particles. How could they claim such a thing? It's allowed because internal energy is never defined in an absolute sense, because chemical and nuclear energy would have to be included, and they are omitted. So we are talking only about a change in internal energy during a process, not the absolute amount of internal energy. If an exothermic or endothermic chemical reaction occurs, the assumption that makes the first law possible would no longer be valid.

delta U = Q-W is like saying the increase in a bank account balance equals deposits minus withdrawals. If you have a chemical reaction that releases heat, that's like earning some interest on the money, so the balance sheet no longer adds up.

Thanks a lot. Very clear explanation. I'm having a good wake-up.
 
To put it another way, the kinetic theory of gases begins by assuming that the particles will rarely interact with each other at all, and that the main thing the particles will do is travel in straight lines in between when they bounce off the container walls. In the rare cases where the particles do interact with each other, the only kind of interactions among them will be perfectly elastic collisions. Such a theory isn't intended to study a case where chemical reactions are happening.
 

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