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Question

Question: Derive relationship between \(H\,and\,U\) ....

Derive relationship between HandUH\,and\,U .

Explanation

Solution

In order to answer this question, to derive the relation between HandUH\,and\,U , first of all we should know that what is the exact term is instead of HandUH\,and\,U . Then we should go through their chemical properties, and just compare the similarities to relate them.

Complete answer:
In the given question, we have to derive the relation between enthalpy (H)(H) and internal energy (U)(U) .
Let H1{H_1} be the enthalpy of the system in the initial state and Hf{H_f} be the enthalpy of the system in a final state. Let UiandVi{U_i}\,and\,{V_i} be the internal energy and volume in the initial state and UfandVf{U_f}\,and\,{V_f} be the internal energy and volume in a final state.
Now, as we know that,
H=U+PVH = U + PV
Therefore,
Hi=Ui+PVi{H_i} = {U_i} + P{V_i} …..(i)
Hf=Uf+PVf{H_f} = {U_f} + P{V_f} …..(ii)
Subtracting equation (i) from (ii), we have:
HfHi=(Uf+PVf)(Ui+PVf) HfHi=(UfUi)+P(VfVi) ΔH=ΔU+PΔV......(iii) \begin{gathered} {H_f} - {H_i} = ({U_f} + P{V_f}) - ({U_i} + P{V_f}) \\\ \Rightarrow {H_f} - {H_i} = ({U_f} - {U_i}) + P({V_f} - {V_i}) \\\ \Rightarrow \Delta H = \Delta U + P\Delta V\,\,\,......(iii) \\\ \end{gathered}
Here, ΔUandPΔV\Delta U\,and\,P\Delta V are the change in internal energy and work energy respectively.
Hence, equation (iii) is the relationship between HandUH\,and\,U .

Note:
Heat effects measured at constant pressure indicate changes in enthalpy of a system and not in changes of internal energy of the system. Using calorimeters operating at constant pressure, the enthalpy change of a process can be measured directly.