Measurement Thermodynamic Properties Multiple Phases

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Thermodynamics is the branch of physics that deals with heat and temperature , and their relation to energy , work , radiation , and properties of matter. The behavior of these quantities is governed by the four laws of thermodynamics which convey a quantitative description using measurable macroscopic physical quantities , but may be explained in terms of microscopic constituents by statistical mechanics. Thermodynamics applies to a wide variety of topics in science and engineering , especially physical chemistry , chemical engineering and mechanical engineering , but also in fields as complex as meteorology.

The initial application of thermodynamics to mechanical heat engines was extended early on to the study of chemical compounds and chemical reactions. Chemical thermodynamics studies the nature of the role of entropy in the process of chemical reactions and has provided the bulk of expansion and knowledge of the field.

Statistical thermodynamics , or statistical mechanics, concerns itself with statistical predictions of the collective motion of particles from their microscopic behavior. A description of any thermodynamic system employs the four laws of thermodynamics that form an axiomatic basis. The first law specifies that energy can be exchanged between physical systems as heat and work.


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In thermodynamics, interactions between large ensembles of objects are studied and categorized. Central to this are the concepts of the thermodynamic system and its surroundings. A system is composed of particles, whose average motions define its properties, and those properties are in turn related to one another through equations of state.

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Properties can be combined to express internal energy and thermodynamic potentials , which are useful for determining conditions for equilibrium and spontaneous processes. With these tools, thermodynamics can be used to describe how systems respond to changes in their environment.

This can be applied to a wide variety of topics in science and engineering , such as engines , phase transitions , chemical reactions , transport phenomena , and even black holes. The results of thermodynamics are essential for other fields of physics and for chemistry , chemical engineering , corrosion engineering , aerospace engineering , mechanical engineering , cell biology , biomedical engineering , materials science , and economics , to name a few.

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This article is focused mainly on classical thermodynamics which primarily studies systems in thermodynamic equilibrium. Non-equilibrium thermodynamics is often treated as an extension of the classical treatment, but statistical mechanics has brought many advances to that field. The history of thermodynamics as a scientific discipline generally begins with Otto von Guericke who, in , built and designed the world's first vacuum pump and demonstrated a vacuum using his Magdeburg hemispheres.

Guericke was driven to make a vacuum in order to disprove Aristotle 's long-held supposition that 'nature abhors a vacuum'. Shortly after Guericke, the English physicist and chemist Robert Boyle had learned of Guericke's designs and, in , in coordination with English scientist Robert Hooke , built an air pump.

In time, Boyle's Law was formulated, which states that pressure and volume are inversely proportional. Then, in , based on these concepts, an associate of Boyle's named Denis Papin built a steam digester , which was a closed vessel with a tightly fitting lid that confined steam until a high pressure was generated.

Later designs implemented a steam release valve that kept the machine from exploding.

By watching the valve rhythmically move up and down, Papin conceived of the idea of a piston and a cylinder engine. He did not, however, follow through with his design. Nevertheless, in , based on Papin's designs, engineer Thomas Savery built the first engine, followed by Thomas Newcomen in Although these early engines were crude and inefficient, they attracted the attention of the leading scientists of the time.

Experimental

The fundamental concepts of heat capacity and latent heat , which were necessary for the development of thermodynamics, were developed by Professor Joseph Black at the University of Glasgow, where James Watt was employed as an instrument maker. Black and Watt performed experiments together, but it was Watt who conceived the idea of the external condenser which resulted in a large increase in steam engine efficiency.

The book outlined the basic energetic relations between the Carnot engine , the Carnot cycle , and motive power. It marked the start of thermodynamics as a modern science. The first thermodynamic textbook was written in by William Rankine , originally trained as a physicist and a civil and mechanical engineering professor at the University of Glasgow. Willard Gibbs. During the years —76 the American mathematical physicist Josiah Willard Gibbs published a series of three papers, the most famous being On the Equilibrium of Heterogeneous Substances , [3] in which he showed how thermodynamic processes , including chemical reactions , could be graphically analyzed, by studying the energy , entropy , volume , temperature and pressure of the thermodynamic system in such a manner, one can determine if a process would occur spontaneously.

