Wednesday 23 January 2019

thermodynamics - What does Enthalpy mean?


What is meant by enthalpy? My professor tells me "heat content". That literally makes no sense. Heat content, to me, means internal energy. But clearly, that is not what enthalpy is, considering: $H=U+PV$ (and either way, they would not have had two words mean the same thing). Then, I understand that $ΔH=Q_{p}$. This statement is a mathematical formulation of the statement: "At constant pressure, enthalpy change may be interpreted as heat." Other than this, I have no idea, what $H$ or $ΔH$ means.


So what does $H$ mean?




Answer



Standard definition: Enthalpy is a measurement of energy in a thermodynamic system. It is the thermodynamic quantity equivalent to the internal energy of the system plus the product of pressure and volume.


$H=U+PV$


In a nutshell, The $U$ term can be interpreted as the energy required to create the system, and the $PV$ term as the energy that would be required to "make room" for the system if the pressure of the environment remained constant.


When a system, for example, $n$ moles of a gas of volume $V$ at pressure $P$ and temperature $T$, is created or brought to its present state from absolute zero, energy must be supplied equal to its internal energy $U$ plus $PV$, where $PV$ is the work done in pushing against the ambient (atmospheric) pressure.


More on Enthalpy :


1) The total enthalpy, H, of a system cannot be measured directly. Enthalpy itself is a thermodynamic potential, so in order to measure the enthalpy of a system, we must refer to a defined reference point; therefore what we measure is the change in enthalpy, $\Delta H$.


2) In basic physics and statistical mechanics it may be more interesting to study the internal properties of the system and therefore the internal energy is used. But In basic chemistry, experiments are often conducted at constant atmospheric pressure, and the pressure-volume work represents an energy exchange with the atmosphere that cannot be accessed or controlled, so that $\Delta H$ is the expression chosen for the heat of reaction.


3) Energy must be supplied to remove particles from the surroundings to make space for the creation of the system, assuming that the pressure $P$ remains constant; this is the $PV$ term. The supplied energy must also provide the change in internal energy, $U$, which includes activation energies, ionization energies, mixing energies, vaporization energies, chemical bond energies, and so forth.


Together, these constitute the change in the enthalpy $U + PV$. For systems at constant pressure, with no external work done other than the $PV$ work, the change in enthalpy is the heat received by the system.



For a simple system, with a constant number of particles, the difference in enthalpy is the maximum amount of thermal energy derivable from a thermodynamic process in which the pressure is held constant.


(Source : https://en.wikipedia.org/wiki/Enthalpy )


OP's question-


What does "make room" mean ? -


For instance, you are sitting on a chair. Then you stand up and stretch your arms. Doing this, you displace some air to make room for yourself. Similarly a gas does some work to displace other gases or any other constraint to make room for itself. To make it more understandable, imagine yourself contained in a box just big enough to contain you. Now, trying stretching your arms. You will certainly have to do a lot of work to completely stretch you arms completely. Air is just like this box except in case of air you have to do negligible work to make room for yourself.


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