Based on Thermodynamics Physics project Based on Thermodynamics

Natural systems tend toward states of minimum energy Thermodynamics a system: Some portion of the universe that you wish to study the surroundings: The adjacent part of the universe outside the system Changes in a system are associated with the transfer of energy a system: Some portion of the universe that you wish to study a glass of water plagioclase the mantle Changes in a system are associated with the transfer of energy lift an object: stored chemical  potential drop an object: potential  kinetic pump up a bicycle tire: chemical  mechanical  heat (friction + compression) add an acid to a base: chemical  heat Natural systems tend toward states of minimum energy

Energy States Unstable: Stable: Metastable: falling or rolling at rest in lowest energy state Metastable: in low-energy perch Figure 5-1. Stability states. Winter (2001) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall.

History A brief history of thermodynamics begins with Otto von Guericke who in 1650 built and designed the world's first vacuum pump and created the world's first ever vacuum (known as the Magdeburg hemispheres). He was driven to make a vacuum in order to disprove Aristotle's long-held supposition that 'nature abhors a vacuum'. Shortly thereafter, Irish physicist and chemist Robert Boyle had learned of Guericke's designs and in 1656, in coordination with English scientist Robert Hooke, built an air pump.

Using this pump, Boyle and Hooke noticed the pressure-temperature-volume correlation. In time, Boyle's Law was formulated, which states that pressure and volume are inversely proportional. Then, in 1679, based on these concepts, an associate of Boyle's named Denis Papin built a bone 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 1697, based on Papin's designs, engineer Thomas Savery built the first engine.

The term thermodynamics was coined by James Joule in 1858 to designate the science of relations between heat and power.[1] By 1849, "thermo-dynamics", as a functional term, was used in William Thomson's paper An Account of Carnot's Theory of the Motive Power of Heat.[9] The first thermodynamic textbook was written in 1859 by William Rankine, originally trained as a physicist and a civil and mechanical engineering professor at the University of Glasgow

Classical thermodynamics Classical thermodynamics is the original early 1800s variation of thermodynamics concerned with thermodynamic states, and properties as energy, work, and heat, and with the laws of thermodynamics, all lacking an atomic interpretation. In precursory form, classical thermodynamics derives from chemist Robert Boyle’s 1662 postulate that the pressure P of a given quantity of gas varies inversely as its volume V at constant temperature; i.e. in equation form: PV = k, a constant. From here, a semblance of a thermo-science began to develop with the construction of the first successful atmospheric steam engines in England by Thomas Savery in 1697 and Thomas Newcomen in 1712. The first and second laws of thermodynamics emerged simultaneously in the 1850s, primarily out of the works of William Rankine, Rudolf Clausius, and William Thomson (Lord Kelvin).

Statistical thermodynamics With the development of atomic and molecular theories in the late 19th century, thermodynamics was given a molecular interpretation. This field is called statistical thermodynamics, which can be thought of as a bridge between macroscopic and microscopic properties of systems.[11] Essentially, statistical thermodynamics is an approach to thermodynamics situated upon statistical mechanics, which focuses on the derivation of macroscopic results from first principles.

It can be opposed to its historical predecessor phenomenological thermodynamics, which gives scientific descriptions of phenomena with avoidance of microscopic details. The statistical approach is to derive all macroscopic properties (temperature, volume, pressure, energy, entropy, etc.) from the properties of moving constituent particles and the interactions between them (including quantum phenomena). It was found to be very successful and thus is commonly used.

Chemical thermodynamics Chemical thermodynamics is the study of the interrelation of heat with chemical reactions or with a physical change of state within the confines of the laws of thermodynamics. During the years 1873-76 the American mathematical physicist Josiah Willard Gibbs published a series of three papers, the most famous being On the Equilibrium of Heterogeneous Substances,

in which he showed how thermodynamic processes could be graphically analyzed, by studying the energy, entropy, volume, temperature and pressure of the thermodynamic system, in such a manner to determine if a process would occur spontaneously. During the early 20th century, chemists such as Gilbert N. Lewis, Merle Randall, and E. A. Guggenheim began to apply the mathematical methods of Gibbs to the analysis of chemical processes

Thermodynamic systems An important concept in thermodynamics is the “system”. Everything in the universe except the system is known as surroundings. A system is the region of the universe under study. A system is separated from the remainder of the universe by a boundary which may be imaginary or not, but which by convention delimits a finite volume. The possible exchanges of work, heat, or matter between

between the system and the surroundings take place across this boundary. Boundaries are of four types: fixed, moveable, real, and imaginary. Basically, the “boundary” is simply an imaginary dotted line drawn around the volume of a something in

which there is going to be a change in the internal energy of that something. Anything that passes across the boundary that effects a change in the internal energy of that something needs to be accounted for in the energy balance equation. That “something” can be the volumetric region surrounding a single atom

resonating energy, such as Max Planck defined in 1900; it can be a body of steam or air in a steam engine, such as Sadi Carnot defined in 1824; it can be the body of a tropical cyclone, such as Kerry Emanuel theorized in 1986 in the field of atmospheric thermodynamics; it could also be just one nuclide (i.e. a system of quarks) as some are theorizing presently in quantum thermodynamics.

