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Ch 15 More Equilibrium: Buffers, Ksp, Kf:

Homework: Read Ch 15 Work out sample/practice exercises in the sections as you read, Chapter 15: 1-33, 34, 43, 48, 52, 56, 60, 64, 72, 76, 78, 80, 86, 90, 98, 108, 118, 120, 128, 138, 140 Bonus Ch 15: 42, 44, 50, 54, 58, 62, 68, 74, 82, 84, 92, 96, 102, 104, 106, 126, 150 Neutralization Reactions: To determine the extent of a neutralization reaction, add the acid Equilibria and/or the base Equilibria and the reverse of the Kw equations together to solve for the overall reaction. You will then find that the neutralization equilibrium constant Kn= (Ka and/or Kb)/Kw. Neutralization reactions generally favor products. Strong acid and Strong base Kn = 1/Kw Strong acid and Weak base Kn = Kb/Kw Weak acid and Strong base Kn = Ka/Kw Weak acid and Weak base Kn = (Ka x Kb)/Kw Strong Acid and Weak Base neutralization Reaction: Weak Base: NH3 (aq) + H2O (l) NH4+1 (aq) + OH-1 (aq); Strong Acid: H+1 (aq) + OH-1 (aq) H2O (l) ; Net: H+1 (aq) + NH3 (aq) NH4+1 (aq); Kb = 1.8 x 10-5 1/Kw = 1.0 x 10+14 Kn = Kb/Kw = 1.8 x 109

Example 1: Show the Kn set-up and solve for the value of Kn for the following a) The strong acid HCl with the strong base KOH

b) The strong acid HCl with the weak base NH3

c) The weak acid HCN with the weak base CH3NH2

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The Common Ion Effect: So far we have studied the acid-base equilibrium reactions in just water. What happens when we add other substances? We will learn in the PbI2 lab that the additions of common ions or even uncommon (spectator) ions affect the activity values of the concentrations according to the Debye-Huckel equation and therefore affect the equilibrium. This can be quite complicated so we generally assume the activity value is equal to the molarity of a solution or the atmospheric pressure of a gas. We will continue with this simplified assumption in the lecture. You will have a chance in the lab to calculate the adjusted activity values. The common ion effect occurs when the same ion is produced by two different components. Lets look at what happens when a weak acid or weak base equilibrium solution has its conjugate added (the common ion effect). For a certain concentration of a weak acid (a reactant) we have learned how to calculate the pH given the Ka value. If we add a salt containing its conjugate base (a product in the weak acid equilibrium reaction) into the solution, the dissociation of the weak acid will decrease and the pH will increase according to Le Chatelliers Principle. Example 2: a) What is the pH of a 0.40 M HF in pure water? Ka = 6.8 x 10-5

b) What is the pH of a 0.40 M HF in 0.20 M KF solution? Ka = 6.8 x 10-5

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Buffered Solutions: Buffered solutions will resist change in pH even after a strong acid or a strong base is added to the solution. This is extremely important in many situations. Examples: Human Blood is buffered around a pH of 7.4, too high or too low will cause sickness and death. Fish tanks, medicines, enzymes, biological applications all generally require a specific pH range to function properly. Without buffers, the simple act of consuming too much acid by drinking soda or lemonade can have terrible effects. It is possible to buffer a solution at any pH. Buffers do not mean neutralized to a pH around 7? You just need to choose an appropriate weak acid or weak base conjugate pair which has a pKa or pKb close to the pH required. Buffers have a buffer capacity. You must have both conjugates of weak acid base pair to maintain a buffer. If you run out of either while adding a strong acid or base then you have reached the end of the buffer capacity. Composition of Effective Buffers: a) Weak acid and weak base conjugate pairs: Buffers need to eliminate strong acids or strong bases when they are added. They can do this because a reaction will always favor creating a weaker acid or weaker base. Adding a strong acid will cause the weak conjugate base in the buffer to accept the extra H+1, forming its weak conjugate acid. Adding a strong base will cause the weak conjugate acid to donate its H+1, creating its weak conjugate base. Buffers will never be created using the conjugate acid/base pairs of something strong/negligible. b) Ratio of Conjugate acid base pairs should be within 1 to 10 or 10 to 1: Generally a buffer solution will have close to equivalent concentrations of each weak acid/weak base conjugate pair. The pH range should be within +1 or 1 of the pKa c) Relatively high concentrations of each: A buffer will generally have a minimum concentration of 0.05 M of each conjugate pair. The greater the concentrations, the better the buffer capacity (amount of acid or base it is able to take on before losing its buffering capabilities).

