Acids and Bases Notes
Acids and Bases Notes
Acids Bases
pH<7.0 pH>7.0
taste sour taste bitter
react with metals to produce hydrogen gas feel slippery
pH paper turns red/orange pH paper turns blue/green
phenolphthalein → colourless phenolphthalein → pink
bromothymol blue → yellow bromothymol blue → blue
cabbage juice → pink cabbage juice → blue
pH and pOH
pH (“power of hydrogen”) is a measure of the acidity of a solution: the lower the pH, the more acidic the solution is and the
higher the pH, the more basic the solution is
pOH is a measure of the basicity (ar alkalinity) of a solution: the lower the pOH, the more basic the solution is and the higher
the pOH, the more acidic the solution is
pH or pOH = 7.0 indicates a neutral solution
The pH Scale
Arrhenius Concept
Acid: substance that will dissociate to give H+ ions
Base: substance that will dissociate to give OH- ions
The Ahhrenius concept provides a good description of strong acids and bases
Strong Acids:
HCl → H+ + Cl- hydrochloric acid HNO3 → H+ + NO3- nitric acid
HBr → H+ +Br- hydrobromic acid HIO4 → H+ + IO4- periodic acid
HI → H+ + I- hydroiodic acid H2SO4 → H+ + HSO4- sulphuric acid
HClO4 → H+ + ClO4- perchloric acid HClO3 → H+ + ClO3- chloric acid
Strong Bases:
LiOH → Li+ + OH- lithium hydroxide Ba(OH)2 → Ba2+ + 2OH- barium hydroxide
NaOH → Na+ + OH- sodium hydroxide Sr(OH)2 → Sr2+ + 2OH- strontium hydroxide
KOH → K+ + OH- potassium hydroxide Ca(OH)2 → Ca2+ + 2OH- calcium hydroxide
RbOH → Rb+ + OH- rubidium hydroxide (note: other group II elements are insoluble in water)
CsOH → Cs+ + OH- cesium hydroxide
pH + pOH =14.00
1.0x10-14 = [H+] [OH-]
pH, pOH, and Significant Figures
For pH and pOH, only the digits after the decimal place are significant.
(ie, pH= 10.20 has two significant digits since there are two numbers after the decimal place; pOH = 1.384 has three significant
digits since there are three numbers after the decimal place)
ex. calculate the [H+], pH, pOH, and [OH-] of 0.0020 M HCl
ex. calculate the [OH-], pOH, pH, and [H+] of 0.010 M Sr(OH)2
The Ahhrenius Concept does not adequately describe some compounds that exhibit acidic or basic properties, so a more general
definition is required.
Bronsted-Lowry Model
Acid: a proton (H+) donor
Base: a proton (H+) acceptor
Acid/Base Equilibria
A weak acid or base is one that does not completely dissociate in water; instead it forms an equilibrium with water.
Acids
ex. HA (aq) + H2O (l) U H3O+ (aq) + A- (aq)
acid base conjugate conjugate
acid base
note: the proton is donated by the acid (HA) and accepted by the base (H2O)
The conjugate acid of water is the hydronium ion (H3O+) which has one additional proton and the conjugate base of HA is A-
which has one less proton.
Bases
ex. B (aq) + H2O (l) U OH- (aq) + BH+ (aq)
base acid conjugate conjugate
base acid
note: the proton is accepted by the base (B) and donated by the acid (H2O)
The conjugate base of water is the hydroxide ion (OH-) which has one less proton and the conjugate acid of B is BH+ which has
one additional proton.
Kb values for Common Bases. The higher the Kb value, the stronger the base.