Lewis , Merle Randall , [5] and E. Guggenheim [6] [7] applied the mathematical methods of Gibbs to the analysis of chemical processes. The etymology of thermodynamics has an intricate history. Pierre Perrot claims that the term thermodynamics was coined by James Joule in to designate the science of relations between heat and power, [10] however, Joule never used that term, but used instead the term perfect thermo-dynamic engine in reference to Thomson's [23] phraseology.

The study of thermodynamical systems has developed into several related branches, each using a different fundamental model as a theoretical or experimental basis, or applying the principles to varying types of systems. Classical thermodynamics is the description of the states of thermodynamic systems at near-equilibrium, that uses macroscopic, measurable properties.

It is used to model exchanges of energy, work and heat based on the laws of thermodynamics.

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The qualifier classical reflects the fact that it represents the first level of understanding of the subject as it developed in the 19th century and describes the changes of a system in terms of macroscopic empirical large scale, and measurable parameters. A microscopic interpretation of these concepts was later provided by the development of statistical mechanics.

Statistical mechanics , also called statistical thermodynamics, emerged with the development of atomic and molecular theories in the late 19th century and early 20th century, and supplemented classical thermodynamics with an interpretation of the microscopic interactions between individual particles or quantum-mechanical states. This field relates the microscopic properties of individual atoms and molecules to the macroscopic, bulk properties of materials that can be observed on the human scale, thereby explaining classical thermodynamics as a natural result of statistics, classical mechanics, and quantum theory at the microscopic level.

Chemical thermodynamics is the study of the interrelation of energy with chemical reactions or with a physical change of state within the confines of the laws of thermodynamics. Equilibrium thermodynamics is the study of transfers of matter and energy in systems or bodies that, by agencies in their surroundings, can be driven from one state of thermodynamic equilibrium to another.

The term 'thermodynamic equilibrium' indicates a state of balance, in which all macroscopic flows are zero; in the case of the simplest systems or bodies, their intensive properties are homogeneous, and their pressures are perpendicular to their boundaries. In an equilibrium state there are no unbalanced potentials, or driving forces, between macroscopically distinct parts of the system. A central aim in equilibrium thermodynamics is: given a system in a well-defined initial equilibrium state, and given its surroundings, and given its constitutive walls, to calculate what will be the final equilibrium state of the system after a specified thermodynamic operation has changed its walls or surroundings.

Non-equilibrium thermodynamics is a branch of thermodynamics that deals with systems that are not in thermodynamic equilibrium. Most systems found in nature are not in thermodynamic equilibrium because they are not in stationary states, and are continuously and discontinuously subject to flux of matter and energy to and from other systems. The thermodynamic study of non-equilibrium systems requires more general concepts than are dealt with by equilibrium thermodynamics. Many natural systems still today remain beyond the scope of currently known macroscopic thermodynamic methods.

Thermodynamics is principally based on a set of four laws which are universally valid when applied to systems that fall within the constraints implied by each. In the various theoretical descriptions of thermodynamics these laws may be expressed in seemingly differing forms, but the most prominent formulations are the following. The zeroth law of thermodynamics states: If two systems are each in thermal equilibrium with a third, they are also in thermal equilibrium with each other.

This statement implies that thermal equilibrium is an equivalence relation on the set of thermodynamic systems under consideration.

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Systems are said to be in equilibrium if the small, random exchanges between them e. Brownian motion do not lead to a net change in energy. This law is tacitly assumed in every measurement of temperature. Thus, if one seeks to decide whether two bodies are at the same temperature , it is not necessary to bring them into contact and measure any changes of their observable properties in time.

The zeroth law was not initially recognized as a separate law of thermodynamics, as its basis in thermodynamical equilibrium was implied in the other laws. The first, second, and third laws had been explicitly stated already, and found common acceptance in the physics community before the importance of the zeroth law for the definition of temperature was realized. As it was impractical to renumber the other laws, it was named the zeroth law.

Measurement of the Thermodynamic Properties of Multiple Phases

The first law of thermodynamics states: The internal energy of an isolated system is constant. This law is an expression of the principle of conservation of energy.

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It states that energy can be transformed changed from one form to another , but cannot be created or destroyed. The first law is usually formulated by stating that the change in the internal energy of a closed thermodynamic system is equal to the difference between the heat supplied to the system and the amount of work done by the system on its surroundings.

Internal energy is a principal property of the thermodynamic state , and is also known as a state function , whereas heat and work modify this state.


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A change of internal energy of a system may be achieved by any combination of heat added or removed and work performed on or by the system.