Acid Base Notes

Acids and Bases
Review: Petrucci et al. Chapter 5, section 5-3. Reading: from chapter 16 of Petrucci et al. Required: Sections 16-1 through 16-5, 16-7. Recommended: Sections 16-8 and 16-9. Examples:16-1 through 16-6, 16-10 through 16-13. Assigned problems: Chapter 16 questions 2, 9, 10, 24, 25, 27, 56, 57a-d, 61, 112
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Properties of Acids and Bases

Acids are a group of compounds with certain common properties: sour taste dissolve carbonates with release of CO2 dissolve metals with release of H2 acids contain hydrogen (except for some Lewis acids) Bases also have certain common properties: bitter taste slippery feel Acids and bases neutralize each other.
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Arrhenius Theory of Acids and Bases (16.1)

Acids are substances that produce hydrogen ions, H+, in solution. Bases are substances that produce hydroxide ions, OH!, in solution. Neutralization: Shortcomings: H+ + OH! " H2O
NH3 + HCHO2 ! NH4+ + CHO2!

The Hydrogen Ion in Solution

H+ is a bare proton. !very concentrated charge !interacts strongly with other molecules In water, H+ forms the hydronium ion, H3O+. !H3O+ is usually hydrated by 3-4 water molecules. !We can use either H+ or H3O+ in equations. H3O+ surrounded by 4 water
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molecules, H11O5+
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Brnsted-Lowry Theory (16.2)

An acid is a A base is a. Examples: H3O+ + OH! " 2H2O acid base H2O + H2O " H3O+ + OH! acid base NH3 + HCHO2 ! NH4+ + CHO2! More general than Arrhenius; gives same results in H2O.
Amphiprotic Substances
Amphiprotic substances can act as either an acid or a base. Examples: H2O + H2O " H3O+ + OH! H2PO4! + H2O " HPO42! + H3O+ H2PO4! + H2O " H3PO4 + OH! H2O and H2PO4! are amphiprotic species
Conjugate Pairs of Acids and Bases

NH3 + H2O ! NH4+ + OH! Acids and bases come in pairs. The acid has one more H+ than the base. NH3 and NH4+ are a conjugate pair. NH4+ is the NH3 is the H2O and OH! are another conjugate pair. H2O is the OH! is the
Identifying Conjugate Acids and Bases

Which is the conjugate base of HPO42!? a) OH! b) H2PO4! c) PO43! Which is the conjugate acid of HSO4!? a) H3O+ b) H2SO4 c) SO42!
Base Ionization Constant

NH3(aq) + H2O(l) ! NH4+(aq) + OH!(aq) Ammonia, NH3, acts as a base in this reaction. The equilibrium constant for the transfer of one proton from the solvent to a base is called the base ionization constant, Kb. For NH3 in water at 25 C:
[ NH+ ][ OH ] -5 4 Kb = = 1.8 " 10 [ NH3 ]
[H2O] does not appear in Kb since water is the solvent. The value of Kb depends on the base, the solvent, and the temperature.
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Acid Ionization Constant

CH3COOH(aq) + H2O(l) ! H3O+(aq) + CH3CO2!(aq) Acetic acid, CH3CO2H, acts as an acid in this reaction. The equilibrium constant for the transfer of one proton from an acid to the solvent is called the acid ionization constant, Ka. For CH3CO2H in water:
[H2O] does not appear in Ka since water is the solvent.
[CH3COO ][H3O ] Ka = = 1.8 " 10-5 [CH3COOH]
The value of Ka depends on the acid, the solvent, and the temperature.
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Identifying Ionization Constants

For which reaction is the equilibrium constant a Kb? a) H2PO4! + H2O ! HPO42! + H3O+ b) H2PO4! + OH! ! HPO42! + H2O c) H2PO4! + H2O ! H3PO4 + OH! For which of the above reactions is the equilibrium constant a Ka?
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Self-Ionization (16.3)
H2O (l) + H2O (l) ! H3O+ (aq) + OH! (aq) Water acts as both an acid and a base in this reaction. The equilibrium constant for the transfer of a proton from the solvent to the solvent is called the self-ionization constant. For water at 25 C: KW is also called the ion product or the autoionization constant. Consequences: ! !
Acid: Base: Solvent:
Ka and Kb for Conjugate Pairs

NH4 + H2O !
+
H3O+
+ NH3
[ NH3 ][H3O+ ] Ka = [ NH+ 4]

" [ NH+ ][ OH ] 4 Ka = [ NH3 ]
NH3 + H2O ! NH4+ + OH2H2O ! H3O+ + OH! !

