Tuesday, June 21, 2016

diffusion - Do particle velocities in liquid follow the Maxwell-Boltzmann velocity distribution?


The Maxwell-Boltzmann velocity distribution arises from non-reactive elastic collisions of particles and is usually discussed in the context of the kinetic theory (for gases). There are various offhand remarks, for example here (slide 5), that state without reference that particles observe a similar velocity distribution in liquid. Is that true? References?



The main reason I'm curious is that it seems as though the mean free path would be extremely short in liquid vs. gas. I'm actually most curious about the nature of the collisions in liquid vs. gas, i.e., are collisions in liquid still (on average) elastic?


EDIT: The linked post on particle velocity in liquids is definitely interesting and weighs in on this question, and I appreciate the distinction made between local position fluctuation vs. long range movement. Still, let me frame this question in a few different ways.




  1. Gillespie proposed a stochastic framework for simulating chemical reactions which is formulated on the idea that non-reactive elastic collisions serve to 'uniformize' particle position so that the assumption of well-mixedness is always satisfied (see page 409 in the linked version). This is formulated from kinetic theory. A corollary to this is that a non-reactive collision between two molecules that are able to react does not induce local correlation, i.e., two particles able to react with each other that just collided, but didn't react are no more likely to react with each other in the next dt than any other particle pair in the volume. Gillespie's algorithm is commonly used in biology where biochemical species are modeled in the aqueous environment of cells. Is this valid, and if so why?




  2. On a microscopic scale, suppose we are interested in two 'A' particles diffusing in one dimension in an aqueous environment. The two A particles collide but don't react. What is their behavior immediately after the collision? Is it a 'reflection' which conserves velocity and might correspond to a Neumann BC? In a gas that approach seems natural, but in liquid the short mean-free path makes me think that diffusive forces would rapidly dissipate any momentum from the A-A collision, which might imply the A particles collide and 'stop'. How should I be thinking about this?





Just to bring it back to the original question, I think both (1) and (2) depend on the statistical velocity behavior of particles in liquid.



Answer



I think Maxwell-Boltzmann distribution should be valid for molecules in liquid too, at least according to classical statistical physics, because the factor $e ^{−\beta p^2/2m}$ in the Gibbs-Boltzmann probability density does not depend on potential energy and is the same whether the molecule is in gas, or a liquid. I do not know if there is a measurement supporting this theoretical result.



are collisions in liquid still (on average) elastic?



Elastic collision means that appreciable change in the kinetic and potential energy of two bodies happens to them only during short time interval and the energy long after that is the same as the energy long before that - the interaction of the two molecules is thought of as a scattering process. In liquids the interaction of the molecules may not be idealizable in this way, as the molecules are believed to be in incessant complicated motion constantly influencing each other (Brownian motion...) This does not seem to be a reason to abandon the Boltzmann statistics, however.


No comments:

Post a Comment

classical mechanics - Moment of a force about a given axis (Torque) - Scalar or vectorial?

I am studying Statics and saw that: The moment of a force about a given axis (or Torque) is defined by the equation: $M_X = (\vec r \times \...