N-butylammonium vermiculite system

It is clear from this chapter that the coulombic attraction theory potential is much better adapted to explain the experimental phenomena described in Chapter 1 than the DLVO theory potential (Equation 1.2). Of course, if you predict an interaction potential, you predict force-distance curves along the swelling axis. There have been a lot of arguments about how direct measurements of forces between spherical colloidal particles refute the coulombic attraction theory. Let us get the facts first. We now examine the experimental curves for the n-butylammonium vermiculite system. 

Until we discovered the constancy of the surface potential from the uniaxial stress results, like most other people, I had been more interested in constant surface charge models. If you do not know how the valency of a macroion varies with the external conditions, it is reasonable to assume it to be constant unless given evidence to the contrary. Given the evidence that y/0 70 mV is roughly constant for the n-butylammonium vermiculite system, what other consequences follow from this In particular, what happens if we apply the coulombic attraction theory with the constant surface potential boundary condition ... 

We may have made some rough approximations, but we now have the leading features of the behavior that we sought, in terms of elementary analytic functions. The predictions for 5 can, of course, be tested. If 0S is constant with respect to electrolyte concentration, we predict that s will also be constant with respect to c, which appears to be a novel result. For 0S = const = 70 mV, as in the n-butylammonium vermiculite system, we predict. t = 2.8. This second prediction is markedly different from the value s = 4.0 predicted from the Donnan equilibrium. In the next chapter we will describe our experimental tests of these two predictions. 

The n-butylammonium vermiculite system is an example of a three-component system of a monodisperse colloid, electrolyte and solvent. There are four constituents in the macroionic solution — the negatively charged clay plates, n-butylammonium ions (counterions), chloride ions (co-ions), and water — but these may not vary independently because they are subject to the restriction that... 

Before setting out on the exact mean field theory solution to the one-dimensional colloid problem, I wish to emphasize that the existence of the reversible phase transition in the n-butylammonium vermiculite system provides decisive evidence in favor of our model. The calculations presented in this chapter are deeply rooted in their agreement with the experimental facts on the best-studied system of plate macroions, the n-butylammonium vermiculite system [3], We now proceed to construct the exact mean field theory solution to the problem in terms of adiabatic pah-potentials of both the Helmholtz and Gibbs free energies. It is the one-dimensional nature of the problem that renders the exact solution possible. 

We do have to be careful in the way we apply the definition of a phase to the n-butylammonium vermiculite system. According to Gibbs [13], a phase is any homogeneous and physically distinct part of a system that is separated from other parts of the system by definite boundary surfaces. Because the gel can be lifted out of the supernatant fluid on a spatula, it clearly justifies description as a phase in the latter sense, but it is inhomogeneous on the nanometer-to-micron (colloidal) length scale. It can only be defined as homogeneous on the macroscopic length scale. The same considerations apply to the tactoid phase. 

One of the major advantages of using the n-butylammonium vermiculite system for polymer adsorption experiments is that we can use the salt concentration to... 

A definite prediction of DLVO theory is that charge-stabilized colloids can only be kinetically, as opposed to thermodynamically, stable. The theory does not mean anything at all if we cannot identify the crystalline clay state (d 20 A) with the primary minimum and the clay gel state (d 100 to 1000 A) with the secondary minimum in a well-defined model experimental system. We were therefore amazed to discover a reversible phase transition of clear thermodynamic character in the n-butylammonium vermiculite system, both with respect to temperature T and pressure P. These results rock the foundations of colloid science to their roots and... 

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