Base Formula/ Conjugate Acid Kb
diethylamine (C2H5)2NH/ (C2H5)2NH2+ 1.3x10-3
ethylamine C2H5NH2/ C2H5NH3+ 5.6x10-4
methylamine CH3NH2/ CH3NH3+ 4.4x10-4
triethylamine (C2H5)3N/ (C2H5)3NH+ 4.0x10-4
ammonia NH3/ NH4+ 1.8x10-5
hydrazine H2NNH2 (or N2H4)/ H2NNH3+ 3.0x10-6
hydroxylamine HONH2/ HONH3+ 1.1x10-8
pyridine C5H5N/ C5H5NH+ 1.7x10-9
aniline C6H5NH2/ C6H5NH3+ 3.8x10-10
ex. NH3 (aq) + H2O (l) U OH- (aq) + NH4+ (aq) [OH − ][ NH 4 + ]
base acid conjugate conjugate Kb =
base acid [ NH 3 ]
ex. Write a Ka/Kb expression for the following acid/base equilibria. Identify the conjugate acid-base pairs.
ex. Complete the following acid-base equilibria. Identify the conjugate acid-base pairs and write a Ka/Kb expression.
ex. When Al3+ is in solution, it forms [Al(H2O)6]3+, the acid equilibrium for this complex is as follows: (Ka = 1.4x10-5)
ex. When Fe3+ is in solution, it forms [Fe(H2O)6]3+. What is the acid equilibrium for this complex? (Ka = 6.0x10-3)
ex. Determine the pOH and pH of a 1.0 M solution of NH3 (Kb = 1.8x10-5).
ex. The pH of a 0.650 M solution of citric acid (H3C6H5O7) is 1.63. Determine Ka.
ex. The pOH of a 0.020 M solution of toluidine (CH3C6H4NH2) is 5.35. Determine Kb.
Percent Dissociation (also called percent ionization)
The percent dissociation of a compound is a measure of the degree of dissociation.
The percent dissociation can be calculated according to the following equation:
amount dissociated
Percent dissociation = x 100% amount dissociated = “x”
initial concentration
ex. Calculate the percent dissociation for a 0.22 M solution of C2H5NH2 (Kb = 5.6x10-4)
ex. A 0.100 M solution of lactic acid (HC3H5O3) is 3.7% dissociated at equilibrium. Calculate the Ka value for lactic acid.
Amphoteric Compounds
amphoteric: a compound that can act as either an acid or a base.
ex. Water is amphoteric: H2O (l) + H2O (l) U H3O+ (aq) + OH- (aq)
note: the autoionization of water produces both a hydronium ion and a hydroxide ion so the resulting solution is neutral.
The equilibrium expression for this reaction is as follows:
K w = [ H 3O + ][OH − ] , where Kw = 1.0x10-14 (Kw is called the dissociation constant of water)
other amphoteric substances include: the hydrogen sulphate ion (HSO4-), the hydrogen sulphite ion (HSO3-), the dihydrogen
phosphate ion (H2PO4-), the hydrogen phosphate ion (HPO42-), the hydrogen sulphide ion (HS-) etc.
K w = K a × Kb Kw = 1.0x10-14, Ka is the acid dissociation constant, and Kb is the base dissociation constant
ex. Which of the following substances is a stronger acid, HF or HCN? Which of the following substances is a stronger base, F-
or CN-?
HF has Ka = 7.2x10-4 and HCN has Ka = 6.2x10-10. Since Ka for HF is greater than Ka for HCN, HF is a stronger acid than HCN.
F- has Kb = 1.0x10-14/7.2x10-4 = 1.4x10-11 and CN- has Kb = 1.0x10-14/6.2x10-10 = 1.6x10-5. Since Kb for CN- is greater than Kb
for F-, CN- is a stronger base than F-.
ex. Which of the following substances is a stronger base, NH3 or C5H5N? Which of the following substances is a stronger acid,
NH4+ or C5H5NH+?
NH3 has Kb = 1.8x10-5 and C5H5N has Kb = 1.7x10-9. Since Kb for NH3 is greater than Kb for C5H5N, NH3 is a stronger base
than C5H5N.
NH4+ has Ka = 5.6x10-10 (given on Ka table) and C5H5NH+ has Ka = 1.0x10-14/1.7x10-9 = 5.9x10-9. Since Ka for C5H5NH+ is
greater than Ka for NH4+, C5H5NH+ is a stronger acid than NH4+.
Comparing Equilibria for Amphoteric compounds
ex. the hydrogen carbonate ion, HCO3- can act as an acid (donating a proton) or a base (accepting a proton)
as an acid: HCO3- (aq) + H2O (l) U H3O+ (aq) + CO32- (aq) Ka = 5.6x10-11
K w 1.0 x10−14
as a base: HCO3- (aq) + H2O (l) U OH- (aq) + H2CO3 (aq) Kb = = −7
= 2.3x10−8
K a 4.3x10
Since Kb>Ka, a solution containing hydrogen carbonate would have a basic pH.
