Le Chatelier's Principle - Chemical equilibrium (Historical) Law of Mass Action In 1864, Cato Maximilian Guldberg and Peter Waage

postulated the expression for the equilibrium constant. aA + bB --> cC + dD K = ([C]c[D]d)/([A]a[B]b The system will try to obey the above equation at all times. This was illustrated in the last lecture in the case of HI being formed from hydrogen and iodine and vice-versa.

Important considerations: (1) The equilibrium constant is normally dimensionless eventhough its evaluation may produce units. (2) The notation Kc is normally used to denote that the equilibrium constant refers to the expression in which the amounts of materials are expressed in molar concentrations. (3) For a particular reaction, the value of the equilibrium constant varies with temperature. Remember, K = kf / kr = (Af/Ar) exp (-(Eaf - Ear)/RT) (4) The notation Kp is used when the amounts of the materials are expressed as gas pressures. (5) For the value of an equilibrium constant to be meaningful, we must specify how the equilibrium reaction is written, i.e., which species are written on the product side and which are written on the reactant side. The equilibrium expression for a reaction written in one direction is the reciprocal of the one for the reaction written in the reverse direction.

Quantitative considerations: When K >> 1, formation of products is favored When K << 1, reactants are favored Relating Kcand Kp: The ideal gas law: PV = nRT rearranges into: P = (n/V)RT

for gases (n/V) will be the molar concentration, [C]: Thus, P = [C]RT and Kp = Kc(RT)(ngas in products-ngas in reactants)

Question: What can affect chemical equilibirium? Le Chatelier's Principle: NaCl(s) <==> Na+(aq) + Cl-(aq) In the laboratory, a saturated aqueous solution of NaCl was prepared. A saturated aqueous solution means that the maximum amount of NaCl which can be dissolved in a given amount of water is present. Additional crystals of NaCl when added to a saturated solution will not dissolve. The constant of equilibrium expression for the dissolution of NaCl in water is given by: Kc = [Na+][Cl-]/[NaCl(s)] The above equation contains the concentration of NaCl in solid NaCl. This concentration is related to the density of solid NaCl and its molar mass. Since the density of NaCl or of any pure solid or pure liquid does not vary with the extent of a reaction, the concentration of any pure solid or liquid can be regarded as a constant and, thus, can be further absorbed into the equilibrium constant: Kc' = [Na+][Cl-] where Kc' = Kc[NaCl(s)]. For dissolution processes, this constant is given a special name: Constant of Solubility Product, and the symbol Ksp. Ksp of NaCl = [Na+][Cl-] The constant of solubility product is, in fact, another statement of solubility. The higher the Ksp value is the higher the solubility. Ksp gives the highest concentration for dissolved species before crystallization or precipitation will occur. If the product [Na+][Cl-] is greater than Ksp of NaCl, NaCl crystals will be formed. Thus, in a saturated solution Ksp = [Na+][Cl-]. The dynamic equilibrium can be easily disturbed by changing any one of these concentrations: either [Na+] or [Cl-].

How does the system respond to a disturbance, the answer is given by Le Chatelier's Principle: If a system at equilibrium is disturbed by a change in temperature, pressure, or the concentration of one of the components, the system will shift its equilibrium position so as to counteract the effect of the disturbance. -Le Chatelier's Principle (1888) "It is known that in the blast furnace the reduction of iron oxide is produced by carbon monoxide, according to the reaction: Fe2O3(s) + 3CO(g) <==> 2Fe(s) + 3CO2(g) but the gas leaving the chimney contains a considerable proportion of carbon monoxide,?. Because this incomplete reaction was thought to be due to an insufficiently prolonged contact between carbon monoxide and the iron ore (confusing a problem with equilibrium with that of kinetics), the dimensions of the furnaces have been increased. In England they have been made as high as thirty meters. But the proportion of carbon monoxide escaping has not diminished, thus demonstrating, by an experiment costing several hundred thousand francs, that the reduction of iron oxide by carbon monoxide is a limited reaction. Acquaintance with the laws of equilibrium would have permitted the same conclusion to be reached more rapidly and far more economically."

