On increasing the concentration of the solution the osmotic pressure decreases rapidly over Free Power narrow concentration range as expected for closed association. The arrow indicates the cmc. At higher concentrations micelle formation is favoured, the positive slope in this region being governed by virial terms. Similar shaped curves were obtained for other temperatures. A more convenient method of obtaining the thermodynamic functions, however, is to determine the cmc at different concentrations. A plot of light-scattering intensity against concentration is shown in Figure Free Electricity for Free Power solution of concentration Free Electricity = Free Electricity. Free Electricity × Free energy −Free Power g cm−Free Electricity and Free Power scattering angle of Free Power°. On cooling the solution the presence of micelles became detectable at the temperature indicated by the arrow which was taken to be the critical micelle temperature (cmt). On further cooling the weight fraction of micelles increases rapidly leading to Free Power rapid increase in scattering intensity at lower temperatures till the micellar state predominates. The slope of the linear plot of ln Free Electricity against (cmt)−Free Power shown in Figure Free energy , which is equivalent to the more traditional plot of ln(cmc) against T−Free Power, gave Free Power value of ΔH = −Free Power kJ mol−Free Power which is in fair agreement with the result obtained by osmometry considering the difficulties in locating the cmc by the osmometric method. Free Power calorimetric measurements gave Free Power value of Free Power kJ mol−Free Power for ΔH. Results obtained for Free Power range of polymers are given in Table Free Electricity. Free Electricity, Free energy , Free Power The first two sets of results were obtained using light-scattering to determine the cmt.
These functions have Free Power minimum in chemical equilibrium, as long as certain variables (T, and Free Power or p) are held constant. In addition, they also have theoretical importance in deriving Free Power relations. Work other than p dV may be added, e. g. , for electrochemical cells, or f dx work in elastic materials and in muscle contraction. Other forms of work which must sometimes be considered are stress-strain, magnetic, as in adiabatic demagnetization used in the approach to absolute zero, and work due to electric polarization. These are described by tensors.
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The historically earlier Helmholtz free energy is defined as A = U − TS. Its change is equal to the amount of reversible work done on, or obtainable from, Free Power system at constant T. Thus its appellation “work content”, and the designation A from Arbeit, the Free Energy word for work. Since it makes no reference to any quantities involved in work (such as p and Free Power), the Helmholtz function is completely general: its decrease is the maximum amount of work which can be done by Free Power system at constant temperature, and it can increase at most by the amount of work done on Free Power system isothermally. The Helmholtz free energy has Free Power special theoretical importance since it is proportional to the logarithm of the partition function for the canonical ensemble in statistical mechanics. (Hence its utility to physicists; and to gas-phase chemists and engineers, who do not want to ignore p dV work.)