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Example 3: Identify which of the following pairs can function as a buffer. For those pairs that cannot function as a buffer, explain why not. a) HNO3 ; KNO3 b) NH4Cl ; NH3 c) NaC2H3O2 ; HC2H3O2 d) HF ; HNO2 e) CH3NH2 ; CH3NH3Br f) H2CO3 ; HCO3-1 g) NaCl ; NaNO3 h) KOH ; H2O

Effective Buffer pH Range: The effective pH range of a buffer over which it can act is generally pKa -1 to pKa+1 of the weak acid. This is within the 1:10 and 10: 1 ratio between weak acidbase conjugates. For an acid: the pKa = log Ka For a base: the pKb = log Kb Conversion: pKw = 14.00 = pKa + pKb for conjugate acid-base pairs Effective pH range: pH = pKa 1 or pOH = pKb 1 Example 4: Determine the effective pH range (pKa +/- 1) for the buffer solutions. a) NH4Cl ; NH3 Kb of NH3 = 1.8 x 10-5

b) NaC2H3O2 ; HC2H3O2 c) H2CO3 ; NaHCO3 d) CH3NH2 ; CH3NH3Br

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Henderson-Hasselbalch Equation to Calculate pH of Buffers : Buffer solutions have a special formula to calculate pH. This is derived by taking the log of both sides of the equilibrium constant using the RICE equation , it assumes that the amount of change is small and negligible compared to the original concentrations of the weak acid/weak base conjugate pairs For ACIDS: pH = pKa + log [base/acid] For BASES: pOH = pKb + log [acid/base] Example 5: Solve for the pH of the 0.40 M HF in 0.20 M KF solution in Example 1 using the Henderson-Hasselbalch equation. Ka = 6.8 x 10-5

Adding Strong Acids and Strong Bases to Buffers: When adding a strong acid or a strong base to a buffer solution the conjugate weak acid or base will decrease as it consumes/neutralizes the strong and its conjugate pair will increase. H+ added will decrease the conjugate weak base and increase the weak acid concentrations OH-1 added will decrease the conjugate weak acid and increase the weak base concentrations This can only occur as long as the concentrations remain in equilibrium. Once the buffer capacity is breached you will no longer have a buffered solution. Example 6: Solve for the pH of 100 ml of the 0.40 M HF/ 0.20 M KF solution after the following is added a) 0.010 mole HCl b) 0.010 mole NaOH

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Acid-Base Titration Curves: Strong Acid / Strong Base Titration: Example 7: An acid-base titration experiment begins with 20.0 ml of 0.300 M HCl in the flask and 0.150 M NaOH in the buret. Both are strong. a) Draw the expected titration graph where pH is the y axis and ml of NaOH added is the x axis, Sketch and label the titration curve including SA or SB, salt, equivalence pt, pH at equiv pt <, =, or > 7, buffer, where color change of indicator should occur.

b)

What are the initial [H+] and pH, in the flask? Clearly identify answers.

c)

What is the pH after 18.0 ml of 0.150 M NaOH has been added to the flask containing 20.0 ml of 0.300 M HCl?

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d)

What volume of 0.150 M NaOH must be added to the original flask of 20.0 ml of 0.300 M HCl to reach the equivalence point?

e)

Write the balanced whole, complete ionic, and net ionic equations of hydrolysis of the salt sodium fluoride (NaCl) and indicate whether the salt is acidic, basic, or neutral.

f)

What is the pH of the solution in the flask at the equivalence point?

g)

Which is the best indicator to use for determining the endpoint of this titration Bromocresol green (pH 4-6) or phenolphthalein (pH 8-10) or either?

h)

What is the pH after 45.0 ml of 0.150 M NaOH has been added to the original flask containing 20.0 ml of 0.300 M HCl?

