Equilibrium

Presented By : Wee Joo Lie 260110083014 Noziyani Abu Hassan 260110083013

CONDITIONS FOR EQUILIBRIUM

At constant temperature and pressure , possesses a negative value of dG (or of G),and that the condition for equilibrium is that dG = 0 (or G = 0). The system consists of a single pure substance at constant temperature and pressure, the substance existing (at this temperature and pressure) in two phases at equilibrium.

 Example : A solid and its melt at the melting point , or a liquid and its vapor at the boiling point.
Since the system is at equilibrium , we know that G = 0,where G is the free energy change per mole associated with the process.

Our general definition of incremental change in a process.

Solid liquid G = Gl Gs
Where Gl and Gs are the molar free energies of the substance in the liquid and solid phases, respectively. ~ But since G = 0,we conclude Gs = Gl at equilibrium. ~For a pure substance , whenever two phases are in equilibrium ,at fixed temperature and pressure, the molar free energy of the substance has the same value in each phase.

 Under these conditions(where the closed system is at equilibrium at fixed temperature and pressure), the chemical potential of each individual component has the same value in all phases.

PHYSICAL PROCESSES
Phase Transitions (Single Component) ~ This substance is capable of existing in 3 states of matter :solid , liquid,and gas(vapor). Which these states are controlled by the values of temperature and pressure is readily displayed on a pressure-temperature phase diagram.

 Line OC describes the melting transition;at any point on this line the solid and liquid phases are in equilibrium , and the value of T corresponding to any given value of P is the melting point at that pressure. line OB the liquid and its vapor are in equilibrium , so the value of T on this line is the boiling point corresponding to the selected P value. Line OA the solid and the vapor are in equilibrium is called sublimation.

 If Hvap should happen to be essentially constant (independent of temperature), we can integrate the Clausius-Clapeyron equation: log P2 =H vap T2 T1 P1 2.3R T1T2

Example
The vapor pressure of water is 17.535mmHg at 20.0C and 31.824mmHg at 30.0C. Calculate the heat of vaporization of water in this temperature interval. Log 31.842 = Hvap 10
17.535 (2.3)(1.987) 293.15 303.15

Hvap

= 10.530cal mol-1

= 10.53 kcal mol-1

Chemical equilibrium
aA +bB = mM + nN ~ where A and B represent the reactant chemical species ; M and N are the product chemical species; and a , b , m , n are stoichiometric coefficients in the balanced reaction.

 The change in free energy (G) is defined (on a per mole basis) as the difference between the final state and the initial state: G = G product - G reactant
G = G + RT ln K ( R = 8.314 Jmol-1) or G = G + 2.303 RT log K ( R = 1.987 calmol-1)

 We recall that the condition for equilibrium is that G = 0. Putting this condition gives the simple result
G = -RT In K The quantity K is called the equilibrium constant for the reaction. It is conventional to write the products in the numerator and the reactants in the denominator.

K = [M]m [N]n [A]a [B]b G is called the standard free-energy change for the reaction, and it is interpreted as the change in free energy, per mole, when the reactants in their standard states are transformed into the products in their standard states.

 Example 1 : For the acid dissociation of acetic acid in water at 25 C, the experimental value of K a is 1.7510-5 . Calculate G for this process G = -2.303 RT log K a = -(2.303)(1.987 cal mol-1 K-1 )(298.15 K) (-4.757) = + 6490 cal mol-1

Free Energy, Enthalpy, and Entropy Changes in Chemical Reactions. We now have at hand all the thermodynamic theory needed to calculate (from the appropriate experimental data) these standard thermodynamic quantities for a chemical reaction: G, H, and S . These are the steps:

1) From measurement of the equilibrium constant K at a given temperature, calculate G from

G = -RT In K 2) From measurements of K at several temperatures, calculate H 3) From G = H - T S , calculate S

Example 2: Dependence of equilibrium constant on temperature for the binding of methyl transcinnamate and 8-chlorotheophylline anion in water
T(C) 15.5 25 40 K(M-1) 11.6 8.7 5.9 T(K) 288.65 298.15 313.15 1/T 0.00346 0.00335 0.00319 Log K 1.064 0.940 0.771

These are data for the equilibrium constant (a stability constant) describing then on covalent association between methyltranscinnamate and 8-chlorotheophyllinate in aqueous solution.Find G, H, and S at 25 C.
G= -(2.303)(1.987 cal mol-1 K-1 )(298.15 K) (log 8.7) = 1282 cal mol-1

log K = - H + C 2.3 RT Slope, m = - H 2.3 R

Y =log K X= 1/T

 Figure 1 shows the plot, which is acceptably straight over the temperature range given in the table; this linearity is consistent with the constancy of H over this temperature range. The slope of the line is 1083K, giving for H.
H = -(2.3)(1.987 cal mol-1 K-1) (1083K) = - 4996 cal mol-1 = - 5.00 kcal mol-1

 S = G - H T = -1.28-(-5.00) kcal mol-1 - 298.15K = -0.0125 kcal mol-1 K-1