Chatper 6 The Chemical Equilibrium

Chemical Equilibrium

Chemical Equilibrium
Chapter objectives Students should be able to: Differentiate between Reversible and Irreversible reactions Explain the concept of Equilibrium constant and factors that determine its magnitude Understand Le Chateliers Principle and how it is used to predict the position of equilibrium Identify other forms of Equilibrium and calculations associated with them e.g. Solubility product, stability constants Understand concepts of Strong and weak electrolytes Explain Strong and weak acids and salts , hydrolysis of salts

6-1 The Chemical Equilibrium

Most chemical systems are governed by equilibria such that if: aA + bB = cC + dD, then

where K is the equilibrium constant, The ratio of the molar concentrations of reactants and products is a constant at certain temperature. The square bracketed terms mean: Molar concentration if the species is a dissolved solute Partial pressure in atm if species is a gas Unity if species is a pure liquid, pure solid, or pure solvent (solvent in an extremely dilute solution). This is also called the Law of mass action

6-1 The Chemical Equilibrium

Equilibrium
is not reached instantaneously can be approached from either direction is a dynamic state amounts of reactants/products can be changed by mass action (adding/ deleting products/reactants) HCO3- + H+ CO2(g) + HOH Ke = [CO2][HOH]/[HCO3-][H+]

6-1 Manipulating Equilibrium Constants

6-2 EQUILIBRIUM AND THERMONDYNAMICS Equilibrium controlled by thermodynamics and chemical reaction Enthalpy, H: Heat of reaction If H is positive, heat is absorbed (acts as a . reactant), reaction is endothermic If H is negative, heat is released (acts as a product), reaction is exothermic Entropy, S: Disorder of reaction If S is positive, products are more disordered than reactants If S is negative, reactants are more disordered than products The combination of entropy and enthalpy in a given reaction determine whether the reaction is spontaneous, or thermodynamically favorable

6-2 EQUILIBRIUM AND THERMONDYNAMICS

This combination is the Gibbs free energy change in the system. . G = H -TS If G is negative, the reaction is spontaneous . If G is positive , the reaction is not spontaneous

How do these situations occur? Heres the key relation between free energy and equilibrium constant: Go /RTK = e , or, G = -RT
ln(K) If K is large (>1), ln(K) is positive, and G is negative the reaction lies towards products.

If K<1 (small), ln(K) is negative, G is now positive, and the reaction lies to the left.

6-2 EQUILIBRIUM AND THERMONDYNAMICS

Le Chateliers Principle

Suppose that a system at equilibrium is subjected to a change that disturbs the system. Le Chtelier's principle states that the direction in which the system proceeds back to equilibrium is such that the change is partially offset.

6-2 EQUILIBRIUM AND THERMONDYNAMICS Le Chateliers Principle

6-2 EQUILIBRIUM AND THERMONDYNAMICS Le Chateliers Principle

Equilibrium state of this system, with concentrations : [H+] = 5.0 M, [Cr2O72- ] = 0.10 M, [Cr3+] = 0.003 0 M, [Br] = 1.0 M, and [BrO3- ] = 0.043 M. Equilibrium is disturbed by adding dichromate to the solution to increase the concentration of [Cr2O72- ] from 0.10 to 0.20 M. Direction of reaction to reach equilibrium Verified by reaction quotient, Q,

Q is evaluated with existing concentrations equilibrium. When the system reaches equilibrium, Q = K.

6-2 EQUILIBRIUM AND THERMONDYNAMICS Le Chateliers Principle

Calculate a reaction quotient Q, (the equilibrium constant expression with nonequilibrium concentrations plugged in). If Q>K, the reaction must proceed to the left If Q<K, the reaction must proceed to the right If Q=K the reaction is at equilibrium

6-2 Le Chateliers Principle and Heat

The term eS/R is independent of T (at least over a limited temperature range in which S is constant). The term eH/RT increases with increasing temperature if H is positive and decreases if H is negative. Therefore, The equilibrium constant of an endothermic reaction (H = +) increases if the temperature is raised.

The equilibrium constant of an exothermic reaction (H = ) decreases if the temperature is raised.

