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Time-asymmetric behavior as embodied in the second law of thermodynamics is observed in {\it individual macroscopic} systems.
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For a historical discussion of Boltzmann and his ideas see articles by M. Klein, E. Broda, L. Flamn in The Boltzmann Equation, Theory and Application
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For a general history of the subject see S.G. Brush, The Kind of Motion We Call Heat
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For interesting biographies of Boltzmann, which also contain many quotes and references, see E. Broda, Ludwig Boltzmann, Man—Physicist—Philosopher
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S. Goldstein, Boltzmann’s approach to statistical mechanics, in: J. Bricmont, et al. (Eds). Chance in Physics: Foundations and Perspectives
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S. Goldstein and J. L. Lebowitz, On the Boltzmann Entropy of Nonequilibrium Systems, Physica D, 193
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S. Goldstein, J. L. Lebowitz, R. Tumulka and N. Zanghi, Canonical typicality, Physical Review Letters
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S. Goldstein, J. L. Lebowitz, R. Tumulka and N. Zanghi, On the Distribution of the Wave Function for Systems in Thermal Equilibrium, Journal of Statistical Physics
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