Solutions
Thermodynamics
Scope
2.1 Fundamental Property Relations
2.2 The Chemical Potential and Phase Equilibria
2.3 Partial Molar Properties
2.4 Fugacity and Fugacity Coefficient of Pure Species
2.5 Estimation of Fugacity and Fugacity Coefficient of Pure Gas, Pure
Liquid, and Pure Solid Systems
2.6 Fugacity and Fugacity Coefficients of Species in a Solution or Mixture
2.7 Estimation of Fugacity and Fugacity Coefficient of a Specie in a Gas
Mixture, Liquid Solution, or Mixed Solid Systems
Scope
2.8 Thermodynamics of Ideal Gas Mixture (partial molar properties,
changes in mixing, and ideal gas mixture properties)
2.9 Thermodynamics of Ideal Solution (partial molar properties,
changes in mixing, and ideal solution properties)
2.10 Thermodynamics of Real Solution and the Excess Properties
2.11 Activity Coefficient of Species in Liquid Solution
2.12 Models to Estimate Activity Coefficient (Margules, van Laar,
Wilson, NRTL, Group Contribution Methods like UNIQUAC and
UNIFAC)
2.1 Fundamental Property Relations
1st Law
For reversible process:
(2nd Law)
Fundamental Fundamental
Property Relation 1 Property Relation 2
Fundamental Property Relations
H = f (S,P)
Fundamental
Property Relation 3 Fundamental
Property Relation 3
Fundamental Property Relations
Fundamental Property Relations
Thermodynamic properties such as temperature, pressure, volume
and entropy are related with each other. Their mutual relations are
called property relations or Maxwell relations, and the equations
showing property relations are derived from the differential form
of thermodynamic potentials. Since thermodynamic potentials are
point functions, they are path-independent. In mathematical terminology,
these functions are exact functions. Therefore, thermodynamic potential
functions do not depend on the order of differentiation. Applying this
property yields four property relations expressed in terms of microscopic
changes for a closed system in thermal equilibrium.
2.2 The Chemical Potential and Phase Equilibria
Chemical Potential for a Single Component
Chemical potential: tendency of a substance to change
Chemical composition
Aggregation state
Location (e.g. diffusion)
P, T, phase, concentration
First Law:
For H:
Subst. for dU:
Def. of G:
Subst. for dH:
Chemical Potential, µ x 1500
Melting point
Temperature, T
Chemical Potential, µ x 1500
Boiling point
liquid
Temperature, T
Same phase: higher concentration higher µ
High µ Low µ
Gas Vacuum
Chemical Potential: 2 Phases
Closed System: dG = VdP – SdT
Open System:
gas N2
Liquid N1
1. Fixed T, P: dT = 0; dP = 0
2. Assume equilibrium: dG = 0
Note:
Mixing of nA moles of A and nB moles of B at constant T and P.
, ,
nA Vm,A nB Vm,B
mixing
Partial Molar Properties
The partial molar property of a given component in solution is defined as the
differential change in that property with respect to a differential change in the
amount of a given component under conditions of constant T and P, and constant
number of all components other than the one under consideration.
𝒊
𝒊 𝑻,𝑷,𝒏𝒋 𝒊
where M is any thermodynamic property.
The concept of partial molar quantity can be applied to any extensive state function
Partial Molar Volume
Benzene – Toluene: form an ideal solution.
Volume of 1 mole pure benzene is 88.9 mL and the volume of 1 mol pure
toluene is 106.4 mL. 195.3 mL solution
Ethanol – Water: form a non-ideal solution.
Volume of 1 mole pure ethanol is 58.0 mL and volume of 1 mole pure water is
58 mL. However, 1 mole water mixed with 1 mol ethanol does not result in 58.0
mL + 18.0 mL, or 76.0 mL but rather 74.3 mL.
When the mole fraction is 0.5, the partial molal volume of ethanol is 57.4 mL
and the partial molal volume of water is 16.9 mL.