Consider the following reactions and identify the conjugate acid-base pairs.
Note, if the second equilibrium is reversed (and the reciprocal of the equilibrium constant is taken), the two equilibria can add up
to give the overall equilibrium (and the K for the equilibrium can be obtained by multiplying K for each of the reactions)
NH3 (aq) + H2S (aq) U HS- (aq) + NH4+ (aq) K =1.0x10-7 x 1.8x109 = 1.8x102
(note: H3O+ (aq) and H2O (l) are cancelled when the equilibria are added)
An important result is that K>1. This is significant since H2S is a stronger acid than NH4+, therefore the equilibrium position is
driven to the right, favouring the products.
This same result could be derived by considering the compounds that act as bases in the reaction:
NH3 (aq) + H2O (l) U OH- (aq) + NH4+ (aq) Kb = 1.8x10-5
HS (aq) + H2O (l) U OH (aq) + H2S (aq)
- -
Kb = 1.0x10-14/1.0x10-7 = 1.0x10-7
Note, if the second equilibrium is reversed (and the reciprocal of the equilibrium constant is taken), the two equilibria can add up
to give the overall equilibrium (and the K for the equilibrium can be obtained by multiplying K for each of the reactions)
NH3 (aq) + H2S (aq) U HS- (aq) + NH4+ (aq) K =1.8x10-5 x 1.0x107 = 1.8x102 (as determined above)
(note: OH- (aq) and H2O (l) are cancelled when the equilibria are added)
(2) HOCl (aq) + C6H5NH2 (aq) U OCl - (aq) + C6H5NH3+ (aq)
HOCl (aq) + C6H5NH2 (aq) U OCl - (aq) + C6H5NH3+ (aq) K = 3.5x10-8 x 3.8x104 = 1.3x10-3
An important result is that K<1. This is significant since C6H5NH3+ is a stronger acid than HOCl, therefore the equilibrium
position is driven to the left, favouring the reactants.
(again, the K value could also be calculated by considering the compounds acting as bases)
Mixtures of Acids
In general, only the strongest acid will significantly contribute to the concentration of hydronium ions.
ex. Calculate the pH of a mixture containing 0.50 M HCl and 0.50 M HF.
Since HCl is a strong acid and HF is a weak acid, the HF will not significantly contribute to the H+ concentration, so the pH can
be calculated from the HCl concentration.
ex. Calculate the pH of a mixture containing 0.10 M HNO2 (Ka = 4.0x10-4) and 0.10 M HCN (Ka = 6.2x10-10)
Since Ka for HNO2 >> than Ka for HCN, only the HNO2 will significantly contribute to [H3O+]. An ICE table can then be used
to determine pH.
Mixtures of Bases
In general, only the strongest base will significantly contribute to the concentration of hydroxide ions.
ex. Calculate the pOH of a mixture containing 0.20 M Sr(OH)2 and 0.20 M NH3.
Since Sr(OH)2 is a strong base and NH3 is a weak base, the NH3 will not significantly contribute to the OH- concentration, so the
pOH can be calculated from the Sr(OH)2 concentration.
ex. Calculate the pOH of a mixture containing 0.50 M C6H5NH2 (Kb = 3.8x10-10) and 0.50 M NH3 (Kb = 1.8x10-5)
Since Kb for NH3 >> than Kb for C6H5NH2, only the NH3 will significantly contribute to [OH-]. An ICE table can then be used
to determine pOH.
ex. A solution contains 1.0 M HF and 1.0 M NaF, Calculate the pH of the resulting solution. (How does this pH compare to a
1.0 M solution of HF?)
ex. A solution contains 1.0 M NH3 and 1.0 M NH4Cl, Calculate the pH of the resulting solution. (How does this pH compare to
a 1.0 M solution of NH3?)