!
KW = [H3O+][OH!]
For any conjugate pair:
The sum of the acid and base ionization reactions equals the self-ionization reaction for the solvent (water). The product of the acid and base ionization constants equals the self-ionization constant for the solvent (water). Example:
Self-Ionization of Water
H2O(l) + H2O(l) ! H3O+(aq) + OH!(aq) For water at 25 C: KW = [H3O+][OH!] = 1.0#10!14 In pure water, [H3O+] = [OH!] = 1.0#10!7 M The minimum concentration of ions in water is 2.0#10!7 M. If [H3O+] > 1.0#10!7 M, then [OH!] < 1.0#10!7 M, If [H3O+] < 1.0#10!7 M, then [OH!] > 1.0#10!7 M, Concentrations of H3O+ and OH! can cover a huge range.
The pH Scale
Used to measure the acidity of aqueous solutions. The logarithmic scale covers a wide range of concentrations. pH (potential of hydrogen ion) is defined as the negative of the base-ten logarithm of the hydrogen ion concentration:
For pure water at 25 C: [H3O+] = 1.0#10!7 M, so pH = 7.00. This is a neutral solution. In acidic solutions, [H3O+] > 1.0#10!7 M, so In basic solutions, [H3O+] < 1.0#10!7 M, so
pOH is defined as the negative logarithm of the hydroxide ion concentration:
pOH and pKW
pKW is defined as the negative logarithm of the selfionization constant of water:
Since
KW = [H3O+][OH!] = 1.0#10!14
!log(KW) = !log[H3O+] ! log[OH!] = !log(1.0#10!14)

pH and pOH
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Interpreting pH and pOH

For each of the following, identify whether the solution is a) acidic b) neutral c) basic (1)! pH = 9.55 (2)! pOH = 8.52 (3)! pH = 7.00 (4)! pOH = 3.58
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pKa is defined as the negative logarithm of an acid ionization constant: pKa = !log(Ka) Example: NH4+ + H2O ! H3O+ + NH3 Ka=5.6#10!10 pKb is defined as the negative logarithm of a base ionization constant: pKb = !log(Kb) Example: NH3 + H2O ! NH4+ + OH! Kb=1.8#10!5
pKa and pKb
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Strong Acids and Bases

Strong acids and bases ionize almost completely in water at ordinary pHs (0 < pH < 14). Common strong acids: hydrogen halides (except HF) and some oxyacids. Common strong bases: hydroxides of the alkali metals and alkaline earths.
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pH of a Strong Acid (or Base) Solution

Find pH and pOH for a 0.010 M solution of HNO3. HNO3 + H2O ! H3O+ + NO3! Solution:
Watch out: This only works if [H3O+] is much greater than 1.0#10!7 M. Use reasoning above: What is the pH of a 1.0#10!8 M solution of HNO3?
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Non-aqueous Solvents
HClO4, HI, HBr, HCl, H2SO4 and HNO3 are strong acids. In water, we can not tell which is stronger ! they all ionize completely. Strong acids can be differentiated by using a solvent that is a weaker base than water.
In diethylether, HClO4 ionizes completely. It is a stronger acid than HCl.

Weak Acids and Bases

Weak acids and bases are usually partially ionized in water at ordinary pHs (0 < pH < 14). Some weak acids (0 < pKa <14) HF, HOCl, HNO2, carboxylic acids. Some weak bases (0 < pKb <14) NH3, amines, aniline
nitrous acid Ka = 7.2#10!4
Relative Strengths of Acids and Bases

The strength of an acid is determined by its pKa. lower pKa ! higher pKa ! The strength of a base is determined by its pKb. lower pKb ! higher pKb ! For a conjugate pair, pKa + pKb = 14.00. So The stronger an acid, The stronger a base,
Conjugates of Weak Acids and Bases

The conjugate base of a weak acid is a) a strong base b) a weak base c) pH neutral (no effect on pH)
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Solubility and Equilibrium Calculations

Review: Petrucci et al. Chapter 5, sections 5-1 and 5-2. Reading: Petrucci et al. Chapter 15, section 15-7. Examples: 15-9 Assigned problems: Chapter 15 questions 15, 32, 63.
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Equilibrium Calculations
Many reactions rapidly reach equilibrium, including: !acid/base reactions !salts entering solution To fully understand these, we must be able to calculate composition from equilibrium constants. Basic principles: !stoichiometry !dynamic equilibrium
The ICE Table - Section 15.7