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Weak Acid / Strong Base Titration: Example 8: An acid-base titration experiment begins with 20.0 ml of 0.300 M HF in the flask and 0.150 M NaOH in the buret. Ka for HF = 6.6 x 10-4. a) Draw the expected titration graph where pH is the y axis and ml of NaOH added is the x axis, Sketch and label the titration curve including WA or WB, SA or SB, salt, equivalence pt, pH at equiv pt <, =, or > 7, buffer, where color change of indicator should occur.

b)

What are the initial [H+], [OH-], pH, pOH, and % ionization for the 0.300 M HF -4 in the flask? Clearly identify answers. Ka for HF = 6.6 x 10

c)

At the half-equivalence point one has an equal concentration of both the conjugate acid and the conjugate base of a weak acid-base pair. This special buffer situation has a pH = pKa. Show the calculation to demonstrate how this equation works and solve for the pH at the half equivalence pt of this titration.

d)

What is the pH after 18.0 ml of 0.150 M NaOH has been added to the flask containing 20.0 ml of 0.300 M HF?

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e)

What volume of 0.150 M NaOH must be added to the original flask of 20.0 ml of 0.300 M HF to reach the equivalence point?

f)

Write the balanced whole, complete ionic, and net ionic equations of hydrolysis of the salt sodium fluoride (NaF) and indicate whether the salt is acidic, basic, or neutral.

g)

Solve for the numerical Kb value for the net ionic equation in the previous step.

h)

What is the pH of the solution in the flask at the equivalence point?

i)

Which is the best indicator to use for determining the endpoint of this titration Bromocresol green (pH 4-6) or phenolphthalein (pH 8-10)? What is the pH after 45.0 ml of 0.150 M NaOH has been added to the original flask containing 20.0 ml of 0.300 M HF?

j)

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Strong Acid / Weak Base Titration: Example 9: An acid-base titration experiment begins with 20.0 ml of 0.300 M NH3 in the flask and 0.150 M HCl in the buret. Kb for NH3 = 1.8 x 10-5. a) Draw the expected titration graph where pH is the y axis and ml of HCl added is the x axis, Sketch and label the titration curve including WA or WB, SA or SB, salt, equivalence pt, pH at equiv pt <, =, or > 7, buffer, where color change of indicator should occur.

b)

What are the initial [H+], [OH-], pH, pOH, and % ionization for the 0.300 M NH3 in the flask? Clearly identify answers. Kb for NH3 = 1.8 x 10-5

c)

What is the pH after 18.0 ml of 0.150 M HCl has been added to the flask containing 20.0 ml of 0.300 M NH3?

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d)

What volume of 0.150 M HCl must be added to the original flask of 20.0 ml of 0.300 M NH3 to reach the equivalence point?

e)

Write the balanced whole, complete ionic, and net ionic equations of hydrolysis of the salt sodium fluoride (NH4Cl) and indicate whether the salt is acidic, basic, or neutral.

f) g)

Solve for the numerical Ka value for the net ionic equation in the previous step. What is the pH of the solution in the flask at the equivalence point?

h)

Which is the best indicator to use for determining the endpoint of this titration Bromocresol green (pH 4-6) or phenolphthalein (pH 8-10)? What is the pH after 45.0 ml of 0.150 M HCl has been added to the original flask containing 20.0 ml of 0.300 M NH3?

i)

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Polyprotic Weak Acid/Strong Base: Polyprotic acids have two or more acid hydrogens that may be lost in a titration with the base. Some special extra equations associated with a diprotic acid (H2A) follows At the first half equivalence point: At the first equivalence point (salt, NaHA): At the second half equivalence point: At the second equivalence point (salt, Na2A): pH = pKa1 pH = (pKa1 + pKa2)/2 pH = pKa2 Kb = Kw/Ka2

Example 10: An acid-base titration experiment begins with 20.0 ml of 0.300 M H2CO3 in the flask and 0.150 M NaOH in the buret. a) Sketch the expected titration curve where pH is the y axis and ml of NaOH added is the x axis.

