Neutralization: Strong Acid-Strong Base

Chapter 15 - Applications of Aqueous Equilibria

GCC CHM152

Molecular: HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l) SA-SB rxn goes to completion (one-way )

Write ionic and net ionic rxns

H+(aq) + Cl-(aq) + Na+(aq) + OH-(aq) Net: H+(aq) + OH-(aq) H2O(l) H2O(l) + Na+(aq) + Cl-(aq)

After neutralization, whats in solution? Do either of the salt ions react with water? What is pH of the salt solution?

Neutralization: Weak Acid-Strong Base

HF (aq) + KOH (aq) KF (aq) + H2O (l) Rxn goes to completion due to SB Write ionic and net rxns: HF(aq) + K+(aq) + OH-(aq) K+(aq) + F-(aq) + H2O(l) Net: HF(aq) + OH-(aq) H2O(l) + F-(aq) After neutralization, whats in solution? Do either of the salt ions react with water?

Neutralization: Strong Acid- Weak Base

HCl (aq) + NH3 (aq) NH4+ (aq) + Cl- (aq) Rxn goes to completion because of strong acid Write ionic and net rxns: H+(aq) + Br-(aq) + NH3(aq) NH4+(aq) + Br-(aq) Net Ionic: H+(aq) + NH3(aq) NH4+(aq) After neutralization, whats in solution? Do either of the salt ions react with water? What will the pH of the solution be, roughly?

What will the pH of the solution be, roughly?

Neutralization: Weak Acid-Weak Base

CH3COOH(aq) + NH3(aq) NH4CH3COO(aq) Reaction does go to completion since no reactant is completely ionized. Ionic: CH3COOH(aq) + NH3(aq) NH4+(aq) + CH3COO-(aq) Net: same The salt remaining after neutralization contains an acidic and a basic ion, so pH depends on their relative Ka and Kb values.

Neutralization Reactions
Predict whether the pH after neutralization will be greater than, less than, or equal to 7 for the following combinations: HNO2 and KOH HCl and LiOH HBr and NH3

Common Ion effect

The shift in equilibrium caused by the addition of a substance having an ion in common with the equilibrium mixture. Adding a common ion suppresses the ionization of a weak acid or a weak base.
The source of the common ion is typically provided by adding a strong acid, a strong base or a soluble salt to the equilibrium reaction mixture.

Common Ion Concept Problem

Given this reaction:
CH3CO2H + H2O H3O+ + CH3CO2-

What happens to the pH of the acetic acid solution if we add NaCH3CO2? [CH3CO2-] Eq shifts [H3O+] , thus pH

Common Ion Effect

CH3CO2H + H2O CH3CO2- + H3O+ 0.100 M CH3CO2H WA soln: pH = 2.879 Add common ion CH3CO2- , pH 0.100 M CH3CO2H, add 0.050 M NaCH3CO2 Mix of WA and conj base: pH = 4.456

Common Ion Problem

What is the pH of 1.00 M HF solution? Ka = 7.0 x 10- 4 What is the pH of 1.00 M HF solution after adding 0.500 M NaF? Ka = 7.0 x 10-4

16.3 Buffer Solution

A solution that resists changes in pH when a small amount of acid or base is added. Buffers are used to control pH e.g. biological buffers maintain the pH of all body fluids Best buffer systems consist of either a) a weak acid and its conjugate base e.g. HC2H3O2 and NaC2H3O2 b) a weak base and its conjugate acid e.g. NH3 and NH4Cl

Which are buffer solutions?

Identify the solutions below that would make good buffer solutions (what criteria need to be met?):
HF and NaF NH3 and NH4Cl KOH and KF CH3COOH and LiCH3COO NaNO3 and HNO3 NaOH and NaCl HCl and NaCH3COO

Buffer Capacity
Buffers only work within a pH range set by the value of Ka:
pH = pKa 1

Buffer Range
Select an appropriate acid-base pair to get within the range of the desired pH. Look at table of Ka values (some are shown on the next screen), calculate pKa, and select an appropriate combination. How would you make a buffer solution with pH = 4.10? What could you use to make this?