Number of Acidic Protons
monoprotic acids: have only one acidic hydrogen atoms (ex. HCl and HC2H3O2)
diprotic acids: have two acidic hydrogen atoms (ex. H2SO4 and H2C2O4)
polyprotic acids: have three or more acidic hydrogen atoms (ex. H3PO4)
H2CO3 + 2H2O (l) U 2H3O+ (aq) + CO32- (aq) K = Ka1 x Ka2 = 4.3x10-7 x 5.6x10-11 = 2.4x10-17
For a diprotic acid, Ka1>Ka2. (The first proton is more easily lost than the second proton.)
Cations
Cations found in strong bases will not hydrolyze.
Cations that are the conjugate acids of weak bases will hydrolyze to produce acidic solutions.
Anions
Anions found in strong acids will not hydrolyze.
Anions that are the conjugate bases of weak acids will hydrolyze to produce basic solutions.
ex. Determine if the pH of the following solutions will be acidic, basic, or neutral.
(1) NaCl
NaOH is a strong base so Na+ will not hydrolyze
HCl is a strong acid so Cl- will not hydrolyze
Since neither the cation or anion hydrolyze, the solution will be neutral
(2) NaNO2
NaOH is a strong base so Na+ will not hydrolyze
NO2- is the conjugate base of the weak acid HNO2, so NO2- will hydrolyze:
NO2- (aq) + H2O (l) U OH- (aq) + HNO2 (aq)
The resulting hydrolysis reaction produces hydroxide ions so the solution is basic.
(3) NH4Cl
HCl is a strong acid so Cl- will not hydrolyze
NH4+ is the conjugate acid of the weak base NH3, so NH4+ will hydrolyze:
NH4+ (aq) + H2O (l) U H3O+ (aq) + NH3 (aq)
The resulting hydrolysis reaction produces hydronium ions so the solution is acidic.
(4) NH4NO2
NO2- is the conjugate base of the weak acid HNO2, so NO2- will hydrolyze:
NO2- (aq) + H2O (l) U OH- (aq) + HNO2 (aq)
NH4+ is the conjugate acid of the weak base NH3, so NH4+ will hydrolyze:
NH4+ (aq) + H2O (l) U H3O+ (aq) + NH3 (aq)
Since both ions hydrolyze, the Ka and Kb values for the resulting equilibria must be compared.
Since Ka > Kb, the hydrolysis of NH4+ will favour the products more than the hydrolysis of NO2-, as a result there will be more
hydronium ions than hydroxide ions and the solution will be acidic.
Calculations for Salts
ex. Calculate the pH and pOH of a 0.20 M solution of NaF.
NaOH is a strong base so Na+ will not hydrolyze
F- is the conjugate base of the weak acid HF, so F- will hydrolyze:
F- (aq) + H2O (l) U OH- (aq) + HF (aq) Kb = Kw/Ka = 1.0x10-14/7.2x10-4 = 1.4x10-11
NH4+ is the conjugate acid of the weak base NH3, so NH4+ will hydrolyze:
NH4+ (aq) + H2O (l) U H3O+ (aq) + NH3 (aq) Ka = 5.6x10-10
Buffers
buffer: is a solution that resists changes in pH.
A buffer contains a weak acid and a salt of its conjugate base (ie. HC2H3O2 and NaC2H3O2)
HC2H3O2 (aq) + H2O (l) U H3O+ (aq) + C2H3O2- (aq)
OR a weak base and a salt of its conjugate acid (ie. NH3 and NH4Cl).
Buffer Calculations
Buffer calculations are based on calculations for solutions with a common ion.
ex. A solution contains 0.50 M HC2H3O2 and 0.50 M NaC2H3O2. Calculate the pH of the solution.
Determine the resulting pH if 0.010 mol of NaOH are added to 1.0 L of this buffer.
Determine the resulting pH if 0.010 mol of HCl are added to 1.0 L of this buffer.
ex. A solution contains 0.25 M NH3 and 0.25 M NH4Cl . Calculate the pH of the solution.
Determine the resulting pH if 0.010 mol of HCl are added to 1.0 L of this buffer.
Determine the resulting pH if 0.010 mol of NaOH are added to 1.0 L of this buffer.
