Minimization of Gibbs
Energy
Key points:
• Standard state conditions vary based on substance (gas, solid, liquid).
• Gibbs energy per kilogram of mixture g is given by the summation of
the chemical potentials of species.
• Chemical equilibrium is achieved by minimizing free energy subject
to mass-balance constraints.
Chemical Potential and Equilibrium
• Chemical potential (μj) describes the energy change when one mole of a
substance is added to a system.
• Standard state defines reference conditions for chemical potential
calculations.
T=T0, P=P0, h=h0, s=s0
• Recommended standard-state pressure ensures consistency in
thermodynamic data.
Total Gibbs Energy of Mixture
λiis the Lagrange multiplier associated with the ith constraint (mass-balance constraint),the
Lagrangian multipliers (ξ) are a mathematical tool used to include constraints
in an optimization problem. By introducing Lagrange multipliers, the task of
minimizing Gibbs energy under constraints can be transformed into an
unconstrained optimization problem. This simplifies the process of finding the
equilibrium composition using methods like the Newton-Raphson algorithm.
Minimization of Gibbs Energy
Iteration
To solve these equations iteratively using the Newton-Raphson method, CAE NASA would follow these steps:
1.Start with initial guesses for nj and λi.
2.Compute the derivatives of G concerning njand using the given chemical potential expressions.
3.Use the constraint equation to update λ.
4.Update njusing the updated λ and the derivatives of G.
5.Calculate the Jacobian matrix, which represents the partial derivatives of the equilibrium equations
concerning the variables (n and λ).
6.Use the Newton-Raphson update equation to refine the guesses for n, and λ in each iteration:
•Linearize the system of equations around an initial guess for the mole fractions and Lagrange multipliers.
•Solve the linearized system for corrections to the guess values.
where Δx is the correction vector, J is the Jacobian matrix, and F(x) is the vector of function values (i.e., the
equilibrium equations).
7.Update the variables (nj and λ) using the correction vector (Δx).
8.Repeat steps 2-7 until convergence is achieved, i.e., until the variables n and λ no longer change significantly
between iterations.
Suppose we have a system with two chemical species: A and B.
Correction Vector (Δx):
•The correction vector represents the adjustments to the initial guesses for the variables (nA, nB, and λ) in each iteration to
improve the solution.
Jacobian Matrix (J):
•The Jacobian matrix contains the partial derivatives of the equilibrium equations with respect to the variables (nA, nB, and λ).
Newton-Raphson Update Equation:
•The Newton-Raphson update equation is given by: Δx=−J−1F(x)
•Here, J−1 represents the inverse of the Jacobian matrix.
•The correction vector (Δx) obtained from this equation is used to
update the guesses for the variables (nA, nB, and λ) in the next
iteration.
Iteration:
•The correction vector (Δx) is added to the current guesses for the variables to obtain updated values.
•This process is repeated iteratively until convergence is achieved, i.e., until the variables nA, nB, and λ no longer change
significantly between iterations.
In the context of chemical equilibrium problems, such as those involving the
minimization of Gibbs energy with Lagrange multipliers, the Newton-Raphson
method is employed to iteratively refine initial guesses for the variables until a
satisfactory solution is obtained. These variables typically represent the
composition of chemical species and Lagrange multipliers associated with
mass-balance constraints.
The Newton-Raphson method is preferred in such problems because it
converges quickly to the solution when the initial guesses are sufficiently close
to the true solution. It is also efficient and can handle complex nonlinear
systems of equations commonly encountered in chemical engineering and
thermodynamics.
Therefore, the main purpose of applying the Newton-Raphson method in
chemical equilibrium problems is to efficiently and accurately find the
composition of chemical species and other variables that satisfy the given
equilibrium conditions, leading to a minimum in the total Gibbs energy.