Outside this range, we see little buffering effect. If you know the desired pH of a buffer solution, you can choose an acid with a pKa near the pH.

Table of Ka values
Acid
HF HNO2 C9H8O4 (aspirin) HCO2H (formic) C6H8O6 (ascorbic) C6H5CO2H (benzoic) CH3CO2H (acetic) HCN C6H5OH (phenol)

Buffer Solutions
HF(aq) + H2O(l) H3O+(aq) + F-(aq) Add HCl, which component of the buffer soln will HCl reaction with (acid or base)?
H+ will react with F- (conj. base)

3.5 x 10 4 4.5 x 10 4 3.0 x 10 4 1.7 x 10 4 8.0 x 10 5 6.5 x 10 5 1.8 x 10 5 4.9 x 10 10 1.3 x 10 10

Ka

Add NaOH, which component of the buffer soln will NaOH react with (acid or base)?
OH- will react with HF (weak acid)

There will be a pH change in each case, but not as much as if the HCl (or NaOH) were added to water.

Buffer Solutions
Figure 15.3

Henderson-Hasselbalch Equation
When solving for [H3O+] at equilibrium and assuming x << [HA] & [A-] for good buffer action, the equilibrium expression Ka = [H3O+][A-] / [HA] can be rearranged to give a simplified calculation:

pH = pKa + log ([A-] / [HA])

Can use moles or M depending on given info

Buffers shockwave animation

Buffer Solutions + HCl

What is the pH of 500.0 mL of 0.10 M formic acid combined with 500.0 mL of 0.20 M sodium formate? Ka = 1.8 x 10-4 pH = pKa + log ([A-]/[HA]) = 4.05
Now add 10.0 mL of 0.50 M HCl
calculate moles of substances, then calculate changes Use a CHANGE Table (initial, change, final)

Buffer Solutions + HCl

To find the new pH, first assume that all the added strong acid reacts with A- to form HA.
How many moles of HA, A-, and H3O+ are in solution? Initial mol HA = (0.10 M) (0.5000 L) = 0.050 mol Initial mol A- = (0.20 M) (0.5000 L) = 0.10 mol mol HCl = (0.0100 L) (0.50 M) = 0.0050 mol Final mol A- = 0.10 mol 0.0050 mol = 0.095 mol Final mol HA = 0.050 mol + 0.0050 mol = 0.055 mol

H3O+ + A- H2O + HA

Can use final moles in H-H equation. Why?

pH = pKa + log ([A-]/[HA]) = 3.98

Buffer +NaOH
What will happen when we add a strong base to a buffer system?
Added base reacts with HA to form A-: HA and A-

Buffer Solutions + NaOH

First assume that all OH- reacts with HF:

HF + OH- H2O + F How many moles of base were added?

mol OH- = (0.500 M) (0.0100 L) = 0.00500 mol OH final mol HA = 0.050 mol - 0.00500 mol = 0.045 mol final mol A- = 0.10 mol + 0.00500 mol = 0.105 mol

HA +

OH-

H2O +

A-

Add 10.0 mL of 0.500 M NaOH to the formic acid/sodium formate buffer. What is the new pH?

pH = pKa + log ([A-]/[HA]) = 4.11 (started at 4.05) In water, pH would change from 7 to 13.

Group Quiz #13

1) Calculate the pH of a 1.25 L buffer solution made up of 0.50 M acetic acid and 0.50 M sodium acetate. Ka = 1.8 x 10-5 2) What is the pH of the solution when 25.00 mL of 0.40 M NaOH is added to the buffer?

pH Titration Curves
Strong Acid-Strong Base Titrations:
The equivalence point is the point at which equimolar amounts of acid and base have reacted (review 1st semester notes on calcs). Graph generated with pH probe Figure 15.6

pH Titration Curves
4 key points on a titration curve
At the beginning (before titrant is added) Before the equivalence point At the equivalence point After the equivalence point

Strong Acid-Strong Base

Draw 4 beakers. 1) Draw 2 moles HCl. 2) Draw what happens when 1 mole NaOH is added. 3) Draw what happens when 2 moles NaOH are added. 4) Draw what happens when 3 moles NaOH are added.