Provides a systematic way of doing these calculations. (1) Write out the balanced chemical reaction. (2)!Under each species, enter: ! The Initial concentration of the species. ! The Change in concentration in moving to equilibrium. This will be in terms of some unknown quantity. ! The Equilibrium concentration (depends on the unknown). (3) Substitute in the equilibrium expression and solve for the unknown.
ICE Table - Example

2SO3(g) ! 2SO2(g) + O2(g) Initially, 0.0200 mol of SO3 are put into an evacuated 1.52 L vessel. At equilibrium at 900 K, there are 0.0142 mol SO3. Find KP (1) (2) (3)
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Variations in the ICE Table

The ICE table is based on moles. Other quantities (concentrations, partial pressures) may be used if they are strictly proportional to moles. Examples: !Concentration = n/V may be used if V is fixed. !Partial pressure may be used if T and V are fixed since PV=nRT
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Using Partial Pressure - Example 15.11

NH4HS(s) ! NH3(g) + H2S(g) KP = 0.108 Excess solid NH4HS is placed in an evacuated flask. Find the partial pressures of NH3 and H2S at equilibrium. Solution: KP = PNH3 PH2S
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A Trickier Problem - Example 15.11

N2O4(g) ! 2NO2(g) KC = 4.61#10!3 0.0480 mole of NO2 is placed in a 0.372 L flask. Find the moles of N2O4 at equilibrium. Reaction N2O4(g) ! 2NO2(g) Initial 0.0000 mol 0.0480 mol Change +x mol -2x mol Equilibrium +x mol (0.0480 - 2x) mol KC = [NO2]2/ [N2O4] = ((0.0480 ! 2x)/V)2 / (x/V) How can we solve this for the unknown number of moles, x?
Methods of Finding the Unknown Concentration

(1) Make a simplifying assumption. (2) Change the starting point, then make a simplifying assumption. For both (1) and (2): !Must think about what is happening physically. !Must test that the assumption is valid. !Does not always work. (3) Use the quadratic equation. !Requires minimal thinking. !Does not always work. (4) Use the method of successive approximations. !Can be tricky to set up right. !Always works if set up right.
Making a Simplifying Assumption

N2O4(g) ! 2NO2(g) KC = 4.61#10!3, V = 0.372 L, initially 0.0480 mole NO2 KC = [NO2]2/ [N2O4] = ((0.0480 ! 2x)/V)2 / (x/V) Try assuming that only a little N2O4 is formed so that 2x << 0.0480: " x $ (0.0480)2 / (VKC) = 1.34 mol 2x is not small compared to 0.0480 mol. x = 1.34 mol implies that [NO2] < 0. Impossible! Conclude:
Changing the Starting Point

If the equilibrium amount of N2O4 is not small, then maybe the equilibrium amount of NO2 is small. Start by changing all the NO2 into N2O4. Reaction N2O4(g) ! 2NO2(g) Old Initial 0.0000 mol 0.0480 mol New Initial 0.0240 mol 0.0000 mol Change !x mol +2x mol Equilibrium (0.0240!x) mol +2x mol KC = [NO2]2/ [N2O4] = (2x/V)2 / ((0.0240!x)/V)
Making the Simplifying Assumption

KC = [NO2]2/ [N2O4] = (2x/V)2 / ((0.0240!x)/V) Try assuming that only a little NO2 is formed so that x << 0.0240: " 4x2 $ 0.0240VKC KC = 4.61#10!3, V = 0.372 L So x $ 0.00321 and nN2O4 = 0.0240 ! x = 0.0208 mol Check how much of the N2O4 has decomposed: x/0.0240 = 0.13, so assumption may be OK.
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Using the Quadratic Equation

If 0 = ax2 + bx + c then From previous slide: 0 = 4x2 + VKCx ! 0.0240VKC a=4 b = VKC c = !0.0240VKC x = 0.00300 and nN2O4 = 0.0210 mol The approximation was pretty good. !This is exact, so why not always use it ? ! !
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A Case Where the Quadratic Equation Fails

Cl(g) + O2(g) ! ClO2(g) KP = 19 at 190K If there are initially 0.040 atm O2 and 1.0#10!11 atm Cl, calculate the partial pressure of ClO2 at equilibrium. Reaction Initial Change Cl(g) + 1.0#10!11 !x O2(g) ! 0.040 !x ClO2(g) 0.0000 atm +x +x atm atm
Equilibrium 1.0#10!11!x 0.040!x
Assuming x << 0.040 gives pClO2 = x = 4.3#10!13 atm. The quadratic equation fails unless you keep more than 11 significant figures in the intermediate results.
Acid-Base Equilibrium Calculations

pH is a critical parameter for many chemical reactions. Acids (and bases) often react very differently from their conjugate bases (and acids). In doing equilibrium calculations: !Identify the important species and reactions. !Make use of mass balance and equilibrium constants (ICE table). !Think about what a reasonable answer would be. !Make simplifying assumptions, if possible.
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Ka of a Weak Acid from Solution pH