For an engine, a fixed boundary means the piston is locked at its position; as such, a constant volume process occurs. In that same engine, a moveable boundary allows the piston to move in and out. For closed systems, boundaries are real while for open system boundaries are often imaginary. There are five dominant classes of systems:

Isolated Systems – matter and energy may not cross the boundary. Adiabatic Systems – heat must not cross the boundary. Diathermic Systems - heat may cross boundary.

Closed Systems – matter may not cross the boundary. Open Systems – heat, work, and matter may cross the boundary (often called a control volume in this case).

As time passes in an isolated system, internal differences in the system tend to even out and pressures and temperatures tend to equalize, as do density differences. A system in which all equalizing processes have gone practically to completion, is considered to be in a state of thermodynamic equilibrium.

In thermodynamic equilibrium, a system's properties are, by definition, unchanging in time. Systems in equilibrium are much simpler and easier to understand than systems which are not in equilibrium. Often, when analysing a thermodynamic process,

it can be assumed that each intermediate state in the process is at equilibrium. This will also considerably simplify the situation. Thermodynamic processes which develop so slowly as to allow each intermediate step to be an equilibrium state are said to be reversible processes.

Thermodynamic states When a system is at equilibrium under a given set of conditions, it is said to be in a definite state. The state of the system can be described by a number of intensive variables and extensive variables.

The properties of the system can be described by an equation of state which specifies the relationship between these variables. State may be thought of as the instantaneous quantitative description of a system with a set number of variables held constant.

Thermodynamic processes A thermodynamic process may be defined as the energetic evolution of a thermodynamic system proceeding from an initial state to a final state. Typically, each thermodynamic process is distinguished from other processes, in energetic character, according to what parameters, as temperature, pressure, or volume, etc., are held fixed.

The seven most common thermodynamic processes are shown below: An isobaric process occurs at constant pressure. An isochoric process, or isometric/isovolumetric process, occurs at constant volume. An isothermal process occurs at a constant temperature.

An adiabatic process occurs without loss or gain of heat. An isentropic process (reversible adiabatic process) occurs at a constant entropy. An isenthalpic process occurs at a constant enthalpy. Also known as a throttling process or wire drawing. A steady state process occurs without a change in the internal energy of a system.

A review of basic thermodynamics: A refresher The ball represents mass exchange The arrow represents energy exchange

The First Law of Thermodynamics Heat and work are equivalent Energy is conserved in any transformation The change of energy of a system is independent of the path taken Energy can be neither created nor detroyed DE = q - w or dE = dq - dw dE = dq - P dV E = internal energy q = heat w = work P = pressure V = volume

Enthalpy dE = dq - P dV H = E + PV dH = dq H = enthalpy The change in the enthalpy of a system (DH) during a reversible change in state at constant pressure is equal to the heat absorbed by the system during that change in state. The enthalpy of formation of compounds and their ions and molecules in aqueous solution is the heat absorbed or given off by chemical reactions in which the compounds, ions, and molecules form from the elements in the standard state (25°C, 1 atm)

Heats of Reaction DH = S nH (products) - S nH (reactants) n = molar coefficient of each reactant/product When DH is positive, the reaction is endothermic (heat flows from the surroundings to the system); When DH is negative, the reaction is exothermic (heat flows from the system to the surroundings

Heats of Reaction DH = S nH (products) - S nH (reactants) For example, evaporation: H2O(l) H2O(g) DH = H(H2O(g)) - H(H2O(l)) DH = (-57.80) - (-68.32) = 10.52 kcal The reaction is endothermic (i.e., sweating is a mechanism for cooling the body)

Heat Capacity When heat is added to a solid, liquid, or gas, the temperature of the substance increases: dq = C dT dq = dH dH = C dT, at constant pressure (important in geochemistry) C = heat capacity T = temperature Heat capacities vary with temperature…

The Second Law of Thermodynamics It is impossible to construct a machine that is able to convey heat by a cyclical process from one reservoir at a lower temperature to another at a higher temperature unless outside work is done (i.e, air conditioning is never free) Heat cannot be entirely extracted from a body and turned into work (i.e., an engine can never run 100% efficiently) — a certain fraction of the enthalpy of a system is consumed by an increase in entropy Every system left to itself will, on average, change toward a condition of maximum randomness — entropy of a system increases spontaneously and energy must be spent to reverse this tendency

The entropy of the universe always increases or “You can’t shovel manure into the rear end of a horse and expect to get hay out of its mouth”

Entropy DS = S nS (products) - S nS (reactants) For example: H2O(l) H2O(g) DS = S(H2O(l)) - S(H2O(g)) DS = 45.10 - 16.71 = 28.39 cal/deg When DS is positive, entropy of the system increases with the change of state; When DS is negative, entropy decreases

The fundamental equation of thermodynamics The ratio of heat gained or lost to temperature will always be the same, regardless of path, for a reversible reaction dE = T dS - P dV When dE = 0, T dS = P dV dS = dq/T = P dV/T Look familiar? dP dT S V = D dS = dq/T — reversible process dS > dq/T — irreversible process