- Flory-Huggins solution theory
Flory-Huggins solution theory is a
mathematical modelof the thermodynamicsof polymer solutions which takes account of the great dissimilarity in molecular sizes in adapting the usual expression for the entropy of mixing. The result is an equation for the Gibbs free energychange for mixing a polymer with a solvent. Although it makes simplifying assumptions, it generates useful results for interpreting experiments. The thermodynamic equation for the Gibbs free energychange accompanying mixing at constant temperatureand (external) pressureis
A change, denoted by , is the value of a
variablefor a solutionor mixtureminus the values for the pure components considered separately. The objective is to find explicit formulas for and , the enthalpyand entropyincrements associated with the mixing process.
The result obtained by FloryRef|1 and HugginsRef|2 is
The right-hand side is a function of the number of moles and volume fraction of
solvent( component), the number of moles and volume fraction of polymer (component ), with the introduction of a parameter chi to take account of the energyof interdispersing polymer and solvent molecules. is the gas constantand is the absolute temperature. The volume fraction is analogous to the mole fraction, but is weighted to take account of the relative sizes of the molecules. For a small solute, the mole fractions would appear instead, and this modification is the innovation due to Flory and Huggins.
We first calculate the "entropy" of mixing, the increase in the uncertainty about the locations of the molecules when they are interspersed. In the pure condensed phases —
solventand polymer — everywhere we look we find a molecule.Ref|3 Of course, any notion of "finding" a molecule in a given location is a thought experimentsince we can't actually examine spatial locations the size of molecules. The expression for the entropy of mixingof small molecules in terms of mole fractions is no longer reasonable when the solute is a macromolecular chain. We take account of this dis symmetryin molecular sizes by assuming that individual polymer segments and individual solvent molecules occupy sites on a . Each site is occupied by exactly one molecule of the solvent or by one monomerof the polymer chain, so the total number of sites is
is the number of solvent molecules and is the number of polymer molecules, each of which has segments.Ref|4
statistical mechanicswe can calculate the entropychange, the increase in spatial uncertainty, as a result of mixing solute and solvent.
where is Boltzmann's constant. Define the lattice "volume fractions" and
These are also the probabilities that a given lattice site, chosen at random, is occupied by a solvent molecule or a polymer segment, respectively. Thus
In addition to the entropic effect, we can expect an "enthalpy" change.Ref|5 There are three molecular interactions to consider: solvent-solvent , monomer-monomer (not the covalent bonding, but between different chain sections), and monomer-solvent . Each of the last occurs at the expense of the average of the other two, so the energy increment per monomer-solvent contact is
The total number of such contacts is
where is the coordination number, the number of nearest neighbors for a lattice site, each one occupied either by one chain segment or a solvent molecule. That is, is the total number of polymer segments (monomers) in the solution, so is the number of nearest-neighbor sites to "all" the polymer segments. Multiplying by the probability that any such site is occupied by a solvent molecule,Ref|6 we obtain the total number of polymer-solvent molecular interactions. An approximation following
mean field theoryis made by following this procedure, thereby reducing the complex problem of many interactions to a simpler problem of one interaction.
The enthalpy change is equal to the energy change per polymer monomer-solvent interaction multiplied by the number of such interactions
The polymer-solvent interaction parameter "chi" is defined as
It depends on the nature of both the solvent and the solute, and is the only "material-specific" parameter in the model. The enthalpy change becomes
Assembling terms, the total free energy change is
where we have converted the expression from molecules and to moles and by transferring
Avogadro's numberto the gas constant.
The value of the interaction parameter can be estimated from the
Hildebrand solubility parameters and
where is the actual volume of a polymer segment.
This treatment does not attempt to calculate the
conformational entropy of folding for polymer chains. (See the random coil discussion.) The conformations of even amorphous polymers will change when they go into solution, and most thermoplasticpolymers also have lamellar crystalline regions which do not persist in solution as the chains separate. These events are accompanied by additional entropy and energy changes.
More advanced models exist, such as the
* [http://www.informit.com/content/images/chap3_0130181684/elementLinks/chap3_0130181684.pdf "Conformations, Solutions and Molecular Weight" (book chapter)] , Chapter 3 of Book Title: Polymer Science and Technology; by Joel R. Fried; 2nd Edition, 2003
* [http://www.composite-agency.com/materials-forum.htm Flory-Huggins in practice: discussion on solubility in polymer based materials]
References and footnotes
Thermodynamicsof High Polymer Solutions," Paul J. Flory "Journal of Chemical Physics," August 1941, Volume 9, Issue 8, p. 660 [http://link.aip.org/getabs/servlet/GetabsServlet?prog=normal&id=JCPSA6000009000008000660000002&idtype=cvips&gifs=Yes Abstract] . Flory suggested that Huggins' name ought to be first since he had published several months earlier: Flory, P.J., "Thermodynamics of high polymer solutions," "J. Chem. Phys." 10:51-61 (1942) [http://www.garfield.library.upenn.edu/classics1985/A1985AFW3100001.pdf "Citation Classic" No. 18, May 6, 1985]
# "Solutions of Long Chain Compounds," Maurice L. Huggins "Journal of Chemical Physics," May 1941 Volume 9, Issue 5, p. 440 [http://link.aip.org/getabs/servlet/GetabsServlet?prog=normal&id=JCPSA6000009000005000440000001&idtype=cvips&gifs=yes Abstract]
# We are ignoring the "free volume" due to molecular disorder in liquids and amorphous solids as compared to
crystals. This, and the assumption that monomers and solute molecules are really the same size, are the main "geometric" approximations in this model.
# For a real synthetic polymer, there is a statistical distribution of chain lengths, so would be an
enthalpyis the internal energycorrected for any pressure- volumework at constant (external) . We are not making any distinction here. This allows the approximation of Helmholtz free energy, which is the natural form of free energy from the Flory-Huggins lattice theory, to Gibbs free energy.
# In fact, two of the sites adjacent to a polymer segment are occupied by other polymer segments since it is part of a chain; and one more, making three, for branching sites, but only one for terminals.
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