A 0.150 M solution of HOCl has pH = 4.18. Find Ka Solution: HOCl + H2O ! H3O+ + OCl! Ka = [H3O+] [OCl!] / [HOCl]
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pH of a Weak Base (or Acid) Solution

For NH3(aq), pKb = 4.75. Find the pH of a 0.025 M aqueous solution of NH3. Solution: Kb = [OH!] [NH4+] / [NH3] = 10!4.75 = 1.8#10!5 Let Cb = initial concentration of base = 0.025 M Reaction NH3 + H2O ! OH- + NH4+ Initial Cb 0 0 M Change !x +x +x M Equil. Cb!x x x M Kb = x2/(Cb!x) Must have 0 < x < Cb. Now solve for x.
Weak Base Solution - continued

Previous slide: Kb = x2/(Cb!x), Cb = 0.025 M, Kb =1.8#10!5 Approximation: Since the base is weak, x might be small.
Check: x/Cb = 0.027, so assumption is OK. [OH-] = x = 6.7#10!4 M ! Using the quadratic equation gives Because concentrations are approximations to activities, the accuracy is worse than this.
Degree of Ionization
The extent to which an acid (or base) ionizes depends on the pH and the pKa (or pKb). HA + H2O ! H3O+ + A! !If pH = pKa, [A!] = [HA]; !If pH > pKa, [A!] > [HA]; !If pH < pKa, [A!] < [HA]; At any given pH, the lower the pKa, the greater the degree of ionization.
Ka = [H3O+][A!]/[HA]
Rearrange: [A!] / [HA] = Ka / [H3O+] = 10(pH!pKa)
Degree of Ionization - Significance

If you can recognize whether an acid or base is mostly ionized or slightly ionized, you can tell what approximation to make. Consider a 0.025 M aqueous solution of NH3 (pKb = 4.75). What will be the pOH if the NH3 fully ionizes? Will the degree of ionization be high or low? Consider a 1.0#10!6 M aqueous solution of NH3. What will be the pOH if the NH3 fully ionizes? Will the degree of ionization be high or low? In very dilute solutions, weak bases and acids fully ionize.
Dilute Solution of a Weak Base (or Acid)

For NH3(aq), pKb = 4.75. Find the pH of a 1.0#10!6 M aqueous solution of NH3. Solution: Kb = 1.8#10!5 >> [NH3]; degree of ionization is large. Let Cb = initial concentration of base = 1.0#10!6 M Reaction NH3 + H2O ! OH- + NH4+ Initial Change Equil.
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Very Dilute Solutions

Q: What is the pH of a 1.0#10!6 M solution of HNO3? A: pH = Q: What is the pH of a 1.0#10!7 M solution of HNO3? A: pH = Q: What is the pH of a 1.0#10!8 M solution of HNO3? A: pH =
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Hydrolysis of Salts - Section 16.7

Salts dissolve in water to produce ions. The ions might undergo proton transfer with water. The conjugate base of a weak acid is a weakly basic anion. The conjugate acid of a weak base is a weakly acidic cation. In aqueous solution, salts can act as acids and/or bases. These are called hydrolysis reactions. Example: dissolution: hydrolysis:
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Hydrolysis of Salts - continued

Example: dissolution: NaF(s) ! Na+(aq) + F!(aq) hydrolysis: F-(aq) + H2O(l) ! OH!(aq) + HF(aq) NaF acts as a base in solution The Na+ ion in solution is a) acidic b) basic c) pH neutral
pH of Salt Solutions
Hydrolysis reactions change the pH. Whether a salt acts as an acid or a base depends on the strengths of the acid and base that form the salt. Salt of a strong acid and a strong base Example: MgBr2 is a salt of HBr and Mg(OH)2. Dissolution: MgBr2(s) ! Mg2+(aq) + 2Br!(aq) Hydrolysis: Mg2+ + 2H2O ! 2H3O+ + Mg(OH)2 Hydrolysis: Br! + H2O ! OH! + HBr
pH of Salt Solutions - continued