Consider titrating 20.00 mL of 0.200 M HCl with 0.100 M NaOH. Find equiv. pt. first!
M= mol 1000 mmol mmol = = L 1000 mL mL

HCl + NaOH Titration

1) 0 mL NaOH, pH is calculated from strong acid. [H3O+] = 0.200 M
pH = -log (0.200) = 0.70

HCl + NaOH Titration

3) 40.00 mL NaOH added; at the equivalence point, neutral salt and water in solution.
mmol acid = mmol base pH = 7 (always 7 for strong acid-strong base!)

2) 5.00 mL NaOH, acid is still in excess; but by how much?

mmol acid mmol base (0.200 M)(20.00 mL) (0.100 M)(5.00 mL) [H3O+] = mmol / total solution volume [H3O+] = 3.50 mmol / 25.00 mL = 0.140 M pH = -log (0.140) = 0.85

4) 50.00 mL NaOH added, base in excess. By how much?

mmol base mmol acid (0.100 M)(50.00 mL) (0.200 M)(20.00 mL) 1.00 mmol base excess / 45.00 mL = 0.01429 M NaOH pOH = -log (0.01429) = 1.85, pH = 12.15

Problems 15.13, 15.14

Weak Acid-Strong Base

Ascorbic acid in flask, KOH is titrant in buret

Weak Acid-Strong Base

Draw 4 beakers. 1) Draw 2 moles weak acid. 2) Draw what happens when 1 mole KOH is added. 3) Draw what happens when 2 moles KOH are added. 4) Draw what happens when 3 moles KOH are added.

Find pH at 4 pts.
Figure 15.8 shows strong and weak acids. Titrate 50.00 mL of 0.100 M ascorbic acid w/ 0.150 M KOH. Find eq. pt., Ka, pKa, and mmols of acid first

Weak Acid-Strong Base

4 regions in titration curve Before adding base: 0.00 mL base Before equivalence point: 10.00 mL base At equivalence point: ???? mL base After equivalence point: 50.00 mL base

Weak Acid-Strong Base

Initial pH before adding base. This is a weak acid. How do we find the pH of a weak acid?
Ka = Initial Change Equilibrium HA 0.100 M -x 0.100 - x H2O H3O+ 0 +x x A0 +x x

Weak Acid-Strong Base

Before equiv. pt.: this is the buffer zone (both weak
acid and its conjugate base are present).

Weak Acid-Strong Base

Before equiv. pt.: 10.00 mL base
Excess acid: 5.00 mmol acid 1.50 mmol base = 3.50 mmol excess acid All strong base is converted to conjugate base: (0.150 M)(10.00 mL) = 1.50 mmol A divide by total volume = 60.00 mL to get concentration Or leave values in moles for Henderson-Hasselbach pH = pKa + log (base/acid) Key Concept Problem 15.15; Problems 15.16, 15.17

Use change table to find mmoles excess acid and mmoles cong. base produced. All strong base is converted to conjugate acid (strong base is completely consumed). [HA] = (mmoles acid mmoles base) / total volume [A-] = mmoles base / total volume pH = pKa + log ([A-] / [HA])

Weak Acid-Strong Base

At equivalence point: Find pH of salt (Ch. 14)
We have seen that the product of a weak acid and a strong base is a basic salt and water. We can expect the pH to be greater than 7. Since all the weak acid has been consumed and converted to its conjugate base at the equivalence point, the mmoles of A- are now known. mmoles A- / total volume = [A-] Conjugate base reacts with water (A- + H2O HA + OH-). Set up ICE table (using Kb) and solve for [OH-] and pH.