The Henderson-Hasselbalch Equation
Determining the pH of any solution containing a weak acid and its conjugate base can be simplified using the following
equation:
⎛ [ A− ] ⎞
pH = pK a + log ⎜ ⎟ where: pKa = -log Ka
⎝ [ HA] ⎠
Determining the pOH of any solution containing a weak base and its conjugate acid can be simplified using the following
equation:
⎛ [ BH + ] ⎞
pOH = pKb + log ⎜ ⎟ where: pKb = -log Kb
⎝ [ B ] ⎠
Preparing Buffers
ex. Calculate the pH of a buffer made by adding 0.50 g of sodium fluoride to 200 mL of 0.10 M hydrofluoric acid. Assume the
volume of the solution remains constant.
ex. Determine the mass of methylammonium chloride (CH3NH3Cl) that should be added to 300 mL of 0.20 M methylamine
(CH3NH2) in order to make a buffer with a pH of 11.40. Assume the volume of the solution remains constant.
Titrations
titration: an analytical procedure in which the concentration of a known solution is used to determine the concentration of an
unknown solution (used for acids and bases, oxidation and reduction, and solubility, etc)
Neutralizations Reactions
To determine the net ionic equation for a neutralization reaction, the spectator ions must be decided. Only strong acids, strong
bases, and soluble salts will dissociate completely to form ions. Weak acids, weak bases, and insoluble salts will not
significantly dissociate.
ex. Write the net ion equation for the following neutralization reactions.
(2) HF + NaOH →
Titration Calculations
ex. What is the volume of 0.50 M HCl required to titrate 150.0 mL of 0.25 M NH3?
ex. What is the concentration if 50.00 mL of HF requires 25.00 mL of 0.10 M NaOH to titrate?
Titration Curve Calculations
(2) 25.00 mL of NaOH has been added pH = (6) 125.0 mL of NaOH has been added pH =
14
13
12
11
10
9
8
pH
7
6
5
4
3
2
1
0
0 25 50 75 100 125 150 175 200
Volume NaOH added (mL)
Strong Acid/Weak Base
ex. A 0.100 M solution of HCl is used to titrate 100.0 mL of a 0.100 M NH3 solution.
(2) 25.00 mL of HCl has been added pH = (6) 125.0 mL of HCl has been added pH =
14
13
12
11
10
9
8
7
pH
6
5
4
3
2
1
0
0 25 50 75 100 125 150 175 200
Volume HCl added (mL)
Summary of Titration Curves
nearing the Change in pH At the
Initial Final
Titration equivalence around equivalence Titration Curve
pH pH
point equivalence point point
Strong Acid
very extreme pH very
added to steady decrease pH = 7
high change low
Strong Base
Strong Base
very extreme pH very
added to steady increase pH = 7
low change high
Strong Acid
Acid/Base Indicators
The equivalence point in an acid base titration is monitored using an acid base indicator. An indicator is a weak acid that
changes colour depending on whether it is in its acidic form or its basic form.
The point in a titration at which the indicator changes colour is called the endpoint. Every indicator changes colour at a specific
pH value called its pKa value. An indicator is selected for a given titration because its pKa value is close to the pH at the
equivalence point.
ex. Bromothymol blue is yellow in its acidic form and blue in its basic form. Bromthymol blue has a pKa value of 7.0 and would
be useful for a titration with an equivalence point around 7 (ie. a strong acid and a strong base)
ex. Phenolphthalein is colourless in its acidic form and bright pink in its basic form. Phenolphthalein has a pKa value of 9.3
would be useful for a titration with an equivalence point around 9 (ie. a weak acid and a strong base)
ex. Methyl red is yellow in its acidic fomr and red in its basic form. Methyl red has a pKa value of 5.1 and would be useful for a
titration with an equivalence point around 5 (ie. a strong acid and a weak base)
Diprotic Titration
If a strong base is titrated with a weak diprotic acid, there will be two equivalence points as shown in the following titration
curve.
(1) Boron compounds (such as BH3 and BF3) with group five element compounds (usually nitrogen or phosphorus, such as NH3
or PH3)
ex. BF3 + NH3 → BF3NH3
The electrons are accepted by the lewis acid, BF3 and donated by the lewis base, NH3.
(Generally, the boron compound acts like the lewis acid and the group five element compound acts like the lewis base._