Statistical Thermodynamics Lecture 8 Theory of Chemical EquilibriaI

Statistical Thermodynamics Lecture 8: Theory of Chemical Equilibria(I)

Chemical Equilibria • A major goal in chemistry is to predict the equilibria of chemical reactions, including the relative amounts of the reactants and products from their atomic masses and structure properties. partition functions reactant chemical potential K equilibrium constant product • Two-state equilibria include: chemical isomerization; the folding of a protein from an unfolded to folded state • The equilibrium constant K is the ratio of numbers of particles in each of the two states at equilibrium. K = NB/NA • The quantity that predicts the chemical equilibria is the chemical potential

Equilibria Condition • Consider the Gibbs free energy of the system: • At constant T and P: • Every molecule is in either state A or B: • Condition for equilibria:

Partition Function for Chemical Reactions • Define a reduced partition function with the ground-state term factored out: • Partition function for chemical potential

• From condition for equilibria: • The above equation gives a way to compute K from the atomic properties of A and B through their partition functions. • Takes no account of the interactions of one molecule with another, it applies only to isolated particles such as those in the gas phase.

More Complex Equilibria K • a, b and c indicate the stoichiometries of species A, B and C. • At constant T and P: • The equilibrium is now subject to two stoichiometric constraints:

• Condition for equilibria: • To express the relative numbers of particles of each species present at equilibrium, a natural definition of the equilibrium constant K arises from rearranging the above equation. difference in ground-state energies:

Finding Ground-State Energies • To define the ground state energies further, we must resolve a matter of the vibrational ground state. • Vibrational energies: n is the quantum number, n = 0, 1, 2, 3 … is the vibrational frequency of the harmonic oscillator Define Ground-State energy as: (well-bottom state) dissociated state with energy Define dissociation energy as: zero-point state with energy (1/2) well-bottom state with energy 0 (dissociated state) (zero-point state)

ΔD: difference between dissociation energies of all products and all the reactants the

Example: Estimation of K K • The dissociation energies are 431. 8 k. J/mol for H 2; 439. 2 k. J/mol for D 2; and 435. 2 k. J/mol for HD So at T = 300 K:

Since at T = 300 K, (hv)/k. T >> 1 There, • Rotation part contributes most, specially, the change in rotational symmetry is the main contributor to this equilibrium. The reaction is driven by the gain in entropy due to the rotational asymmetry of the products.

Pressure-Based Equilibrium Constants • Because pressures are easier to measure than particle numbers for gases, it is often more convenient to use equilibrium constants Kp based on pressures rather than equilibrium constant K based on the particle numbers • Multiple both sides by

Chemical Potentials in terms of Partial Pressures • Here • It divides the chemical potential into a part that depends on pressure k. Tlnp, and a part that does not μ 0 • μ 0 is called the standard-state chemical potential, which is depend on temperature

Le Chatelier’s Principle • Any perturbation away from a stable equilibrium state must increase the free energy of the system. • The system will respond by moving back toward the state of equilibrium. K • Suppose a fluctuation changes the number of B molecules by an amount d. NB. • Define a reaction coordinate the system has proceeded to B. • The total number of particles is fixed: • To move toward equilibrium, d. G ≤ 0, so , the factional degree to which , so , must have opposite signs. • If , then the direct toward equilibrium is < 0, N B will decrease. • Le Chatelier’s principle refers to the tendency of system to return to equilibrium by moving in a direction opposite to that caused by an external pertuibation

Temperature Dependence of Equilibrium • Measure K(T) at different temperatures, learn the enthalpy and entropy of the reaction, which is useful for constructing or testing microscopic models. K • At constant T and P, the condition for equilibrium is • The pressure based equilibrium constant is • Recall , which depends on temperature

• Chemical potential can be divided into partial molar enthalpy and entropy components. • If , are independent of temperature:

van’t Hoff relation • The relation provides a useful way to plot data to obtain • van’t Hoff plots show ln. K versus 1/T, the slope is • Water is more dissociated at higher temperatures • For dissociation, Δh 0 >0, is the characteristic of bond-breaking processes • The enthalpy change is positive, so dissociation must be driven by entropy • The plot illustrates a common feature: they are often linear, so Δh 0 is independent of temperature

integration • Can be used to find how Kp depends on temperature if know Δh 0 or determine Δh 0 if Kp(T) is measured • Example: calculate enthalpy of dissociation of water: At T = 1500 K, ln. Kp = -13. 147 ; at T = 2257 K, ln. Kp = -6. 4 At T = 1500 K:

Gibbs-Helmholtz Equation • Generalize beyond chemical equilibria and the gas phase to any dependence of a free energy G(T) on temperature with v= T and u = G to express the temperature derivative of G/T as Gibbs-Helmholtz Equation