Weak Acid-Strong Base

At equivalence point:
5.00 mmol acid and 5.00 mmol base So 5.00 mmol conj. base (A-) in flask with 83.33 mL total volume = 0.0600 M A ICE table: A- + H2O HA + OH Kb = Kw / Ka Kb = (x2/0.0600-x) x = [OH-]; then find pH

Weak Acid-Strong Base

After the equivalence point: Excess OHions
More than enough base is added to react with all the acid in the flask. No HA remains, it is all converted to A-. pH is determined primarily from excess [OH-]. [A-] is a minor contributor and doesnt need to be calculated. [OH-] = (mmoles base mmoles acid)/ total volume

Weak Acid-Strong Base

After the equivalence point:
50.00 mL of 0.100 M acid (5.00 mmol) and 50.00 mL of 0.150 M base (7.50 mmol) 7.50 mmol OH- added 5.00 mmol acid present = 2.50 mmol remaining OH divide by total volume = 0.0250 M OH pOH = -log (0.09091 M) = 1.60 pH = 14 1.60 = 12.39

Group Quiz #14

Exactly 50.00 mL of 0.20 M hydrazoic acid (Ka = 1.9 x 10-5) are titrated with a 0.15 M KOH solution. Calculate the pH when 66.67 mL of base have been added:

Half Equivalence Point

33.34 mL base added (half the volume needed to get to equivalence point): [HA] = (10.00 mmol 5.00 mmol) [A-] = 5.00 mmol [HA] = [A-] pH = pKa + log ([A-]/[HA]) = pKa

Animations:
http://www.chembio.uoguelph.ca/educmat/chm19104/chemtoons/chemtoons.htm

Weak Base-Strong Acid

Figure 15.10

Acid-Base Indicators

Calculations are similar to weak acid/strong base; opposite values; extra steps to find pH values. See pages 613 - 615 for outline.

Polyprotic Acid Titrations

One eq. pt. for each proton 2 eq. pts. and 2 half eq. pts. Figure 15.11 Alanine with NaOH

Diprotic Acid Titration

A: acid in water B: pKa1; 1st H removed; 50% H2A, 50% HA C: 1st equiv. pt. (HA-) D: pKa2; 2nd H removed; 50% HA-, 50% A2 E: 2nd equiv. pt. (A2-), all acid reacted F: only excess base

Complex Ion Equilibria

Formation of complex ions can increase solubility of an insoluble salt Complex ion: ion containing a central metal cation bonded to one or more molecules or ions which are called ligands. The ligands act as Lewis bases (e.g. NH3, H2O, OH-)

16.4 Complex Ion Equilibria

Lewis acid-base reactions also reach a state of equilibrium Metal ion + ligand complex ion Kf = [complex ion]/[metal ion][ligand] (formation constant) Hg2+ + 4I- HgI42 Kf = [HgI42-]/[Hg2+][I-]4

Complex Ion Equilibria

Complex ions are often formed stepwise: Hg2+ + I- HgI+ Kf1 = [HgI+]/[Hg2+][I-] = 7.9 x 1012 HgI+ + I- HgI2 Kf2 = [HgI2]/[HgI+][I-] = 1.0 x 1011 HgI2 + I- HgI3Kf3 = [HgI3-]/[HgI2][I-] = 5.0 x 103 HgI3- + I- HgI42Kf4 = [HgI42-]/[HgI3-][I-] = 2.5 x 102
Demo: orange tornado

Complex Ion Equilibria

Add all four equations together: Hg2+ + 4I- HgI42Kf = [HgI42-]/[Hg2+][I-]4 Kf = Kf1 x Kf2 x Kf3 x Kf4 = 1.0x1030 Values of Kf are listed in Table 15.4; they have a wide range of values and thus of stabilities. Unlike Bronsted-Lowrey polyprotic acids, successive Kf values may not differ by large factors, so there may be many species coexisting. See Figure 15.11.

