Two quick/dumb questions regarding thermodynamics

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    Thermodynamics
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Discussion Overview

The discussion revolves around two questions related to thermodynamics: the relationship between the change in enthalpy and heat capacity with respect to temperature, and the calculation of enthalpy changes during chemical reactions using standard enthalpies of formation. Participants explore the reasoning behind these concepts and the validity of certain analogies used to understand them.

Discussion Character

  • Exploratory
  • Technical explanation
  • Conceptual clarification
  • Debate/contested

Main Points Raised

  • One participant questions the expression ##\bigg(\frac{\partial \Delta H_{vap/fusion maybe something else} }{\partial T} \bigg)_p=\Delta Cp## and seeks clarification on its meaning.
  • Another participant challenges the initial participant's method of comparing enthalpy changes to measuring heights, asking why this analogy would not work.
  • A participant expresses uncertainty about why the enthalpy of a reaction equals the difference in enthalpies of formation, relying on their analogy of mountains and heights to make sense of the concept.
  • One participant explains that the enthalpy of a system is a function of state and that changes in enthalpy can be evaluated using Hess's law, suggesting that the path taken between states does not affect the overall change.
  • The same participant clarifies that the superscript 0 in the heat of reaction equation indicates that conditions are held constant, specifically temperature and pressure, while transitioning from reactants to products.

Areas of Agreement / Disagreement

Participants express varying degrees of understanding regarding the relationship between enthalpy changes and the concept of state functions. There is no consensus on the initial participant's analogy or the interpretation of the equations presented.

Contextual Notes

Some participants reference Hess's law and the conditions under which enthalpy changes are calculated, but there are unresolved questions about the derivation and implications of the equations discussed.

Who May Find This Useful

Individuals interested in thermodynamics, particularly students or practitioners seeking clarification on enthalpy changes and the application of state functions in chemical reactions.

davidbenari
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First question is : why is ##\bigg(\frac{\partial \Delta H_{vap/fusion maybe something else} }{\partial T} \bigg)_p=\Delta Cp ## I can't wrap my head around that and nowhere other than my class can I find such an expression.

The other question is regarding the calculation of stuff (say H, S, G, A) during chemical reactions as (for example, enthalpy of a reaction):

##H_{reaction}=\Bigg(\sum \nu_i \Delta Hº\Bigg)_{products}- \Bigg(\sum \nu_i \Delta Hº\Bigg)_{reactants}##

Namely I don't get why adding Deltas ##\Delta## of formation (I'm excepting entropy here) will give the correct enthalpy of the reaction.

I have a very naive argument that defends this expression which I will give just to see what happens:

I imagine two mountains of different height. Here height is refers to the thermodynamic variable in question and its strictly a Delta with respect to the ground. If I have two states, my way to check the height between them is to substract one Delta from the other.

This sounds dumb though.

Any help would be nice. Thanks!
 
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davidbenari said:
If I have two states, my way to check the height between them is to substract one Delta from the other.
What makes you think this method wouldn't work?
davidbenari said:
why is (∂ΔH vap/fusionmaybesomethingelseT ) pCp
What do you think it should be?
 
Bystander said:
What makes you think this method wouldn't work?
Well if I consider enthalpy for example, it's a bit mysterious. Why would the enthalpy of a reaction be equal to the difference of the enthalpies of formation? The only way I can make sense of it is through my dumb analogy of mountains and heights.

Bystander said:
What do you think it should be?
Well, I don't know what it should be. I've finally seen a derivation on google after a lot of time, which makes sense to me at least. Namely they say:

##H_{reaction}=H_{products}-H_{reactants}## If I take the partial derivative of the LHS then its decomposed into two partial derivatives on the RHS which are just Cp's and its therefore a change in Cp.
 
The answers to both your questions relate to the fact that the enthalpy of a system is a function of state and, in each case, you are determining the change in enthalpy between two equilibrium states. To do this, it doesn't matter what path you follow between the two equilibrium states. So you can choose any convenient route. These evaluations can be done by applying Hess's law. Are you familiar with the derivation and application of Hess's law?

In the equation you wrote for the heat of reaction, those superscript 0's means that you are doing whatever is necessary to hold the final temperature the same as the initial temperature, and you are starting out with the pure reactant gases in stoichiometric proportions and going to the pure product gases in corresponding stoichiometric proportions (all at 1 atm.)

Chet
 

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