Statistical Thermodynamics Lecture 8: Theory of Chemical Equilibria(II)

Equilibrium between Liquid and Gas • Consider a system of liquid in equilibrium with its vapor at constant T and P • Free energy depends only on the chemical potentials and numbers of particles in the two phase • If total number of molecules is conversed: • The condition for equilibrium is d. G = 0 , so

Lattice Model • How to compute • Model liquid as a lattice of particles of a single type, liquid particles occupied the crystalline lattice, with every site occupied by one particle • The translational entropy of the lattice particles is zero, since pairs of particles trade positions, the rearrangement can’t be distinguished, S = 0 • Two particles of type A in terms of ‘bond’ energy: w. AA < 0 • This energy applies to every pair of particles that occupy neighboring lattice sites • Consider the liquid system has total of N particle, each particle has z nearest neighbors (coordinate number of lattice)

Lattice Model – Vapor Pressure • Recall: • Equilibrium condition: • This describes the vapor pressure P of the molecule A escape the liquid • The vapor pressure is a measure of the density of vapor-phase molecule • As the AA bonds are made stronger, w. AA becomes more negative, P decreases because molecule prefer to bond together in the liquid rather than to escape to the vapor phase • If w. AA is fixed, increasing the temperature increases the vapor pressure

Clapeyron Equation • In last example, we see at fixed T and P, the equilibrium between liquid and vapor • Two points (P 1, T 1) and (P 2, T 2) at which the liquid and vapor are in equilibrium • The chemical potential at point 2 involves a small perturbation from point 1 • Total differential equation

• Based on Maxwell relation • Rearrange is partial molar change of entropy is partial molar change of volume • At phase equilibrium: with is partial molar change of enthalpy Clapeyron equation

• The molar volume of the gas phase is much larger than the molar volume of the liquid, so Clausius-Clapeyron equation • Integrate the equation, when is independent of p and T:

• Vapor pressure of benzene versus 1/T • lnp is linearly proportional to 1/T, and therefore Δh is independence of T and p • Δh can be obtained from slope and used to predict a boiling point with (p 2, T 2) if another boiling point (p 1, T 1) is known

Example: Apply of Clausius-Clapeyron Equation • If water boils at T 1 = 373 K and P 1 = 1 atm. At a high altitude where P 2 = ½ atm, what is the boiling temperature T 2 ? Δh = 40. 66 k. J/mol • Water boils at lower temperature at higher altitudes

Mixture: Entropy • Suppose there are NA molecules of species A, and NB molecules of species B. Together, they completely fill a lattice of N lattice sites • The multiplicity of states is the number of spatial arrangements of the molecules: • Define the mole fraction: • To simplify further: let x = x. A, so 1 -x = x. B

Mixture: Energy • In the lattice model, the total energy is the sum of the noncovalent bonds (or contact) of all the pairs of nearest neighbors • There are three possible types noncovalent bonds in the mixture: AA, BB, AB • The total energy of the system: is the number of AA bonds, is the number of BB bonds, is the number of AB bonds, , , are the corresponding noncovalent interactions • Each lattice site has z sides, and every contact involves two sides. The total number of sides of type A can be expressed in terms of numbers of contacts:

• Solve the two equation to get and In this expression, the only unknown is , the number of AB contact, we need to use some approximation to estimate it

The Mean-Field Approximation • The mean-field approximation: for any given numbers NA and NB, the particles are mixed as randomly and uniformly as possible. • Consider a specific site next to an A molecule, based on the approximation, the probability that a B molecule occupy the neighboring site is equal to the probability that any site is occupied by B: • There are z nearest-neighbor sites for each A molecule, the average number of AB contacts made by that particle A molecule: • The total number of A molecules is NA, so

where we define a dimensionless quantity called the exchange parameter:

The Free Energy and Chemical Potential of Mixture • The free energy of a mixed solution of NA number of A molecules and NB number of B molecules: • The chemical potential for A is found by taking the derivative of F with respective to NA, holding NB constant: other terms • The chemical potential of one component in solution depends on mole fraction

Activity and Standard State • The more general case: is the activity coefficient is the standard state chemical potential • In terms of molar concentration c is the actual concentration with unit mol/L , co is the standard concentration. Usually, co is set to 1 mol/L. At low concentration of c,

Equilibrium in Solutions • The equilibrium condition : • is the standard free energy change of the reaction • is the concentration based equilibrium constant

Statistical Mechanical Consideration is the chemical potential of species i in a solution of N water molecules is the free energy of solution with one molecule i and N water is the free energy of solution with only N water is the partition function with one molecule I and N water is the partition function of solution with only N water We use the relation: