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SURFACE TENSION 2 SPS Lectures January 2006. Wayne Lawton Department of Mathematics National University of Singapore http://math.nus.edu.sg/~matwml matwml@nus.edu.sg.
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SURFACE TENSION 2SPS Lectures January 2006 Wayne Lawton Department of Mathematics National University of Singapore http://math.nus.edu.sg/~matwml matwml@nus.edu.sg
We explain molecular cause of surface tension using thermodynamic concepts that explain the role of both energy and entropy – cutting edge concepts in biochemistry and life sciences. ABSTRACT • The Journal of Chemical Physics -- September 1, 2000 -- Volume 113, Issue 9, pp. 3882-3893 • Spatial and energetic-entropic decomposition of surface tension in lipid bilayers from molecular dynamics simulations • Erik Lindahl and Olle Edholm • Theoretical Physics, Royal Institute of Technology, SE-100 44 Stockholm, Sweden
Thermodynamics ENTROPY 1st Law 2st Law Statistical Mechanics Boltzmann’s tombstone
Entropy of a System With Two Subsystems EQUIPARTITION EP Theorem Microstates have equal probability Corollary Two subsystems in thermal equilibrium with constant total energy will maximize therefore Hence 2nd Law EP Theorem (Boltzmann) Each translational or rotational component of the random thermal motion of a molecule has an average kinetic energy
We consider a constant volume system whose entropy S = S(E) that is in thermal equilibrium with an infinite reservoir that has temperature T A = HELMHOLTZ FREE ENERGY Theorem Energy will flow into / out of the system so as to minimize A(E) = E – TS(E) Proof At thermal equilibrium the total entropy is is maximized for every value of therefore Remark
ENDOTHERMIC REACTIONS We consider a system consisting of molecules that can be in states 1 or 2 having respective energies Theorem The fraction p of molecules in state 1 satisfies Proof For a system of N molecules the binomial theorem and Stirling approx and the result follows since
SURFACE TENSION THERMODYNAMICS 2nd Law&surf. ten. Enthalpy Guggenheim-Hill [1] incorporate into hence into Gibbs Free Energy Systems in therm. equil. minimize G
TUTORIAL PROBLEMS 1. Boltzmann’s formula uses the natural log and log W gives information in nats. How many bits of information = 1 nat ? 2. Derive A(p) endothermic in reactions 3. Study the role of entropy in the chemical equilibrium formula in http://en.wikipedia.org/wiki/Chemical_equilibrium
RESEARCH PROJECTS • Carry out experiments described in • http://www.iit.edu/~smile/ch8623.html 2. Carry out experiments described in [3]
REFERENCES [1] Chemistry of Interfaces, M. J. Jaycock and G. D. Parfitt, Ellis Horwood, Chichester, 1986. [2] Dynamics of Surface Phenomena, P. Joos, Ridderprint, Utrecht, 1999. [3] Science with Soap Films, D. Lovett, Institute of Physics Publishing, Bristol, 1994.