Salt of a strong acid and a weak base NH4NO3 is a salt of HNO3 and NH3 (pKb=4.74) dissolution: NH4NO3(s) ! NH4+(aq) + NO3!(aq) hydrolysis: NH4+ + H2O ! H3O+ + NH3 hydrolysis: NO3! + H2O ! OH! + HNO3
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Salt of a weak acid and a strong base NaF is a salt of HF (pKa=3.18) and NaOH. dissolution: NaF(s) ! Na+(aq) + F!(aq) hydrolysis: Na+ + H2O ! H3O+ + NaOH hydrolysis: F- + H2O ! OH! + HF
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Salt of a weak acid and a weak base NH4F is a salt of HF (pKa=3.18) and NH3 (pKb=4.74). dissolution: NH4F(s) ! NH4+(aq) + F!(aq) hydrolysis: NH4+ + H2O ! H3O+ + NH3 hydrolysis: F! + H2O ! OH! + HF Both ions hydrolyze. Is the solution acidic or basic? For NH4+, pKa = 14.00 ! 4.74 = 9.26 For F!, pKb = 14.00 ! 3.18 = 10.82
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Buffers and Acid-Base Titrations

Reading: Sections 17-2 through 17-4 and 17-6 of Petrucci Review: Section 5-7. Examples: 17-3 through 17-6; 17-7(a)&(c), 17-8(a),(c)&(d). Problems: Chapter 17 questions 2, 6, 7, 8, 9, 11a-e, 16, 98 Suggested problems: Chapter 17 questions 43, 44, 45, 46.
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Adding Base to a Weak Acid Solution

HF is a weak acid; it partially ionizes in water: HF + H2O ! H3O+ + F! pKa = 3.18 What effect does adding NaOH have on this equilibrium? NaOH " Na+ + OH! H3O+ + OH! " H2O Consequences: ! !
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Adding Acid to a Salt of a Weak Acid

NaF is a salt of a weak acid (HF). It hydrolyzes in water: F! + H2O ! OH- + HF pKb = 10.82 What effect does adding HCl have on this equilibrium?HCl + H2O " H3O+ + Cl! H3O+ + OH! " 2H2O Q: Compared to adding HCl to pure water, when HCl is added to a solution of NaF, the decrease in pH is a) smaller b) the same c) larger CHEM 1001 3.0 Acids & Bases 55
Solution of a Weak Acid and its Salt (17.2)

Example: Solution of HF and NaF in water. HF + H2O ! H3O+ + F! pKa = 3.18 !Adding acid shifts the equilibrium to the left. This largely offsets the reduction in pH. !Adding base shifts the equilibrium to the right. This largely offsets the increase in pH. !Significant amounts of acid or base can be neutralized since the solution contains substantial [HF] and [F!]. !
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Acid-Base Buffer Systems

A solution containing a weak acid and its conjugate base:
Benzoic acid
benzoate
Acetic acid
Acetate
The conjugate base is added as a salt or by adding a strong base to the weak acid. OR A solution containing a weak base and its conjugate acid: Trimethylammonium added as salt or by adding a strong acid to the weak base.
Applications of Buffer Solutions

Many chemical processes require control of pH. !The rates and mechanisms of many chemical reactions are sensitive to pH. !pH affects the structure of and charges on proteins. !The activity of enzymes is very sensitive to pH. !Human blood is buffered to a pH of 7.4 !Many industrial chemical processes require controlled pH.
Acid-Base Buffers
An acid-base buffer is a solution that is resistant to changes in pH. When an acid or base is added to a buffer, the change in pH is small. For a solution to be an effective buffer, it must contain: (1) !This allows for the neutralization of both acids and bases. (2) !Otherwise most of the acid or base has reacted with H2O.
pH of a Buffer Solution
For a mixture of an acid and its conjugate base: Reaction HA + H2O ! H3O+ + Initial [HA]0 0 Change !x x Equil. [HA]0!x x A! [A!]0 x [A!]0+x
Simplifying assumptions from previous slide: x << [HA]0 and x << [A!]0 Ka = [H3O+][A!]/[HA] $ x [A!]0 / [HA]0 [H3O+] = x = Ka [HA]0 / [A!]0
pH of a Buffer Solution - continued

In a buffer, we have: [H3O+] = Ka [HA] / [A!] Take the negative logarithm of both sides: !log[H3O+] = !logKa ! log([HA]/[A!]) pHbuffer = pKa + log([A!]/[HA]) This is called the Henderson-Hasselbalch equation. ! !
Buffer Range
In a buffer we need comparable amounts of HA and A!, say: 0.1 < [A!] / [HA] < 10 Taking logarithms: !1.0 < log([A!]/[HA]) < 1.0 Substitute into the Henderson-Hasselbalch equation: pHbuffer = pKa + log([A!]/[HA]) pHbuffer = pKa 1.0 Conclusion:
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Preparing Buffer Solutions

