3.012 Fundamentals of Materials Science Fall 2005 Lecture 24: 12.07.05 Flory-Huggins Theory Today: LAST TIME .........................................................................................................................................................................................2 Lattice Models of Solutions .........................................................................................................................................................2 ENTROPY OF MIXING IN THE FLORY-HUGGINS MODEL ...................................................................................................................3 CONFIGURATIONS OF A SINGLE CHAIN.............................................................................................................................3 COUNTING CONFIGURATIONS FOR A COLLECTION OF CHAINS ................................................................................4 THE ENERGY OF MIXING IN THE FLORY-HUGGINS MODEL..............................................................................................................7 The Bragg-Williams approximation ...........................................................................................................................................9 PREDICTIONS FROM THE FLORY-HUGGINS MODEL .......................................................................................................................11 REFERENCES ...................................................................................................................................................................................14 Reading: Dill and Bromberg Ch. 31 ‘Polymer Solutions,’ pp. 593-605. Supplementary Reading: Announcements: Final quiz: Tuesday, Dec. 20 1:30pm-4:30pm DuPont Same format and length as first 2 quizzes; you will have 3 hrs but quiz should only take 2 hrs Equation sheet is allowed, as in prior quizzes Review sessions (tentatively): Thermo/Stat Mech review: Friday, Dec. 16, 5-7pm (normal recitation room) Structure review: Sunday, Dec. 18, time TBD (normal recitation room) Thermo coverage on Quiz 3: lectures 17-24 Lecture 25 – Flory-Huggins theory continued 1 of 14 12/7/05! 3.012 Fundamentals of Materials Science Fall 2005 Last time Lattice Models of Solutions • Lattice models are a form of COARSE GRAINING, where only the most important molecular details of a system are retained in a statistical mechanical model. This is a powerful approach to create stat mech models where meaningful predictions can be made for complex materials. We began a derivation of the free energy of mixing for a polymer solution based on Flory-Huggins theory: nnp = number polymer chains M = total lattice sites = ns + Nnp N = number of segments per chain s = number of solvent molecules Figure by MIT OCW. Lecture 25 – Flory-Huggins theory continued 2 of 14 12/7/053.012 Fundamentals of Materials Science Fall 2005 Entropy of mixing in the Flory-Huggins model CONFIGURATIONS OF A SINGLE CHAIN How do we calculate W, the number of uniques states in the polymer system? We start by looking at the number of ways to place a single polymer chain on the lattice, ν1: o What are the number of conformations for first bead? o With the first bead placed on the lattice, what is the number of possible locations for the second segment of the chain? o Moving on to placement of the third segment of the chain: Lecture 25 – Flory-Huggins theory continued 3 of 14 12/7/053.012 Fundamentals of Materials Science Fall 2005 o We repeat this process to place all N segments of the chain on the lattice, and arrive at ν1, the total number of configurations for a single chain: COUNTING CONFIGURATIONS FOR A COLLECTION OF CHAINS o We can follow the same procedure used for a single chain to obtain the number of configurations possible for an entire set of np chains. We start by placing the FIRST SEGMENT OF ALL np CHAINS. The number of configurations for the first segment of all np chains is νfirst: ! "first= M(M #1)(M # 2)(M # 3) $ $ $ (M # (np#1)) =M!(M # np)!o The number of configurations for the (N -1) remaining segments of all np chains is ν subsequent: ! "subsequent= z #1( )M # npM$ % & ' ( ) * + , - . / z #1( )M # np#1M$ % & ' ( ) * + , - . / 00 0 z #1( )M # 2npM$ % & ' ( ) * + , - . / 00 0 z #1( )M # N np#1( )# N #1( )M$ % & & ' ( ) ) * + , , - . / / ! "subsequent=z #1M$ % & ' ( ) np(N#1)M # np( )!(M # Nnp)!o Putting these two configuration counts together, we have the total number of configurations for the collection of np chains of N segments each: ! W ="first"subsequentnp! The factor of np! Corrects for the over-counting since the polymer chains are indistinguishable, and we can’t tell the difference between two configurations with the same polymer distributions but different chain identities: Lecture 25 – Flory-Huggins theory continued 4 of 14 12/7/05Pure PolymerFigure by MIT OCW.Figure by MIT OCW.Figure by MIT OCW.3.012 Fundamentals of Materials Science Fall 2005 o Applying Stirling’s approximation: ! ln x!" x ln x # x, …arriving at a final result: ! "#Smix= $kbnsln%s+ npln%p[ ]Lecture 25 – Flory-Huggins theory continued 6 of 14 12/7/053.012 Fundamentals of Materials Science Fall 2005 The energy of mixing in the Flory-Huggins model Molecules form bonds with one another, attract, and repel one another by electrostatic, polar, or Van der Waals interactions-changing the internal energy of the system. Figure by MIT OCW. Figure by MIT OCW. To account for these interactions in a lattice model, we need to first calculate the enthalpy of mixing. At constant pressure, the enthalpy of mixing will be related to the internal energy of mixing in the following way: We will assume in the lattice model that the change of volume on mixing is zero-thus the second term = ΔUmix drops out and ΔHmix . We can directly formulate an expression for the energy of mixing in the model: The internal energy of the solution is obtained by considering the contacts between molecules on the lattice: ! mij=# i - j contacts"ij= energy per i - j contact! Usolution= # contacts( )"energycontact# $ % & ' ( The total number of contacts made by polymer segments or solvent molecules on the lattice can be related to the coordination number and the contact numbers mij: Lecture 25 – Flory-Huggins theory continued 7 of 14 12/7/053.012 Fundamentals of Materials Science Fall 2005 total solvent contacts:
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