b) Solve for the initial pH of the 20.0 ml of 0.300 M H2CO3

c) Solve for the pH at first half equivalence point

d) Solve for the pH at the first equivalence point

e) Solve for the pH at second half equivalence point

f) Solve for the pH at the second equivalence point

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Solubility Equilibria, Ksp: The Solubility Product equilibrium constant (Ksp) involves slightly soluble solids, (ionic compounds that we earlier labeled as solid when looking at the solubility rules). These compounds dissolve less than 0.020 M at 25C in water. In reality almost all ionic compounds at least partially dissolve. A small amount of the insoluble ionic compound dissolves into its individual ions creating an equilibrium with the ionic solid as a reactant and its ions in the product. Ksp values are generally small (much less than 1) so few ions (products) exist at equilibrium. Ksp reactions affect the world around us, examples includedissolving tooth enamel in acid (soda) solutions, development of kidney stones, and cave formations. Example 11: Write Ksp reactions and Ksp expressions. Example: PbI2 (s) Pb+2 (aq) + 2 I-1 (aq) a) CuCO3 (s) Ksp = [Pb+2][I-1]2

b) Fe(OH)3 (s)

c) Ca3(PO4)2 (s)

Solubility: The solubility (g/L) or molar solubility (mol/L) is the quantity of the solid that dissolves to form a saturated solution. When comparing Ksp values to determine relative solubility strengths , the number of ions the solid breaks into is important.

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Example 12: First looking at the Ksp, estimate which solid you think will have the greatest molar solubility before any calculations are performed. Second calculate the molar solubilities and equilibrium ion concentrations for the solids in just water. Given: AgCl Ksp = 1.8 x 10-10 Ag2CrO4 Ksp = 1.2 x 10-12 Ca3(PO4)2 Ksp = 2.0 x 10-29

Example 13: Saturated Mg3(AsO4)2 contains 16 mg/L of Mg3(AsO4)2 at 25C. Calculate the molar solubility and Ksp. (MW = 350.7)

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Reaction Quotient, Qsp: When two ionic solutions are mixed, they may form a solid in a double displacement reaction. To determine if a precipitate will form, compare Qsp to Ksp Qsp > Ksp Qsp = Ksp Qsp < Ksp precipitate will form: The human eye is not very sensitive, If Qsp/Ksp > 1000 the solid will become visible (cloudy) to the naked eye. solution is just saturated, but no solid Unsaturated solution, no solid

Example 14: Will a CaSO4 solid form, will it be visible to a human eye if the following separate solutions are mixed in equal volumes (total volume doubles) in each part. Ksp for CaSO4 = 2.4 x 10-5 a) 0.0040 M Ca(NO3)2 added to 0.0040 M Na2SO4

b) 0.040 M Ca(NO3)2 added to 0.040 M Na2SO4

c) 0.40 M Ca(NO3)2 added to 0.40 M Na2SO4

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Factors that Affect Solubility: Temperature: The Ksp value will change as the temperature changes. For example, PbCl2 has a greater solubility as the temperature increases. This was useful in our separation of Group 1 ions lab. Ksp at 25C Molar solubility Ksp at 100C Molar solubility at 25C at 100C -5 -3 1.7 x 10 0.016 M 6.9 x 10 0.12 M PbCl
2

Common ion: Solubility decreases in the presence of a common ion. Solubility increases if a basic compound is added to an acidic solution or an acidic compound is added to a basic solution. Example 15: Ca(OH)2 Ksp = 6.5 x 10-6

Solve for the molar solubility, ion concentrations, and pH for (a) solid Ca(OH)2 in water

(b) solid Ca(OH)2 in a solution of 0.10 M CaCl2 (aq)

(c) solid Ca(OH)2 in a buffered solution of pH = 11.20

Simultaneous Equilibria: Many chemical reactions involve simultaneous Equilibria, more than one competing at the same time. An example to consider is a slightly soluble salt (Ksp) that ionizes to make a weak acid or weak base (Ka or Kb).

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Example 16:

Mg(OH)2 Ksp = 1.6 x 10-12 NH3 Kb = 1.8 x 10-5 Consider that 0.10 mole NH3 and 0.10 mole Mg(NO3)2 are added to enough water to dilute to 1.00 L. a) Will the Mg(OH)2 precipitate and will it be visible to the eye? For this problem the [Mg+2] = 0.10M, the [OH-1] must be solved using the Kb reaction for NH3

b)

How many moles of NH4Cl must be added to prevent the precipitation of the Mg(OH)2 in the 1.00L solutions containing 0.10 mole NH3 and 0.10 mole Mg(NO3)2? By buffering the solution the [OH-1] concentration can remain low enough to avoid precipitation. Use your known Ksp to solve for the max [OH-1]: Ksp = [0.10M Mg+2][OH-1]2. Then convert to the pOH and use the buffer equation to solve for the minimum molarity of NH4Cl required to avoid precipitation.