Solubility equilibria
Dissolution of slightly soluble salts in water
important biological examples:
tooth decay - tooth enamel dissolves in acidic soln formation of kidney stones - salts precipitate in kidney

15.10 Solubility Equilibria

Many ions combine to form solid precipitates in aqueous solutions. (Solubility rules) These insoluble salts dissolve to a small extent and form a saturated solution. The undissolved solid and the dissociated ions in solution establish an equilibrium system that is characterized by the solubility product constant, Ksp.

Example. The dissolution of AgBr

AgBr(s) Ag+(aq) + Br -(aq) Ksp = [Ag+][Br -]
Ksp is the solubility product constant - the equilibrium constant for insoluble salts It is a measure of how soluble a salt is in H2O For salts with the same # of ions, the smaller the Ksp, the less soluble the salt. Table 15.2 shows some Ksp values

Write the solubility equilibrium reactions and Ksp expressions for a) MgF2 b) Ca3(PO4)2. A) MgF2(s) Mg2+(aq) + 2F-(aq) Ksp = [Mg2+][F-]2 B) Ca3(PO4)2 (s) 3Ca2+ (aq) + 2PO43- (aq) Ksp = [Ca2+]3[PO43-]2

Solubility/Ksp Practice
Ksp for silver bromide is 7.7 x 10-13. Calculate the molar and gram solubility (solve for x). The solubility of calcium sulfate is found experimentally to be 0.67 g/L. Calculate the value of Ksp for calcium sulfate. Ksp for copper (I) oxide is found to be 2.0 x 10-15. Calculate the molar and gram solubility. The solubility of calcium hydroxide is 0.233 g/L. Calculate Ksp. Worked example 15.8 15.10, Problems 15.21 15.24

Solubility/Ksp Practice
AgBr: x = 8.8 x 10-7 M; x = 1.6 x 10-4 g/L CaSO4: Ksp = 2.4 x 10-5 Cu2O: x = 7.9 x 10-6 M; x = 1.1 x 10-3 g/L Ca(OH)2: Ksp = 1.24 x 10-7

Solubility
Ksp can be used to calculate the solubility, which can be compared for any salts. Solubility (S) = molar concentration of dissolved salt; ion concentrations are related to this by their coefficients. Examples: AgCl: [Ag+] = S [Cl-] = S Ksp = (S)(S) Ag2S: [Ag+] = 2S [S2-] = S Ksp = (2S)2(S) Fe(OH)3: [Fe3+] = S [OH-] = 3S Ksp = (S)(3S)3

Common Ion Effect

Solubility is decreased when a common ion is added AgCl(s) Ag+(aq) + Cl-(aq) Common ion effect: add more Cl- to precipitate Ag+ from solution. Saturated solution of AgCl: Find (x) Ksp = 1.70 x 10-10 Add 0.100 M Cl 0.100 >> 1.30 x 10-5, so [Cl-]= 0.100 M

What is the new [Ag+]? Note this is x in ICE!

Common Ion Effect

What will happen if I add solid NaF to a solution of saturated SrF2? SrF2(s) Sr2+(aq) + 2F-(aq) Problem 15.101: a) Calculate the molar solubility of strontium fluoride in pure water (Ksp = 4.3 x 10-9).

Common Ion Effect

SrF2(s) Sr2+(aq) + 2F-(aq) (in water) Equil: x 2x Ksp = [Sr2+][F-]2 = 4.3 x 10-9 x = 1.0 x 10-3 M SrF2(s) Sr2+(aq) + 2F-(aq) (in NaF) Initial: 0 0.010 Equil: x 0.010 + 2x Ksp = [Sr2+][F-]2 = 4.3 x 10-9

Calculate the molar solubility of strontium fluoride in 0.010 M sodium fluoride.

x = 4.3 x 10-5 M

Worked ex 15.11, Problem 15.25

Effect of pH on Solubility
Addition of an acid can increase the solubility of an insoluble basic salt. E.g. CaF2(s) Ca2+(aq) + 2F-(aq) Add strong acid (e.g. HCl) provides H3O+ ions: H3O+ + FHF + H2O Adding H+ causes [F-] , equilibrium shifts right to form more F- & solubility of CaF2 .