These statements can be understood in terms of Le Chtelier's principle as follows. Consider an endothermic reaction:

Heat +Reactants

Products

If the temperature is raised, then heat is added to the system. The reaction proceeds to the right to partially offset this change.

6-2 TYPES OF EQUILIBRIUM Constants

6-3 Solubility Product The solubility product is the equilibrium constant for the reaction in which a solid salt dissolves to give its constituent ions in solution. Solid is omitted from the equilibrium constant because it is in its standard state.

A solution containing excess, undissolved solid is said to be saturated with that solid. The solution contains all the solid capable of being dissolved under the prevailing conditions.

6-3 Solubility Product Example The solubility product, Ksp, is a special type of equilibrium constant given to a solution containing sparingly soluble salts. If the solution is not saturated, no precipitate will form. The product is called the ion product, Qsp. Qsp < Ksp= Undersaturated solution Qsp = Ksp = Saturated solution Qsp > Ksp= Oversaturated solution

6-3 Solubility Product Example Determining Ksp from Solubility

PROBLEM: (a) Lead (II) sulfate is a key component in lead-acid car batteries. Its solubility in water at 250C is 4.25x103g/100mL solution. What is the Ksp of PbSO4?

(b) When lead (II) fluoride (PbF2) is shaken with pure water at 250C, the solubility is found to be 0.64g/L. Calculate the Ksp of PbF2.
PLAN: Write the dissolution equation; find moles of dissociated ions; convert solubility to M and substitute values into solubility product constant expression. (a) PbSO4(s)

SOLUTION:

Pb2+(aq) + SO42-(aq) K = sp [Pb2+][SO42-] 4.25x10-3g 1000mL mol PbSO4 = 1.40x10-4M 100mL soln L 303.3g PbSO4 PbSO4 1.96x10-8 Ksp = [Pb2+][SO42-] = (1.40x10-4)2 =

6-3 Solubility Product Example Determining Ksp from Solubility

(b) PbF2(s) 0.64g L soln

Pb2+(aq) + 2F-(aq) mol PbF2 245.2gPbF2

Ksp = [Pb2+][F-]2

= 2.6x10-3 M 7.0x10-8

Ksp = (2.6x10-3)(5.2x10-3)2 =

6-3 Determining Solubility from Ksp PROBLEM: Calcium hydroxide (slaked lime) is a major component of mortar, plaster, and cement, and solutions of Ca(OH)2 are used in industry as a cheap, strong base. Calculate the solubility of Ca(OH)2 in water if the Ksp is 6.5x10-6. PLAN: Write out a dissociation equation and Ksp expression; Find the molar solubility (S) using a table. Ca(OH)2(s) [Ca2+][OH-]2 Ca(OH)2(s) Ca2+(aq) + 2OH-(aq) Ksp =

SOLUTION:

Concentration (M) Initial Change Equilibrium

Ca2+(aq) + 2OH-(aq) 0 +S S 0 + 2S 2S

Ksp = (S)(2S)2 S = 3 6.5x106 4

= 1.2x10x-2M

6-3 Common Ion effect

For the ionic solubility reaction the product [Ca2+][ SO42-] is constant at equilibrium in the presence of excess solid CaSO4.

If the concentration of Ca2+ were increased by adding another source of Ca2+, such as CaCl2, then the concentration of must decrease so that the product [Ca2+][ ] remains constant. In other words, less CaSO4(s) will dissolve if Ca2+ or is already present from some other source.
This application of Le Chtelier's principle is called the common ion effect.

A salt will be less soluble if one of its constituent ions is already present in the solution.