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Dissolving precipitates: Precipitates dissolve when Qsp < Ksp. The following three reaction types remove ions from the solution to shift the reaction forward and dissolve the solid. 1) Convert ions to weak electrolytes: Insoluble metal hydroxides dissolve in acids Zn(OH)2 (s) + 2H+1 2 H2O (l) + Zn+2 (aq) In this case the OH-1 ions are removed by reacting with the acid and creating water. 2) Convert ions to another species by oxidation reduction reactions: Insoluble metal sulfides dissolve in hot HNO3 3PbS (s) + 8H+1 + 2 NO3-1 3 S (s) + 2NO (g) +4 H2O (l) +3 Pb+2 In this case the S-2 ions are removed by reduction reaction and converting the ions to solid sulfur. 3) Convert ions into another form a complex ion: Many cations form complex ions as we saw in the group 1 lab Ag+1 + 2 NH3 Ag(NH3)2+1 Another example Cu(OH)2 (s) + 4 NH3 (aq) Cu(NH3)4+2 (aq) + 2 OH-1 (aq) In this case the Cu+2 ions are converted to Cu(NH3)4+2 (aq). Formation of Complex Ions: Many metal ions have an ability to form a complex ion, which is an assembly of a metal ion (a Lewis acid) and some simple multiple of the Lewis bases (those able to donate a share of an electron pair) bonded to it. The Lewis bases can include OH-1, CN-1, NH3, and others. The Appendix lists formation constants (Kf). The reverse reaction is the dissociation constant (Kd) equilibrium reactions and Kd = Kf-1. Equilibrium of Complex Ions, Kf or Kd: Kf is the formation constant of a complex ion Kd is the dissociation constant of a complex ion When solving problems, to ignore the x which is added or subtracted from a number, x must be small.

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Example 17:

Ni(NH3)6+2 Kf = 1.2 x 10-9

a) Calculate the [Ni+2] in a solution that has 0.010 M Ni(NH3)6+2 in 0.10 M NH3.

b) Calculate the [NH3] in a solution that has 0.020 M Ni(NH3)6+2 in 0.010 M Ni+2

c) Calculate the equilibrium concentrations of each species in a solution that has 100 ml of 0.20 M Ni+2 added to 100 ml of 0.10 M NH3

Amphoteric Oxides and Hydroxides: Amphoteric is applied to the behavior of insoluble oxides and hydroxides that can be made to dissolve in either acid or base solutions. These substances can dissolve in acid to create the metal ions Al(OH)3 + 3 H+1 3 H2O (l) + Al+3 (aq) And they dissolve in strong base solutions Al(OH)3 + OH-1 Al(OH)4-1 (aq) For more information on these substances read the book, but do not worry about the details.

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Precipitation and Separation of Ions: The end of this chapter goes into details of qualitative analysis to determine the unknown ions in a solution. You should be able to understand the general concepts and be able to work out a problem dealing with fractional precipitation, but the test will not question the details. We have done separations of group 1 cations and anions in the lab. We will have another lab with more cations at a later time. The Unit 2 test will not ask specific directions on how to separate specific ions. Fractional Precipitation (A Separation Process): It is possible to separate ion mixtures if one ion will precipitate before another due to the difference in molar solubilities. Another influence is temperature: Ksp values alter as the temperature values change. solid AgCl Ksp at 25C Molar solubility at 25C 1.8 x 10-10 1.3 x 10-5 M Ksp at 100C 2.3 x 10-8 Molar solubility at 100C 1.5 x 10-4 M

1.7 x 10-5 1.6 x 10-2 M 6.9 x 10-3 0.12 M PbCl2 We used this difference in our lab as we separated the Pb+2 ions by heating the chloride solids in hot water. Example 18: A solution contains 0.10 M Ag+1 and 0.10 M Pb+2. HCl is added to form precipitates (ignore volume change due to HCl added). Use the table above to solve for the concentration of chloride ion that is required to initiate precipitation of each cation at 25C? What percent of the first ion to form a precipitate remains when the second just begins to precipitate at 25C