DG is for isothermal thus dH =0?

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Homework Help Overview

The discussion revolves around the thermodynamic properties of internal energy (U) and enthalpy (H) in isothermal processes, particularly focusing on the implications of changes in these properties when temperature is held constant. Participants are exploring the relationships between Gibbs free energy (G), Helmholtz free energy (A), and their dependence on temperature and entropy.

Discussion Character

  • Conceptual clarification, Assumption checking, Mixed

Approaches and Questions Raised

  • Participants are questioning the assumption that ΔH and ΔU are zero for isothermal processes, particularly in non-ideal systems. There is discussion about the role of temperature and the potential impact of changes in the number of moles of gas on enthalpy.

Discussion Status

The discussion is active, with participants providing insights into the conditions under which U and H can be considered functions of temperature alone. Some have suggested that for non-ideal gases, other variables may need to be considered, and there is an exploration of how changes in gas moles might influence enthalpy.

Contextual Notes

There is an ongoing examination of the definitions and relationships between thermodynamic potentials, with references to Maxwell relations and the implications of ideal versus non-ideal gas behavior. The discussion highlights the complexity of thermodynamic systems beyond simple assumptions.

sparkle123
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If U, H are functions of T only, then ΔU and ΔH should be zero for isothermal processes
ΔG and ΔA are only defined at constant T (thus define isothermal processes)
ΔG = ΔH – TΔS thus equals -TΔS always (since ΔH=0)?
this makes no sense since from previous calculations I have done in many problems ΔH has nonzero value
similarly, ΔA = ΔU - TΔS= -TΔS?
Please help clear my confusion, thanks.
 
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U and H are functions of only temperature if the gas is ideal (in which case ΔH=ΔU=0 for an isothermal process). For a non-ideal system, temperature is not the only relevant variable.
 
The fundamental thermodynamic relation is:
[tex] dU = T \, dS - P \, dV[/tex]
which would imply that the internal energy U is a function of entropy S and volume V as natural variables. The partial derivatives can be read off from this differential form:
[tex] T = \left(\frac{\partial U}{\partial S}\right)_{V}, \; P = -\left(\frac{\partial U}{\partial V}\right)_{S}[/tex]
Because the mixed second partial derivatives have to be equal, we have the following identity:
[tex] \left(\frac{\partial T}{\partial V}\right)_{S} = -\left(\frac{\partial P}{\partial S}\right)_{V}[/tex]
which is one of the Maxwell relations.

The other therodynamic potentials are Legendre transfroms:
[tex] \begin{array}{lcr}<br /> H = U + P \, V & dH = T \, dS + V \, dP & H = H(S, P) \\<br /> <br /> A = U - T \, S & dA = -S \, dT - P \, dV & A = A(T, V) \\<br /> <br /> G = U - T \, S + P \, V & dG = -S \, dT + V \, dP & G = G(T, P)<br /> \end{array}[/tex]
You should be able to deduce the other three Maxwell relations from these expressions.
 
danago said:
U and H are functions of only temperature if the gas is ideal (in which case ΔH=ΔU=0 for an isothermal process). For a non-ideal system, temperature is not the only relevant variable.

Wow is this really it?
perhaps changes in moles of gas is also a factor?
 
sparkle123 said:
Wow is this really it?
perhaps changes in moles of gas is also a factor?

If we are talking about the total enthalpy (i.e. in units of energy), then yes it will change with the number of moles of gas; however the specific enthalpy (i.e. energy/mole) will remain unchanged.
 

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