Group Quiz #15

Calculate the solubility, both molar and gram, of copper(II) hydroxide. Ksp = 1.6 x 10-19 Calculate the molar solubility of copper(II) hydroxide when 0.10 M copper(II) nitrate is added.

10

pH and solubility
E.g. For the following salts, predict whether the salt will dissolve in an acidic solution. A. AgBr _____________ B. CdCO3 _____________ C. PbCl2 _____________ D. BaS _____________

Adding NH3 to AgCl solution increases the solubility of AgCl:

1) AgCl(s) Ag+(aq) + Cl-(aq) K1 = 1.7 x10-10 +(aq) + 2NH (aq) Ag(NH ) +(aq) K = 1.6 x 107 2) Ag 3 3 2 2 3) AgCl(s) + 2NH3(aq) Ag(NH3)2+(aq) + Cl-(aq)

Knet = K1 x K2 = 2.7 x 10-3

Mixture of AgCl and AgBr can be separated: 5 M NH3 dissolves AgCl, but not AgBr.

Precipitation of Ionic Cmpds

Note: book refers to IP, same idea as Q (value of concentration ratios NOT necessarily at equilibrium) Compare Q and K. System will shift until Qsp = Ksp (a saturated solution) Example: We want to know if precipitate will form when 0.150 L of 0.10 M lead (II) nitrate and 0.100 L of 0.20 M sodium chloride are mixed? Find Qsp and relate it to Ksp.

Precipitation of Ionic Cmpds

Worked Example 15.14: Will a precipitate form when 0.150 L of 0.10 M lead (II) nitrate and 0.100 L of 0.20 M sodium chloride are mixed? What is the precipitate that will form? What are Ksp and the equilibrium expression? Find total concentration of each ion once mixed. Problem 15.29

Precipitation
PbCl2(s) Pb2+(aq) + 2Cl-(aq) Calculate moles of each ion. Convert moles to concentration using total volume. Plug concentrations into Qsp equation. If Qsp > Ksp, rxn shifts left (toward solid) and precipitate will form. If Qsp < Ksp, rxn shifts right (toward ions) and precipitate will not form.

Precipitation of Ionic Cmpds

Q > Ksp Supersaturated; ppt forms Q = Ksp Saturated Q < Ksp Unsaturated; no ppt forms 2.45 mg of magnesium carbonate is placed in 1.00 L of water. Will it all dissolve? Ksp =
4.0 x 10-5

Find molarity of solid. Write equilibrium expression for solubility. Calculate Qsp.

11

Precipitation of Ionic Cmpds

What are the silver and bromide ion concentrations if 0.0244 g of AgBr and 0.0111 g of NaBr are put into 1.00 L of water? Will AgBr dissolve completely? Write solubility equilibrium expressions for AgBr and NaBr. Calculate Qsp. Qsp = [Ag+][Br -] [Ag+] = 1.30 x 10-4 M, [Br-] = 1.30 x 10-4 + 1.08 x 10-4 M Ksp = 7.7 x 10-13 Qsp > Ksp, what does this mean? Not all of the AgBr can dissolve

Group quiz 16
Will a solution containing 4.0 x 10-5 M Cland 2.0 x 10-4 M Ag+ form a precipitate of AgCl? Ksp = 1.70 x 10-10 (Hint: think Q)

Worked example 15.14, Problem 15.29

Qualitative Analysis
Skipping section 15.14: Selective Precipitation 15.15 Qualitative analysis is used to identify unknown ions in a solution.
152LL should read this section before qual lab!

Each ion can be precipitated out by addition of selective reagents. Purely qualitative research, like solving a puzzle.

12