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Equilibrium I love chemistry!!! What is Equilibrium? • A dynamic condition in which 2 opposing changes occur at equal rates in a closed system Ex. A phase change can be a physical condition that can be described to be in equilibrium Solid + ∆H Liquid Other examples of Equilibrium • Vapor pressure Patm Pgas • Saturated solutions NaCl(s) Na+(aq) + Cl-(aq) LeChatlier’s Principle • A system will remain at equilibrium until something occurs to change this condition • When a system at equilibrium is disturbed by an application of stress, it attains a new equilibrium position that minimizes that stress What are the possible stressors? • • • • • Change in temperature Change in pressure Change in volume Addition or removal of reactants Addition or removal of products Understanding how to minimize the stress • Equilibrium is like a teeter totter • When stress is placed on it, the system must adjust to rebalance itself Using color to predict shifting ∆H + Co(H2O)6+2(aq) + 4Cl-(aq) CoCl4-2(aq) + 6H2O(l) Pale pink Deep blue At equilibrium, the color of a beaker containing this system would be violet (light purple) What would you see if the following possible stressors were Introduced according to LeChatlier? •Addition of Co(H2O)6+2 •Removal of Cl-(aq) •Removal of H2O(l) •Addition of CoCl4-2(aq) •Addition of ∆H •Removal of ∆H •Increase Pressure •Decrease Pressure Sample Problem #1 2NO2(g) N2O4(g) + ∆H Very dark brown 1. 2. Very light brown 3. 1. 2. 3. *At equilibrium, the system will display a medium brown color as shown in flask #2 2NO2(g) Very dark brown N2O4(g) +∆H Very light brown Where would the shifting take place when the following possible stressors are added? What would you see experimentally? • Removal of heat • Increase in pressure • Addition of NO2(g) • Decrease in pressure • Removal of N2O4(g) • Addition of CO2(g) • Addition of heat • Increase in volume of container • Decrease in volume of container 1. 2. 3. 1. #1 represents a shift to the right (lighter brown color) #2 represents the original equilibrium situation #3 represents a shift to the left (darker brown color) 2. 3. Things to remember about equilibrium shifting • Pure solids and liquids will not have an effect on equilibrium • Only gases will be affected by a change in pressure or volume How do you know which side of the equilibrium expression is favored? • Sometimes at equilibrium, there is a higher concentration of reactants or products • To determine this by: • 1. Looking at the equilibrium constant • 2. Looking at the reversible arrows shown in the equation HBr(aq) + H2O(l) H3O+(aq) + Br-(aq) The forward reaction shown above is favored, therefore there is a higher concentration of products than of reactants at equilibrium H2CO3(aq) + H2O(l) H3O+(aq) + HCO3-(aq) The reverse reaction shown above is favored, therefore there is a higher concentration of reactants than of products at equilibrium • In some cases, both the forward and reverse reactions occur nearly at the same rate before chemical equilibrium is established. Neither reaction is favored • Do not just assume that if you see an equilibrium arrow ( ) that neither side of the system is favored. Use the equilibrium constant to determine for sure! The equilibrium expression (Keq) • After equilibrium has been achieved, the concentrations of products and reactants remain constant • The ratio of the concentrations should also remain constant ***The only stressor that can affect these concentration ratios is temperature ***Keq is temperature dependant How do you find Keq? • Keq is the constant that represents the ratio of the mathematical product to the mathematical reactant • The general equation for an equilibrium expression is as follows: nA + mB xC + yD *n, m, x, y = coefficients from balanced chemical equation *A, B, C, D = molarities of reactants and products nA + mB Keq = xC + yD [C]x [D]y [A]n [B]m *Keq will only change if temperature changes *Only gases and aqueous solution concentrations will be included in Keq *Pure solids and liquids are omitted because their concentrations cannot change Sample Problem • Consider the following equilibrium equation at 425°C: H2(g) + I2(g) 2HI(g) 1. Write the Keq expression for this reaction 2. Determine Keq mathematically when given the following concentrations: [H2] = .015M, [I2] = .015M, [HI] = .11M 3. Using the known Keq from #2 and given the following concentrations for H2 and I2, determine the concentration of HI: [H2] = .018M, [I2] = .018M How to use Keq to determine if the reactants, products or neither are favored? • If Keq > 1, the forward reaction (products) are favored • If Keq < 1, the reverse reaction (reactants) are favored • If K = 1, neither reaction is favored (the concentrations of both products and reactants should be equal) • For the previous sample problem, which of the reactions is favored? H2(g) + I2(g) 2HI(g)