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Additional Reading Statistical Mechanics - Chapter 4

Lauren Pollock Mathematics Inglés 19 fichas

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  1. 1First Order Phase TransitionThe Gibbs potential is continuous from one phase to another but in a first order phase transition, the first derivatives of the Gibbs potential are discontinuous. This discontinuity originates from the difference in density and specific entropy between the two phases.
  2. 2Second Order Phase TransitionThe first derivative of the Gibbs potential is continuous but the second derivative is discontinuous.
  3. 3Vapour PressureThe pressure at which gas and liquid coexist at thermal equilibrium during the transition region
  4. 4Latent HeatThe energy released or absorbed during a constant temperature process. The heat released during a phase transition is due to the differing entropies of coexisting phases. When a unit amount of phase 1 is converted into phase 2, an amount of latent heat is liberated: l = T_0(s_2-s_1)
  5. 5Critical PointThe point at which gas and liquid have equal density and specific entropy. Phase transition becomes 2nd order.
  6. 6Triple PointThe line along which the gas, liquid and solid can all coexist projects onto the triple point in the PT diagram. The temperature at which all 3 phases can coexist in equilibrium.
  7. 7Critical IsothermA constant temperature line on the PT diagram which has an inflection point at the critical point.
  8. 8Clayperon Equation(∂Δg/∂T)_P * (∂T/∂P)_Δg * (∂P/∂Δg)_T = -1
    In equilibrium Δg = 0
    dP/dt = l/(TΔV)
  9. 9Intermolecular Potential EnergyDependent on the magnitude of the intermolecular forces and the position the molecules have relative to each other at any instant of time.
    1. Repulsive core - due to the electrostatic repulsion between electron clouds
    2. Attractive tail - due to the mutual electrostatic polarisation
  10. 10Van der Waals Equation of State1. Hard core replusion leads to V_eff = V-b
    2. Reduction due to attraction of neighbouring molecules P =Pkinetic - a/V^2
    (V - b)(P + a/V^2) = RT
  11. 11Virial ExpansionExpresses the pressure of a many particle system in equilibrium as a power series in the number density.
    PV/RT = 1 + 1/V(b - a/RT)
  12. 12Van der Waals IsothermsAt T=T_c, the roots merge. At TT_c, one real root and one complex conjugate pair.
  13. 13Isothermal CompressibilityDescribes the behaviour of a solid or liquid when the external pressure is changed
    β_T = -1/V (∂V/∂P)_T
  14. 14MetastableThe stability of a dynamical system in a configuration other than the systems state of least energy (all state defining parameters reach and maintain stationary values).
    Positive compressibility = Metastable
    Negative compressibility = Unstable
  15. 15CavitationFormation of vapour cavities in a liquid (bubbles).
  16. 16Spinodal DecompositionMechanism for the rapid separation of 2 phases into two coexisting phases - it is local and spontaneous
  17. 17NucleationA physical process in which the change of state occurs around certain focal points known as nuclei
  18. 18Condition for phase coexistenceIn a 1st order transition, coexisting phases have the same P and T. Therefore the condition for equilibrium is therefore that the total Gibbs potential be minimum.
    G = g_1m_1 + g_2m+2
    Condition for phase coexistence:
    Δg = g_1 - g_2 = 0 - i.e. coexisting phases must have equal chemical potential.
  19. 19Maxwell ConstructionVdW isotherm is a monotomic function of V for T>T_c. Below T_c, kink displaying negative compressibility - due to assumption density is uniform. 1st order transition actually involves break up in a mix of phase derivatives.

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Mathematics Fichas sobre Additional Reading Statistical Mechanics - Chapter 4, creado por Lauren Pollock el 18/05/2017.
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Lauren Pollock
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