Abstract
In this chapter we briefly discuss the possibility of including further interactions in the thermodynamic description, and the release of the previously applied constraints in simple systems. Thus the possibility of the formal treatment of anisotropic deformations, of magnetic, electric and gravitational fields, of systems containing electrically charged particles, and surface effects is briefly described. We also discuss somewhat more detailed the thermodynamics of a couple of interactions that occur more frequently in the chemical praxis; namely the thermodynamics of surfaces and of systems containing electrically charged particles.
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- 1.
Note that stress has an opposite sign with respect to pressure, thus the term to enter into the energy increment is positive.
- 2.
In many cases, the magnetization M is that of the unit volume or molar volume. Here, it means the total magnetization of the whole system, i.e., the unit volume magnetization multiplied by the volume.
- 3.
This difference is typical only in states not too close to the critical point.
- 4.
The word makes allusion to the shape of the crescent Moon. The diminutive form μηνισκος of the Greek word μηνη (a name for the Moon) means the waning crescent. (It survived in the Latin name mensis meaning a month.)
- 5.
If the conditions mentioned are not fulfilled, i.e., the surface is not hemispherical, the pressure acting on the surface can be evaluated as a consequence of the mechanical equilibrium taking into account the actual geometry of the surface. This is the case if wetting is weak, or if the surface is flatter than spherical in a thicker tube.
- 6.
Michael Faraday (1791–1867) was an English chemist and physicist. His most important achievements are in the field of electrochemistry and electromagnetism. He discovered the laws named after him, stating that the transport of a given amount of substance always means the transport of a well-determined amount of electric charge. The unit of capacity, farad is also named after him. (Not to be confused with the chemical unit of charge, faraday.)
- 7.
The person who laid down the principles of electric theory is the American inventor, scientist and politician Benjamin Franklin (1706–1790). He imagined electricity – similarly to heat – as a liquid. According to his interpretation, the charge of bodies containing a lot of electric fluid is “positive” (or “vitreous” using an elder name, as this property occurs when rubbing glass), while the charge of bodies containing little electric fluid is “negative” (or “resinous” using an elder name, as this property occurs when rubbing amber). The movement of the liquid is the electric current. This interpretation still survives in the theory of electricity, where charge carriers are not considered but “the quantity of electric charge”.
- 8.
The unit ppb is the acronym of “parts per billion”. The ratio 0.1 ppb is roughly equivalent to one person over the entire population of Earth.
- 9.
Peter Joseph Wilhelm Debye (1884–1966) was a Dutch physicist, working at German and Swiss universities, and finally at Cornell University in the United States. He received the Nobel-prize in chemistry in 1936, also for contributions to the knowledge of molecular structure through his investigations on dipole moments. He published the theory for dilute electrolyte solutions – later named after the two scientists – together with Hückel in 1923. Erich Armand Joseph Hückel (1896–1980) was a German physicist and mathematician. His most important work is the introduction of simplified quantum mechanical methods to describe molecular orbitals (later called the Hückel MO theory), which also led to the interpretation of the aromatic structure. He co-authored the Debye-Hückel theory while working with Debye in Zürich.
- 10.
We consider as the potential of the phase the inner potential, which can be measured inside the phase, in contrast with the outer potential, which can be measured on the surface of the phase at an infinitely small distance.
- 11.
The name is derived from the family name of the Bolognese medical doctor, Luigi Galvani (1737–1798). He was the first to describe the device nowadays called an electrochemical cell, which he discovered while dissecting frogs, and first interpreted its electric power as the product of living cells. The galvanic cell is the version where – if joining the terminal wires – a spontaneous electric current is flowing. The other version is called an electrolytic cell, in which an external voltage drives a current of opposite direction to that of the galvanic cell.
- 12.
The names anode, cathode, and electrode have been introduced by Faraday who discovered the migration of ions. The actual forms of these names were proposed to Faraday by the scientist and priest William Whewell (1794–1866). The Greek word ανοδος refers to the rising sun, while καθοδος to the setting sun, thus expressing the opposite direction of the current at the two terminals with respect to the cell. The (positive) current enters the cell on the anode and leaves the cell on the cathode. The word electrode is a generalized expression referring to a current passing thorough a half cell.
- 13.
Prior to the introduction of the SI, the reference pressure was 1 atm = 1.01325 bar. As a consequence, electrode potentials found in tables referenced to a hydrogen pressure of 1.01325 bar are higher than the currently used values referenced to 1 bar by 0.169 mV (0.000169 V).
- 14.
To expand, let us add the term \(RT \left({\rm ln}\; m^{z}_{\rm NO_3^{-}}\; {\rm -ln}\; m^{a}_{\rm NO_3^{-}} +\;{\rm ln}\; \frac{m^{a}_{\rm NO_{3}^{-}}}{{m^{z}_{\rm NO_3^{-}}}} \right)=0\).
Further Reading
Bard AJ, Inzelt GY, Scholz F (eds) (2008) Electrochemical dictionary. Springer, Heidelberg
Denbigh KG (1981) The principles of chemical equilibrium, 4th edn. Cambridge University Press, Cambridge
Guggenheim EA (1985) Thermodynamics: an advanced treatment for chemists and physicists, 7th edn. North Holland, Amsterdam
IUPAC Task Group (1994) Standard quantities in chemical thermodynamics. Fugacities, activities and equilibrium constants for pure and mixed phases (IUPAC Recommendations 1994). Pure Appl Chem 66:533–552
Mohr PJ, Taylor BN, Newell DB (2007) CODATA recommended values of the fundamental physical constants: 2006. National Institute of Standards and technology, Gaithersburg, MD
Silbey LJ, Alberty RA, Moungi GB (2004) Physical chemistry, 4th edn. Wiley, New York
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Keszei, E. (2012). Extension of Thermodynamics for Additional Interactions (Non-Simple Systems). In: Chemical Thermodynamics. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-19864-9_9
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DOI: https://doi.org/10.1007/978-3-642-19864-9_9
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