Sure. Without thermodynamics, physical chemistry is blind.

I agree with Zaved. Chemical thermodynamics is specially important to analyze cycles such as internal combustion engines, or any process in which it is expected to take advantage of energy released by the means of chemical reactions. You can see an example of this in the book by Smith, Van Ness and Abbott, on the last chapter, where they demonstrate a lost work calculation for a steam plant, including the combustion of the fuel in boiler to produce steam.

I agree with Zaved. BTW, I have found an estimation for increasing of entropy H from below for controlled processes (addition to the Second Law of thermodynamics).

\Delta H >= const/T^2 where T is the time of transition from one stationary state to another one. Is it new?

Have you checked the link given with my question? I am certain this will help you to come up with better picture on your work. Good Luck!

I was a bit hesitant to get into this discussion, but I'll try for an answer. First, let's set the terms straight:

a) Chemical thermodynamics: applying the terminology of thermodynamics which was created to describe steam engines on chemical processes. This is still a macroscopic approach and therefore the draft you posted is "not chemical thermodynamics".

b) Statistical thermodynamics: this is the usage of microscopic modelling to explain the outcome of macroscopic, classical thermodynamic observations. Just using microscopic energies in macroscopic equations is not enough.

Now, for the actual content: it seems to me that the description of "positioned atoms" that you use is very similar to the origin of the r-6 van der Waals forces (Keesom , Debye , London dispersion interactions). For an overview, see e.g. Butt/Graf/Kappl "Chemistry and Physics of Interfaces" and for a full derivation of the London dispersion force see Desjonqueres/Spanjaard "Concepts in surface physics".

These forces are actually in use in statistical thermodynamics for quite some time, e.g. from the intermolecular Sutherland potential (http://www.sklogwiki.org/SklogWiki/index.php/Sutherland_potential) you can derive the van der Waals state equation of real gases (here's an updated version of the lecture I attended back in the day, it's chapter 6.1: https://www.tkm.kit.edu/downloads/ss2015_statphys/Theory_F_2014-1Schmalian.pdf). Since the van der Waals equation is probably one of the most-used state equations to account for non-ideality of gases, I suppose the importance of accounting for microscopic effects is well-established.

The above-presented discussion of the colleague covers quite a large previously studied topics in different eras, which not only fall under different sections of thermodynamics, but some topics also fall under the area of materials science. I personally appreciate writing these scientific details. However, my question was “Can chemical thermodynamics be an essential part to understand the entropy and different irreversible cycles? If, in the view of respected colleague, the study of entropy and different irreversible cycles should not fall under the “chemical thermodynamics” then what is the suggestion of colleague, so that we can think on that suggestion.

As long as the discussion is productive, appealing and adding new scientific information, there is no reason to hesitate. Please feel free to write your point of view on my questions.

For your kind information, my some preprint articles discussed what is the role of van der Waals forces under new insights (https://arxiv.org/abs/1604.07144v21, https://arxiv.org/abs/1609.08047v33, https://arxiv.org/abs/1611.01255v31). Again, my three studies were also published in last two years (https://doi.org/10.1021/acsanm.0c02022, https://doi.org/10.1007/s13204-018-0937-z, https://doi.org/10.1002/sia.6593) discussing the roles of van der Waals forces with new insights.

Yes, it help to understand entropy changes in systems. Actually there are no much different between chemical thermodynamic and physical thermodynamics. In physical thermodynamic work equal to Pressure * volume change. the expansions are referred as positive. but in chemistry the expansions are get negative sign. Work equal to - Pressure * volume change

Physics

dU = dq - dw ( dw= PdV)

chemistry

dU = dq + dw (dw= -PdV)

I think that the importance of including chemical processes into entropic considerations has been acknowledged by everyone who posted here at this point and is not really doubted by anoyone seriously.

My point was not that microscopic effects should not be accounted for (which would be weird for someone who did his PhD in a group called "Physical Chemistry of Microscopic Systems"), but there is a formalism for that which has to be used in order to get a meaningful result. In the linked preprint microscopic energies are just put into macroscopic thermodynamic equations and that is not the way this physics works. The steps are:

1) Consider the microscopic energies (non-thermodynamically). This leads to the aforementioned intermolecular forces and thus interatomic or intermolecular interaction potentials such as Lennard-Jones, Buckingham, Sutherland or others.

2) Calculation of a partition function/sum of states/autocorrelation function (in a dynamic approach) or some other statistical quantity that allows the usage of methods based on the ergodic hypothesis.

3) Derivation of macroscopic quatities from the statistical function, e.g. the desired entropy. There are multiple ways to do this, but one of them has to be used.

Now, again, the example in the preprint: if the formalism is applied to this segment of physics properly, you will end up with a equation of state of a real gas. In the case of the derivations I linked above you end up with the van der Waals equation. That means, if you derive an entropy from a real gas equation of state, may it be van der Waals, Redlich-Kwong or Virial, you automatically have taken these effects into account for your macroscopic model.

well done. with such good insight many areas of chemical thermodynamics and physical chemistry can be opened. keep it up and my best wishes