6-3 Calculating the effect of Common Ion on Solubility

PROBLEM: In Sample Problem 19.6, we calculated the solubility of Ca(OH)2 in water. What is its solubility in 0.10M Ca(NO3)2? Ksp of Ca(OH)2 is 6.5x10-6. PLAN: Set up a reaction equation and table for the dissolution of Ca(OH)2. The Ca(NO3)2 will supply extra [Ca2+] and will relate to the molar solubility of the ions involved. SOLUTION: Concentration(M) Initial Change Equilibrium Ca(OH)2(s) Ca2+(aq) + 2OH-(aq) 0.10 +S 0.10 + S 0 +2S 2S

Ksp = 6.5x10-6 = (0.10 + S)(2S)2 = (0.10)(2S)2

S=

S << 0.10

6.5x106 4

= 4.0x10-3

Check the assumption: 4.0x10-3 0.10M x 100 = 4.0%

6-3 Separation by Precipitation Predicting whether a precipitate will form

PROBLEM:

A common laboratory method for preparing a precipitate is to mix solutions of the component ions. Does a precipitate form when 0.100L of 0.30M Ca(NO3)2 is mixed with 0.200L of 0.060M NaF?

PLAN:

Write out a reaction equation to see which salt would be formed. Look up the Ksp valus in a table. Treat this as a reaction quotient, Q, problem and calculate whether the concentrations of ions are > or < Ksp. Remember to consider the final diluted solution when calculating concentrations. CaF2(s) Ca2+(aq) + 2F-(aq) Ksp = 3.2x10-11

SOLUTION:

mol Ca2+ = 0.100L(0.30mol/L) = 0.030mol mol F- = 0.200L(0.060mol/L) = 0.012mol Q = [Ca2+][F-]2 =

[Ca2+] = 0.030mol/0.300L = 0.10M [F-] = 0.012mol/0.300L = 0.040M

(0.10)(0.040)2 = 1.6x10-4

Q is >> Ksp and the CaF2 WILL precipitate.

6-3 Calculating the effect of Complex-Ion Formation on Solubility

PROBLEM: In black-and-white film developing, excess AgBr is removed from the film negative by hypo, an aqueous solution of sodium thiosulfate (Na2S2O3), through formation of the complex ion Ag(S2O3)23-. Calculate the solubility of AgBr in (a) H2O; (b) 1.0M hypo. Kf of Ag(S2O3)23- is 4.7x1013 and Ksp AgBr is 5.0x10-13. PLAN: Write equations for the reactions involved. Use Ksp to find S, the molar solubility. Consider the shifts in equilibria upon the addition of the complexing agent. SOLUTION: AgBr(s) Ag+(aq) + Br-(aq) Ksp = [Ag+][Br-] = 5.0x10-13

(a) S = [AgBr]dissolved = [Ag+] = [Br-]

Ksp = S2 = 5.0x10-13 ; S = 7.1x10-7M

(b)

AgBr(s)
Ag+(aq) + 2S2O32-(aq) AgBr(s) + 2S2O32-(aq)

Ag+(aq) + Br-(aq)
Ag(S2O3)23-(aq) Br -(aq) + Ag(S2O3)23-(aq)

Calculating the Effect of Complex-Ion Formation on Solubility

Koverall = Ksp x Kf =

[Br-][Ag(S2O3]23[AgBr][S2O32-]2

= (5.0x10-13)(4.7x1013) = 24

Concentration(M) Initial Change Equilibrium Koverall = S2

AgBr(s) + 2S2O32-(aq) = 24 1.0 -2S 1.0-2S S 1.0-2S

Br-(aq) + Ag(S2O3)23-(aq) 0 +S S = (24)1/2 0 +S S

(1.0-2S)2

S = [Ag(S2O3)23-] = 0.45M

6-4 Complex formation Lewis acids and bases If anion X precipitates metal M+, High concentration of X causes solid MX to re dissolve. The increased solubility arises from the formation of complex ions, such as which consist of two or more simple ions bonded to each other. Lewis Acids and Bases In complex ions such as PbI+, PbI2-, PbI4-,

Iodide is said to be the ligand of Pb2+.

A ligand is any atom or group of atoms attached to the species of interest.

6-4 Complex formation Lewis acids and bases

Pb 2+ acts as a Lewis acid and I acts as a Lewis base. A Lewis acid accepts a pair of electrons from a Lewis base when the two form a bond: The product of the reaction between a Lewis acid and a Lewis base is called an adduct. The bond between a Lewis acid and a Lewis base is called a dative or coordinate covalent bond.

