Ch 21b - A Thermodynamics Primer/Review

We’ve spent most of Ch21b learning about the microscopic world, one that is defined by quantum mechanics. Such understanding has emerged only relatively recently within the history of chemistry, much of what we know about the transformation of chemical systems was gleaned from studies of macroscopic samples before the advent of the Schrödinger equation. Chief among these advancements was thermodynamics. The power of this discipline lies in its generality. The field developed from observations of the natural world, it stands on its own. No molecular details of the system under study enter into classical thermodynamic analyses. The desire to bridge the macroscopic and microscopic worlds lies at the heart of statistical thermodynamics, a subject we will consider for the remainder of the quarter. Here we’ll briefly review the fundamental “laws” of thermodynamics, in order to provide the necessary backdrop for the molecular/statistical analysis that is based on the collective behavior of extremely large numbers of microscopic quantum mechanical systems.
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if A is in thermal equilibrium with C and B is also in thermal equilibrium with C. A C B Page 2 23Feb2007 . and C. it states: For three systems A. Briefly. work. internal energy. B. then A and B are in thermal equilibrium with each other. and heat play an important role in the understanding of chemical phenomena.The “Zeroth” Law of Thermodynamics The quantitative concepts of temperature. The need to define an absolute temperature scale was not recognized until after the first and second laws of thermodynamics were established.Ch 21b .

volume and temperature (P. V. Extensive variables can be converted into intensive variables by dividing be a measure of the amount of substance (the molar volume. Those variables that depend on the size of the system are referred to as extensive (such as V.Ch 21b . State variables include things like pressure. T. these are called state functions. energy). those that do not are referred to as intensive (P. for example).Thermodynamic State Variables/Functions When a system is at equilibrium under a given set of conditions. T). for example). certain quantities do not depend upon the path take by the system. Some thermodynamic state functions we will be concerned with include: U = internal energy S = entropy H = enthalpy (classically. it is said to be in a definite state. As we’ll see next. U + PV) A = Helmholtz free enegy = U – TS G = Gibbs free energy = H – TS Page 3 23Feb2007 .

and the heat absorbed by the system is q. since it is path independent. Mathematically: dU = dq + dw where the differentials are meant to emphasize infinitesimal changes. The work done on the system during this change is w.The First Law of Thermodynamics This law is. while dq and dw are known as inexact differentials since their value depends upon the path taken by the system. Suppose a system is brought from state A to state B. A Page 4 B ∫ dU = 0 23Feb2007 . Cyclic processes bring the system back to its initial state. is referred to as an exact differential.Ch 21b . The first law states that while w and q depend on the path taken by the system. and is the internal energy. dU. This sum is a state function. their sum does not. and so for such processes the internal energy change is zero. essentially. a statement of the conservation of energy.

) is infinitesimal. the entropy of the system and its surroundings remains constant.The Second Law of Thermodynamics The second law is a bit more abstract. For a reversible process. and can be stated many ways. which is a state function. etc. Mathematically: dS = dqrev/T where the differentials are again meant to emphasize infinitesimal changes. the entropy of the system and its surroundings increases. T. Reversible processes are those in which the driving force (a difference in P. the first and second laws can be combined to yield the well known perfect gas equation: dU Page 5 = TdS – PdV (heat + work) 23Feb2007 . Reversible ΔS = SA – SB = ∫ dqrev/T Irreversible or S A – SB > ∫ dqirrev/T Given the formulation above.Ch 21b . One is: There is a quantity S. called entropy. Any other change is called irreversible or spontaneous. In an irreversible process.

for example. This enables us to calculate the absolute entropy of a substance via the expressions S – S0 = ∫ dqrev/T and S0(T=0) = 0 where the integral runs from 0 to T. a system develops internal constraints that prevent the achievement of internal equilibrium (glasses cannot turn into crystalline solids. which can be written in several forms. has an additive constant associated with its calculation. The restriction to states of internal equilibrium is important. at low T). an exact differential. deals with this constant.The Third Law of Thermodynamics (Nernst Heat Theorem) The second law relates the infinitesimal change in entropy. Frequently. The integral needed to calculate the change in entropy. during the approach to T = 0. however.Ch 21b . Page 6 23Feb2007 . The third law. One formulation is: In any system in internal equilibrium undergoing an isothermal process between two states. to that in the infinitesimal change in the heat exchanged (which is inexact since it depends on the path of the system) under isothermal conditions. the entropy change of the process approaches zero as the temperature of the system approaches zero.

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