Chemists and biologists often need to prepare solutions with a specific, constant pH. To make a buffer with a specific pH: !Find an acid with a pKa within 1 unit of the required pH. !Use the Henderson Hasselbach equation to determine the required ratio of acid to conjugate base. !Make the buffer solution. !Use a pH meter to check the pH. Add acid or base as needed to get the correct pH.
Preparing a Buffer
Acid Citric Acid Benzoic acid Acetic acid Carbonic acid Ammonium ion Phenol pKa 3.13 4.20 4.77 6.36 9.25 9.89
To prepare a buffer with pH = 3.50, which acid should be used? In order to get the correct pH, what do we add to this acid?
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Preparing a Buffer - Example

To prepare a buffer with pH = 3.50: The pKa of Citric acid is closest to Acid pKa desired pH. Citric Acid 3.13 Find ratio of acid to base: Benzoic acid 4.20 Acetic acid 4.77 [HA]/[A!] = [H3O+]/Ka = 10pKa!pH Carbonic acid 6.36 !] = 103.13!3.50 = 0.43 [HA]/[A Ammonium ion 9.25 Phenol 9.89 if [A!] = 0.10 M (>100Ka) then [HA] = 0.043 M. For one litre of buffer solution, add 0.043 mol of citric acid and 0.100 mol of citrate. OR 0.143 mole of citric acid and 0.100 mol of NaOH
Adding Acids or Bases to a Buffer

Henderson-Hasselbalch equation: pH = pKa + log([A!]/[HA]) !Adding an acid decreases [A!] and increases [HA]. So it lowers the pH. !Adding a base increases [A!] and decreases [HA]. So it raises the pH. !Qualitatively, this is just like any other solution. But in a buffer, the pH changes are much smaller. Q: How much does the pH change when acid or base is added? A: Calculate the changes in [HA] and [A!].
pH Change in a Buffer
Find the pH of a solution after adding 3.0#10!3 mol HCl to 1.0 litre of water. [H3O+] =
Given a citric acid-citrate buffer with [A!]0 = 0.100 M, [HA]0 = 0.043 M, and pH = 3.50 ([H3O+] = 3.16#10!4 M). Find the pH after adding 3.0#10!3 mol HCl to 1.0 litre of this buffer.
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pH Change in a Buffer
Solution: Calculate the changes in [HA] and [A!] HA [A!] = [HA] = pH = pKa + log([A!]/[HA]) + H 2O ! H 3O + + A!
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Effect of Buffer Concentration

Given a citric acid-citrate buffer with [A!]0 = 0.100 M, [HA]0 = 0.043 M, and pH = 3.50. What happens to the pH if we double both [A!]0 and [HA]0? a) pH increases b) pH decreases c) pH remains about the same
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Buffer Capacity
The buffer capacity is the amount of acid or base that the buffer can neutralize. pH = pKa + log([A!]/[HA]) Increasing both [A!]0 and [HA]0 does not change the pH (Only approximately true since we really should be using activities instead of concentrations.) However, the buffer capacity will increase, therefore: ! !
Identifying Buffer Solutions

Which of the following could be buffers? 1) KH2PO4 and H3PO4 2) NaClO4 and HClO4 3) C5H5N (pyridine) and C5H5NHCl 4) Na2CO3 and NaHCO3 5) NaOH and HCl 6) NaOH and H3PO4
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Determining pH - Section 17.3

Two widely used methods: !A pH meter uses an electrode that produces a voltage that is a linear in pH. !Acid-base indicators change color depending on pH. An indicator is a weak acid that has a different color than its conjugate base. Hin + H 2O ! H 3O + + In! acid color base color Acid color dominates for pH Base color dominates for pH
Acid-Base Indicator Examples

pH = Phenolphthalein pKa = 9.1 pH =
Bromthymol blue pKa = 7.1

Phenolphthalein
Colourless acid form HIn-
Pink base form In2-
The color change is due to a change in electronic structure when the acidic proton is removed (and H2O is lost).
Phenolphthalein
Colourless acid form HIn-
Pink base form In2-
The color change is due to a change in electronic structure when the acidic proton is removed (and H2O is lost).
Acid-Base Titrations - Section 17.4

