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The constant of vander Waal's equation can be related to the coefficients of the virial equation. Vander Waal's equation provides a good overall description of the real gas PVT behavi
The excluded volume b, introduced by vander Wall's as an empirical correction term, can be related to the size gas molecules. To do so, we assume the excluded volume is the result of the pairwise comi
The average translational kinetic energies and speeds of the molecules of a gas can be calculated.The result that the kinetic energy of 1 mol of the molecules of a gas is equal to 3/2 RT can be u
The free energy property leads to convenient expressions for the volume and pressure dependence of internal energy, enthalpy and the heat capacities.All the properties of a chemical system, a sample o
The fugacity is a pressure like quantity that is used to treat the free energy of nonideal gases.Now we begin the steps that allow us to relate free energy changes to the equilibrium constant of real,
The free energy of a gas depends on the pressure that confines the gas. The standard free energies of formation, like those allow predictions to be made of the possibility of a reaction at 25&de
The equilibrium constant can be treated as a particular type of molecular distribution. Consider the simplest gas-phase reaction, one in which molecules of A are converted to molecules of B. the react
The entropy due to the rotational motion of the molecules of a gas can be calculated. Linear molecules: as was pointed out, any rotating molecule has a set of allowed rotational energies. For a
The molecular, or statistical, basis of the third law can be seen by investigating S = k in W.The molecular deductions of the preceding sections have led to the same conclusions as that stated in the
The equation S = k in W relates entropy to W, a measure of the number of different molecular level arrangements of the system.In the preceding developments it was unnecessary to attempt
The thermal part of the internal energy and the enthalpy of an ideal gas can be given a molecular level explanation. All the earlier development of internal energy and enthalpy has been "thermodynam
The temperature reliance of internal energy and enthalpy depends on the heat capacities at constant volume and constant pressure. The internal energy and enthalpy of chemical systems and the energy
Energy changes in some chemical reactions can be used to deduce the energies of chemical bonds. Our understanding of the molecular basis of thermodynamic properties is extended when we ask why the e
Partition function; that the translational energy of 1 mol of molecules is 3/2 RT will come as no surprise. But the calculation of this result further illustrates the use of quantized states and the p
For motion in one dimension, the distribution of the molecules over quantum states, speeds, and energies can be deduced.Here we show that the energy of a macroscopic gas sample can be described on the
The Schrodinger wave equation generalizes the fitting-in-of-waves procedure.The waves that "fit" into the region to which the particle is contained can be recognized "by inspection" only for a few sim
Three dimensional applications of the Schrodinger equation are introduced by the particle-in-a-box problem.So far only a one-dimensional problem has been solved by application of the Schrodinger equat
Laser action relies on a non-Boltzmann population inversion formed by the absorption of radiation and vibrational deactivation that forms a long lived excited electronic state. An excited state mole
An extension of the kinetic molecular theory of gases recognizes that molecules have an appreciable size and deals with molecule-molecule collisions. We begin studies of elementary reactions by inve
The main objective of this particular aspect of Physical Chemistry is to examine the relation between free energies and the mechanical energy of electromotive force of electrochemical cells. The ionic
Ion Selective Electrodes An ion selective membrane can be used to form an electrochemical cell whose emf depends on the concentration of that ion. Before we proceed to an important application of em
The contribution of an electrolyte, or an ion electrolyte, is reported as the molar of a conductance. The definition of the molar conductance is based on the following conductivity cell in which the
Transference numbers and molar conductors can be used to calculate ionic mobilities. This tables under is giving the transference numbers for positive ions at 25 degree C and the values obtained by e
Passage of a current through a solution can produce an electrolysis reaction.Much additional information on the properties of the ions in an aqueous solution can be obtained from studies of the passag
Ionic dissociation depends on the dielectric constant of the solvent.The Arrhenius that ions are in aqueous solutions in equilibrium with parent molecular species allows many of the properties of ioni