First law of thermodynamics situation

Click For Summary
SUMMARY

The discussion centers on the application of the first law of thermodynamics in a scenario involving an insulated tank of hydrogen and oxygen undergoing a chemical reaction to form water. The participants highlight the contradiction between the first law, expressed as ΔU = Q - W, and the increase in internal energy due to temperature rise during the reaction. They emphasize that the first law must be generalized to account for changes in the number of particles (N) and the chemical potential (μ), as traditional interpretations assume constant N and neglect chemical and nuclear energy contributions. The conversation concludes that the kinetic theory of gases is not suitable for analyzing systems where chemical reactions occur.

PREREQUISITES
  • Understanding of the first law of thermodynamics (ΔU = Q - W)
  • Familiarity with internal energy concepts and temperature dependence
  • Knowledge of chemical potential (μ) and its role in thermodynamic systems
  • Basic principles of the kinetic theory of gases
NEXT STEPS
  • Research the generalized form of the first law of thermodynamics, including chemical potential
  • Study the relationship between internal energy and temperature in chemical reactions
  • Explore the implications of exothermic and endothermic reactions on thermodynamic laws
  • Examine the limitations of the kinetic theory of gases in reactive systems
USEFUL FOR

Students of thermodynamics, chemists, and physicists interested in the interplay between thermodynamic laws and chemical reactions.

fluidistic
Gold Member
Messages
3,932
Reaction score
283
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!
 
Science news on Phys.org
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.
 

Similar threads

  • · Replies 46 ·
2
Replies
46
Views
6K
  • · Replies 5 ·
Replies
5
Views
2K
  • · Replies 13 ·
Replies
13
Views
2K
  • · Replies 23 ·
Replies
23
Views
3K
  • · Replies 9 ·
Replies
9
Views
3K
  • · Replies 3 ·
Replies
3
Views
2K
  • · Replies 135 ·
5
Replies
135
Views
8K
  • · Replies 14 ·
Replies
14
Views
2K
  • · Replies 10 ·
Replies
10
Views
3K
  • · Replies 4 ·
Replies
4
Views
1K