Why is first TD law different for chemical reactors

In summary, the conversation discusses the first law of thermodynamics for open systems, which states that the total change of system energy is equal to the transferred heat and work. The energy balance of a CSTR reactor is also discussed, where the total change of system energy is equal to the energy transferred via mass flux and the energy change within the system. There is a question about where to put the total enthalpy differential in the derivation, with one option being to include it in the term for total change of system energy. However, it is concluded that the total differential belongs to the term for the integral of system enthalpy along the system volume. There may be some issues with the correctness of certain equations and a recommended resource for learning more
  • #1
ussername
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I've learned that first thermodynamic law for some open system is in the form of:

Energy+Conservation+Friction+Loss+%28Viscous%29+Mechanical+Work+Heat.jpg

where total change of system energy ##\frac{\partial E}{\partial \tau }## is equal to the transferred heat and work.
Total change of system energy ##\frac{\partial E}{\partial \tau }## is equal to the energy transferred via mass flux (surface integral) plus energy change within the system (volume integral).

Now I've seen energy balance of CSTR reactor and it is in the form of:
tKdm2rH.png


Full derivation is here or here.

I think ##\frac{\partial E}{\partial \tau }## in the bottom picture means total change of system (internal) energy, because further in the derivation it is replaced with total enthalpy differential and it is substituted with CSTR mass balance:
$$\frac{\partial n_{i}}{\partial \tau }=F_{i}^{0}-F_{i}+V\cdot \upsilon _{i}\cdot r_{V}$$
which makes sense only if ##\frac{\partial E}{\partial \tau }## is total change of energy.

If ##\frac{\partial E}{\partial \tau }## in the bottom picture means total change of system energy then it is not the same equation as in the first picture.

Can anybody explain?
 
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  • #2
I have correctness problems with both the insets in your post, and one of the links. In my judgment and experience, the development that is done correctly is this one: http://jbrwww.che.wisc.edu/home/jbraw/chemreacfun/ch6/slides-enbal.pdf. If you wish to learn more about correctly-done energy balances (both for mechanical energy and thermal energy), see Bird, Stewart, and Lightfoot, Transport Phenomena.
 
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  • #3
My second picture is from the link you posted.

I had basically problem to understand where to put enthalpy total differential H=f(T,p,n):
$$\frac{\partial H}{\partial \tau}=\dot{H}_{out}-\dot{H}_{in}+\frac{\partial }{\partial \tau}\left (\int_{V}^{ }\frac{\partial H}{\partial m}\,dm \right )$$
First I thought that ##\frac{\partial H}{\partial \tau}## is the total enthalpy change of the system so the total differential H=f(T,p,n) should belong to there.
But the derivation says that total differential belongs to this term:
$$\frac{\partial }{\partial \tau}\left (\int_{V}^{ }\frac{\partial H}{\partial m}\,dm \right )$$and it seems partially logical because this integral adds elements of system enthalpy ##dH## along the system volume, so this integral is equal to the system enthalpy.
 
  • #4
ussername said:
My second picture is from the link you posted.

I had basically problem to understand where to put enthalpy total differential H=f(T,p,n):
$$\frac{\partial H}{\partial \tau}=\dot{H}_{out}-\dot{H}_{in}+\frac{\partial }{\partial \tau}\left (\int_{V}^{ }\frac{\partial H}{\partial m}\,dm \right )$$
First I thought that ##\frac{\partial H}{\partial \tau}## is the total enthalpy change of the system so the total differential H=f(T,p,n) should belong to there.
But the derivation says that total differential belongs to this term:
$$\frac{\partial }{\partial \tau}\left (\int_{V}^{ }\frac{\partial H}{\partial m}\,dm \right )$$and it seems partially logical because this integral adds elements of system enthalpy ##dH## along the system volume, so this integral is equal to the system enthalpy.
Are you saying that the equations in the second inset you posted are incorrect? Are you familiar with the derivation of the open system (control volume) version of the first law of thermodynamics?
 

1. Why is the first TD law different for chemical reactors?

The first TD law, also known as the Law of Conservation of Energy, states that energy cannot be created or destroyed, only transferred or transformed. This law applies to all systems, including chemical reactions. However, in chemical reactors, the first TD law may appear different because it is often used in the context of heat transfer and enthalpy changes. This is due to the fact that chemical reactions involve both energy transfer and transformation, unlike other systems where energy is only transferred.

2. How does the first TD law apply to chemical reactors?

The first TD law applies to chemical reactors in the sense that the total energy of the reactants must be equal to the total energy of the products. This means that in a closed system, the heat released or absorbed during a chemical reaction must be balanced by the change in internal energy and work done by the system.

3. Can the first TD law be violated in chemical reactors?

No, the first TD law cannot be violated in chemical reactors or any other system. This law is a fundamental principle of thermodynamics and has been proven to hold true in all physical and chemical processes. Any apparent violations of this law can be explained by incomplete data or a misunderstanding of the system.

4. How does the first TD law affect the efficiency of chemical reactions?

The first TD law has a significant impact on the efficiency of chemical reactions. In order for a reaction to be efficient, the heat released or absorbed must be minimized in order to maximize the amount of energy available for useful work. This is why many chemical reactions are carried out at specific temperatures and pressures to optimize their efficiency.

5. Are there any exceptions to the first TD law in chemical reactors?

There are no exceptions to the first TD law in chemical reactors. However, in some cases, the heat released or absorbed during a reaction may not be accurately measured or accounted for, leading to discrepancies in the energy balance. Additionally, some reactions may appear to violate the law due to the presence of catalysts, which can lower the activation energy and increase the rate of a reaction without changing the total energy involved.

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