Acid-base titrations are used to analyze the quantity of acid or base in an unknown sample. acid + base "H2O + salt At the equivalence point: moles of acid = moles of base ! VA = volume of acid of unknown concentration CA CB = known concentration of the base VB = volume of base added at equivalence.
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Acid-Base Titration Terminology

The titrant is the strong acid or strong base solution that is added in a measured volume. The equivalence point can be detected by using a pH meter. The end point is an experimental approximation of the equivalence point, identified with an acid-base indicator. The titration error is the difference between the equivalence point and the end point. How close is the end point to the equivalence point? What indicator should be used?
Titration Curve of a Strong Acid
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pH during Titration of a Strong Acid

During the titration of a strong acid with a strong base: !Initial pH !During the titration, the acid is gradually neutralized. Before the equivalence point: !At the equivalence point: pH = 7 !Beyond the equivalence point:
!What about near the equivalence point?

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pH near the Equivalence Point

Titration of 25.00 mL of 0.100 M HCl with 0.100 M NaOH. At the equivalence point: VB = 25.00 ml and pH = 7. Find the pH at VB = 24.95 ml (1 drop short of equivalence). Solution: nA = nB = [H3O+] = By same method, one drop past equivalence, pH = Conclusion: Near equivalence, pH changes very rapidly.
Titration of a Weak Acid

The titrant must be a strong base. The initial pH is determined by the concentration and pKa of the acid. During the titration, the acid is gradually converted to its conjugate base. The solution is a buffer.
At half way to the equivalence point,
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Equivalence Point for Titration of a Weak Acid

At the equivalence point in the titration of a weak acid with a strong base, all the weak acid is converted to the conjugate base. HA + OH- " A- + H2O The question then is: what is the pH of the weak BASE? Near the equivalence point, the change in pH is much less dramatic than in the titration of a strong acid.
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Titration Curve of a Weak Acid
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pH during Titration of a Weak Acid

Titrating 25.00 mL of 0.100 M acetic acid (CH3COOH, pKa = 4.74) with 0.100 M NaOH. Initial pH: HA + H2O ! H3O+ + A!
Buffer region (10% to 90% neutralized): where nA = CAVA, nB = CBVB At the half-equivalence point:
Titration of a Weak Acid - continued

At the equivalence point: The solution is that of a salt of the conjugate base. This hydrolyzes: A! + H2O ! HA + OH!
"! Suitable indicators: thymol blue (pKa=8.8) phenolphthalein (pKa=9.1) Beyond the equivalence point, the pH is determined by the amount of excess base.
Titration of a Weak Base

One should titrate a weak base with a) a weak acid b) a strong acid c) a strong base At the half equivalence point in the titration a) pH = 7 b) pH = pKb for the base c) pH = pKa for the conjugate acid At the equivalence point in the titration a) pH < 7 b) pH = 7 c) pH > 7
Solubility and Equilibrium Calculations

Reading: Petrucci et al. Chapter 18, sections 18-1 through 18-5. Examples: 18-1 through 18-4 Assigned problems: Chapter 18 questions 1, 2, 4a-c, 15, 16a-b, 31, 37.
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Solubility
!Some liquids can dissolve in each other in any amount. Example: ethanol and water. !Many liquids can only dissolve in each other to only a limited degree. Example: benzene and water. !Solids will dissolve in liquids, but there is always a limit. !Solubility is the amount of a substance that can dissolve in a given amount of another substance (usually a liquid). !Units should be M (mol L!1) but other units are often used (such as grams per 100 mL, mg/mL). !Important for separations and quantitative analysis.
Non-Dissociating Solute
We can treat dissolution as a chemical reaction. Example: sucrose (s) ! sucrose (aq) At 25 C, KC = 1.97 and KC = [sucrose (aq)] The solubility of sucrose in water is 1.97 M. 1.!If [sucrose (aq)] = 1.97 M, the solution is 2.!If [sucrose (aq)] < 1.97 M, the solution is 3.!If [sucrose (aq)] > 1.97 M, the solution is
The Solubility Product Constant - Section 18.1

When salts dissolve in water, they usually dissociate. The equilibrium constant for this process is called the solubility product constant, Ksp. Example: AgCl(s) ! Ag+(aq) + Cl!(aq) Ksp = [Ag+][Cl-] = 1.8#10-10 at 25 C. Q: How much AgCl can dissolve in water at 25 C?
From stoichiometry, At equilibrium The solubility of AgCl is