6-4 Complex Formation

Effect of Complex Ion Formation on Solubility If Pb2+ and I only reacted to form solid PbI2, then the solubility of Pb2+ would always be very low in the presence of excess I.

6-4 Compolex Fomation

High concentrations of I cause solid PbI2 to dissolve. Due to the formation of a series of complex ions: (6-12) The species PbI2(aq) in Reaction 6-13 is dissolved PbI2, containing two iodine atoms bound to a lead atom.. At low I concentrations, the solubility of lead is governed by precipitation of PbI2(s). At high I concentrations, Reactions 6-12 through 6-15 are driven to the right (Le Chtelier's principle Total concentration of dissolved lead is considerably greater than that of Pb 2+ alone

6-5 Protic Acids and Bases

An acid is a substance that increases the concentration of H3O+ (hydronium ion) when added to water.

A base decreases the concentration of H3O+. base increases the concentration of OH in aqueous solution.
The word protic refers to chemistry involving transfer of H+ from one molecule to another. The species H+ is also called a proton because it is what remains when a hydrogen atom loses its electron. Hydronium ion, H3O+, is a combination of H+ with H2O. H3O+ is a more accurate representation than H+ for the hydrogen ion in aqueous solution,

6-5 Protic Acids and Bases Bronsted Lowry Acids and Base

Brnsted and Lowry classified acids as proton donors and bases as proton acceptors. HCl is an acid (a proton donor) and it increases the concentration of H3O+ in water: The Brnsted-Lowry definition does not require that H3O+ be formed. This definition can therefore be extended to non aqueous solvents and even to the gas phase:

6-5 Protic Acids and Bases The nature of H+ and Bases

It is certain that the proton does not exist by itself in water. The simplest formula found in some crystalline salts is H3O+. For example, crystals of perchloric acid monohydrate contain pyramidal hydronium (also called hydroxonium) ions:

6-6 pH Relationship between Ka and Kb

Solvent Autoprotolysis or self-ionization Water is the most common: H2O + H2O = H3O+ +OHH2O= H+ +OH- Kw = [H+][OH-] = 1.0 x 10-14 Also occurs in all protic solvents due to reactive H+. 2 CH3CH2OH = CH3CH2OH2 + + CH3CH2OpH pH = -log [H+] pH > 7 is basic, pH<7 is acidic pH + pOH = pKw = 14.00 at 25oC

6-7 Strengths of Acids and Bases

Acids and bases are commonly classified as strong or weak, depending on whether they react nearly completely or only partially to produce H+ or OH.

A strong acid or base is completely dissociated in aqueous solution. That is, the equilibrium constants for the following reactions are large.

No undissociated HCl or KOH exists in aqueous solution. For most purposes, the hydroxides of the alkaline earth metals (Mg2+, Ca2+, Sr2+, and Ba2+) can be considered to be strong bases,

6-7 Strong acids bases and Their relative strengths

Acid and Base Strengths Acid and base strengths may be determined by using a differentiating solvent. That is, selecting a solvent which will accept(or donate) a proton to one acid (or base) but not another (example: use of glacial acetic acid as solvent to compare HClO4 and HCl acid strength). a leveling solvent is one in which all acids or bases are dissociated to the same degree and have equal acid (or base) strengths.

Weak acids and bases All weak acids, denoted HA, react with water by donating a proton to H2O

The equilibrium constant is called Ka, the acid dissociation constant. A weak acid is one that is only partially dissociated in water. The equilibrium constant Kb is called the base hydrolysis constant. By definition, a weak base is one for which Kb is small.

Relation between Ka and Kb A most important relation exists between Ka and Kb of a conjugate acid-base pair in aqueous solution. We can derive this result with the acid HA and its conjugate base A.

Acid Base Dissociation Constants

Polyprotic Acids and Bases can donate or accept more than one proton Ka or Kb are sequentially numbered - Ka1,Ka2,Ka3 Kb1,Kb2,Kb3

Relationship Between Ka and Kb

[ H ][ A ] Ka [ HA]
Kb [ HA][OH ] [ A ]

K w Ka Kb [ H ][ A ] [ HA ][ OH ] [ H ][OH ] [ HA ] [ A ]

K w Ka Kb