Observations from the laboratory: (1) Addition of 1 mL concentrated HCl (12M) to 4 mL of a saturated solution of NaCl causes NaCl to crystallize. Concentrated HCl contains water and its addition increases the volume of the solution. However, one should keep in mind that it is 12M in Cl-. From the experiment you performed before Le Chatelier's experiment, you were told that a saturated solution of NaCl is only 5.4 M which means that, at the most 5.4M of [Na+] and 5.4M of [Cl-] can exist in solution. Addition of HCl results in a dramatic increase in [Cl-] and disturbs the equilibrium. Upon addition of concentrated HCl, the reaction quotient [Na +][Cl-] becomes greater than Ksp of NaCl. Crystallization of NaCl thus occur to relieve this stress. (2) Addition of ethanol (a compound very much capable of hydrogen-bonding with water) reduces the amount of available water molecules needed for separating the Na+ and Cl- ions. Thus, one can look at this situation as an increase in the effective

concentration of the dissolved ions (due to less solvent available) and, likewise, causes precipitation of NaCl. (3) Adding solid NaNO3 to a saturated solution of NaCl also causes crystallization of NaCl. Increasing [Na+] definitely disturbs the equilibrium and the system readjusts by crystallizing NaCl out until the product [Na+][Cl-] becomes equal again to Ksp. (4) Adding concentrated NaNO3(aq) does not cause crystallization of NaCl. Once again, from the experiment you performed before this one, you were told that the concentration of a saturated NaNO3 solution is about 7.6 M. The saturated NaCl is about 5.4M. Mixing equal volumes of these two solutions does not increase the product [Na+][Cl-]. Since the NaNO3 solution is rich in Na+, [Na+] in the original NaCl solution does go up (to about 6.5M). However, to precipitate NaCl, it is not just [Na+] that determines whether NaCl will precipitate or not, the [Cl-] concentration also requires our attention. Since the concentrated solution of NaNO3 is devoid of Cl- ions, its addition actually reduces [Cl] since, remember, we are also adding water in the process. The [Cl-] is essentially reduced to half of its original value, it is now 2.7 M. Clearly, the product [Na+][Cl-](6.5 x 2.7) is less than the original value for the saturated solution (5.4 x 5.4). Contrast this to the result when one adds concentrated HCl, the previous experiment. Adding 1 mL of 12M HCl effectively increases [Cl-] to 6.7 while reducing [Na+] to about 4.7 (Concentrated HCl is about 40% HCl, so adding 1 mL is essentially adding only 0.6 mL of water). The product 6.7 x 4.7 is greater than 5.4 x 5.4, thus, resulting in crystallization.

Change in reactant or product concentration If a chemical system is at equilibrium and we add a substance (either a reactant or a product), the reaction will shift so as to reestablish equilibrium by consuming part of the added substance. Conversely, removal of a substance will result in the reaction moving in the direction that forms more of the substance. Remember that this is a change in concentration so changing the amount of a pure solid or liquid which is already in equilibrium should not make the reaction consume the additional solid or liquid. Example, if solid NaCl is already in equilibrium with a saturated solution of

NaCl, adding more pure NaCl solid will not cause additional dissolving. Conversely, removal of some of the solid NaCl which is in equilibrium with a saturated solution of NaCl will not cause further crystallization of NaCl from the saturated solution. Effects of volume and pressure changes These effects are present when the two opposing reactions are of different molecularity. In solution, volume changes can be achieved by addition of solvent. Changing the volume effectively changes concentration. Adding more solvent is essentially a dilution. If the number of solute species on the reactant side is not the same as on the product side, then volume changes can cause a shift in equilibrium. Increasing the volume favors the process with lower molecularity. Increasing the volume then will cause the system to shift in the direction that increases the number of solute species. This is the same for reactions involving gases. Decreasing the volume of the container causes an equilibrium mixture of gases to shift in the direction that reduces the number of moles of gas. For gases, increasing the pressure by adding one of the gases participating in the reaction, will also disturb equilibrium (This is essentially a change in reactant or product concentration). Increasing the total pressure of a reaction vessel by adding a spectator gas does not affect equilibrium. Remember that volume changes can only have effect if the number of solute species or gas species in the reactant side is not equal to the if the number of solute species or gas species in the product side.

Effect of Temperature One can treat heat as a reactant (for an endothermic process) or a product (for an exothermic process and the same principle used for changes in concentration of reactants or products can be used to deduce the effect of heat on an equilibrium reaction