Calculating Ksp from Solubility - Section 18.2

MgNH4PO3 ! Mg2+(aq) + NH4+(aq) + PO33!(aq) The solubility of MgNH4PO3 is 5.8#10!5 M. Q: Find the value of Ksp for MgNH4PO3.
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Calculating Solubility from Ksp

Mg3(AsO4)2(s) ! 3Mg2+(aq) + 2AsO43!(aq) For Mg3(AsO4)2, Ksp = [Mg2+]3[AsO43!]2 = 2.0#10!20 Q: Find the solubility of Mg3(AsO4)2 (moles of Mg3(AsO4)2 dissolved per liter).
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The Common Ion Effect - Section 18.3

Adding a common ion to a solution of a slightly soluble salt suppresses the solubility of the salt. Examples: AgCl(s) ! Ag+ + Cl! Ksp = 1.8#10!10 Add: NaCl(s) ! Na+ + Cl! Cl! is a common ion. By LeChtelier's principle, adding it shifts the AgCl equilibrium to the left. OR Add: AgNO3(s) ! Ag+ + NO3! The common ion, Ag+, suppresses the solubility of AgCl.
The Common Ion Effect - Example 18.4

PbI2(s) ! Pb2+ + 2I! Q: Ksp = 7.1#10!9 Compare the solubility of PbI2 in water to its solubility in 0.10 M Pb(NO3)2. Find the solubility of PbI2 in water.
(1)
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Example 18.4 - continued

PbI2(s) ! Pb2+ + 2I! Ksp = 7.1#10!9 (2) Find the solubility of PbI2 in 0.10 M Pb(NO3)2. Let S = moles of PbI2 dissolved per liter. At equilibrium: [Pb2+]
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Other Influences on Solubility - Section 18.4

Salt effect - Ions influence each other electrostatically. This causes activities to be lower than concentrations and increases solubility. Specific ion interactions - Can increase or decrease activity. Ion pairs decrease activity and increase solubility. Simultaneous reactions can change concentrations of ions. Example: CaCO3(s) ! Ca2+ + CO32! CO32! + H2O(l) ! OH! + HCO3! Reaction of CO32! with H2O increases solubility of CaCO3.
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Criteria for Precipitation - Section 18.5

The ion product, Qsp, is used to decide if a salt may precipitate. Example: PbI2(s) ! Pb2+ + 2I! Ksp = [Pb2+]eq[I!]2eq Qsp = [Pb2+]init[I!]2init If Qsp < Ksp, the solution is If Qsp = Ksp, the solution is If Qsp > Ksp, the solution is
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Applying the Criteria for Precipitation

Q: 10.0 mL of 0.015 M Pb(NO3)2 are mixed with 20.0 mL of 0.030 M KI. Will a precipitate form? Solution: Pb(NO3)2, KI, and KNO3 are all very soluble.
Q: Will a precipitate form?


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Acids and Bases

CHEM 1001 3.0

Acids & Bases 1

Properties of Acids and Bases

Arrhenius Theory of Acids and Bases (16.1)

NH3 + HCHO2 ! NH4+ + CHO2!

The Hydrogen Ion in Solution

Acids & Bases 4

Brnsted-Lowry Theory (16.2)

Conjugate Pairs of Acids and Bases

Identifying Conjugate Acids and Bases

Base Ionization Constant

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Acid Ionization Constant

[H2O] does not appear in Ka since water is the solvent.

[CH3COO ][H3O ] Ka = = 1.8 " 10-5 [CH3COOH]

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Identifying Ionization Constants

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Acid: Base: Solvent:

Ka and Kb for Conjugate Pairs

[ NH3 ][H3O+ ] Ka = [ NH+ 4]

NH3 + H2O ! NH4+ + OH2H2O ! H3O+ + OH! !

For any conjugate pair:

pOH is defined as the negative logarithm of the hydroxide ion concentration:

pOH and pKW

pKW is defined as the negative logarithm of the selfionization constant of water:

!log(KW) = !log[H3O+] ! log[OH!] = !log(1.0#10!14)

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Interpreting pH and pOH

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pKa and pKb

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Strong Acids and Bases

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pH of a Strong Acid (or Base) Solution

Acids & Bases 21

In diethylether, HClO4 ionizes completely. It is a stronger acid than HCl.

Weak Acids and Bases

nitrous acid Ka = 7.2#10!4

Relative Strengths of Acids and Bases

Conjugates of Weak Acids and Bases

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Solubility and Equilibrium Calculations

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The ICE Table - Section 15.7

ICE Table - Example

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Variations in the ICE Table

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Using Partial Pressure - Example 15.11

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