Why Does Enthalpy Decrease on Isothermal Compression?

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SUMMARY

In an isothermal system containing oxygen, increasing the pressure from 0 to 10 MPa results in a decrease in enthalpy due to the behavior of real gases. The relationship between enthalpy change (ΔH), internal energy change (ΔU), and pressure-volume work (ΔPV) is defined by the equation ΔH = ΔU + ΔPV. For real gases, the enthalpy is influenced by pressure, as indicated by the equation ∂H/∂p = (V - T(∂V/∂T)), which is zero for ideal gases. This indicates that as pressure increases, the internal energy decreases, leading to a reduction in enthalpy.

PREREQUISITES
  • Understanding of thermodynamic principles, specifically isothermal processes.
  • Familiarity with the equations of state for gases, including PV = nRT and PV = ZRT.
  • Knowledge of the concept of internal energy and its relation to enthalpy.
  • Basic understanding of real gas behavior versus ideal gas behavior.
NEXT STEPS
  • Study the implications of real gas behavior on thermodynamic properties using "Introduction to Chemical Engineering Thermodynamics" by Smith and Van Ness.
  • Learn about the Maxwell relations and their applications in thermodynamics.
  • Explore the concept of compressibility factors (Z) and their role in real gas calculations.
  • Investigate the relationship between pressure, volume, and temperature in non-ideal gases using generalized dimensionless graphs.
USEFUL FOR

Students and professionals in chemical engineering, thermodynamics, and physical chemistry who are seeking to understand the behavior of gases under varying pressure conditions, particularly in isothermal processes.

sero2000
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Homework Statement



Basically I just want to know why if I increase the pressure from 0 to 10MPa in a isothermal system containing oxygen, the enthalpy will decrease?

Homework Equations



Delta H = Delta U + delta PV

PV = nRT

PV = ZRT


The Attempt at a Solution



During a tutorial, I was actually told that because of the compression, the compressed molecules will have less space to move around which results in a decrease in internal energy. Honestly I don't get it.

If I have a compression taking place, doesn't that mean Work is done on the system? Wouldnt that mean in order to keep the system isothermal, energy would have to be removed from the system? which results in enthalpy being reduced?

In that case and also because at 10MPa the gas is not ideal, I used PV = ZRT but I can't find the link between this and Delta H = Delta U + delta PV.

Any help in clearing this doubt is really appreciated :D
 
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sero2000 said:

Homework Statement



Basically I just want to know why if I increase the pressure from 0 to 10MPa in a isothermal system containing oxygen, the enthalpy will decrease?

Homework Equations



Delta H = Delta U + delta PV

PV = nRT

PV = ZRT


The Attempt at a Solution



During a tutorial, I was actually told that because of the compression, the compressed molecules will have less space to move around which results in a decrease in internal energy. Honestly I don't get it.

If I have a compression taking place, doesn't that mean Work is done on the system? Wouldnt that mean in order to keep the system isothermal, energy would have to be removed from the system? which results in enthalpy being reduced?

In that case and also because at 10MPa the gas is not ideal, I used PV = ZRT but I can't find the link between this and Delta H = Delta U + delta PV.

Any help in clearing this doubt is really appreciated :D
Enthalpy is independent of pressure only for an ideal gas. For a real gas beyond the ideal gas region,
[tex]\frac{∂H}{∂p}=\left(V-T\frac{\partial V}{\partial T}\right)[/tex]
Note, for an ideal gas, this is zero. There are generalized dimensionless graphs and tabulations in thermo books of the integral of this expression based on the corresponding states principal. You can use these to estimate the change in enthalpy for oxygen, from knowledge its critical properties. See Introduction to Chemical Engineering Thermodynamics by Smith and Van Ness.

Chet
 

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