Introduction

 Acids
o All acids contain at least one hydrogen atom
o H+ ions are responsible for the characteristic
reactions of acids
 Base
o Substances that react with acids in neutralization
reactions
 Alkalis
o Solutions containing hydroxide ions that are
formed when bases dissolve in water
o Soluble base that release OH- when dissolved in
water
 Salt
o A compound formed when the hydrogen ion in an
acid is replaced by a metal ion
o Not every H in an acid is replaceable
 Ex) ethanoic acid only carboxyl group H

Reactions of Acids and Base

Neutralization Reactions
 Neutralization: A chemical reaction where a base and an acid react to form a salt and water
 Acid base reactions will always produce a salt and water
 Salt and water are neither acidic nor basic  neutral solutions
 Neutralization reactions are exothermic as heat is released
Example)

Acid + Metal  Salt + Hydrogen

 Unreactive metals such as copper and silver do not react with dilute acids
 Examples:
 Ionic equations can also be written:

 Species which do not change during a reaction are called spectator ions and are cancelled out in
the ionic equation
 Net reaction:

Acid + base  Salt + Water

 Known as neutralization reactions
 Examples:

Acid + Carbonate/hydrogencarbonate  salt + water + carbon dioxide

 Examples:

 Ionic equations can also be written:

Arrhenius Theory
 Acids: Substances that produce hydrogen ions, H+ when dissolved in water
 Bases: Substances that produce hydroxide ions, OH- when dissolved in water

Brønsted-Lowry theory
 Before the Brønsted-Lory theory acids and bases were distinguished by their taste, acids taste
sour, bases taste bitter
  Focuses on the transfer of H+ ions during an acid-base reactions
 According to the Brønsted-Lowry theory, a substance behaves as an acid when it donates a proton
to a base. A substance behaves as a base when it accepts a proton from an acid.
o A Brønsted-Lowry acid is a proton (H+) donor
o A Brønsted-Lowry base is a proton (H+) acceptor

 Ex)
v H does not exist in solution just by itself – always bonded to a water molecule

+¿¿
 Acids can be a combination of hydrogen ions (H ) and an anion ex)
HCl , HNO3 , H C2 H 3 O 2
−¿¿
 Bases can be a combination of hydroxide ions (OH ) and metal cations ex) NaOH , KOH
o However, sometimes a hydrogen next to a metal signifies a base such as NaH
 Act of donating cannot happen in isolate – requires a substance to play the role of an acceptor

 Acid-Base Conjugate Pairs: A conjugate pair is two species which differ by a single proton:
o When acid loses a proton, it will become the conjugate base
o When base gains a proton, it will become the conjugate acid
+¿¿
 To find the conjugate acid of a species, add one H
+¿¿
 To find the conjugate base of a species, takeaway one H

Amphiprotic
 Substances that can behave as either acids and bases, depending on what they react with, and can
therefore donate or receive protons
o Amphiprotic: A chemical species capable of accepting and donating protons, thus
able to act as a Brønsted-Lowry acid and a base
 H2O is amphiprotic as it is able to donate a proton to form a
−¿¿ +¿¿
OH or accept a proton to form H 3 O therefore acting
as a Brønsted-Lowry acid or base
 Ex) HCO3- (hydrogen carbonate ion)

Amphoteric
 A species that can act as an acid or base, including reactions that do not involve a proton
 Amphiprotic specifically relates to the Brønsted-Lowry acid-base theory, where the
emphasis is on the transfer of a proton. Amphoteric is a more general term that isn’t just
confined to proton transfer
 All amphiprotic species are also amphoteric but not all amphoteric species are amphiprotic
 Example)

pH and pOH
 The pH scale can be used to indicate whether a solution is
acidic, alkaline or neutral
 Modern chemical laboratory
o pH is measured using pH meter
o pH can be estimated using universal indicator
 “ p” represents taking the negative logarithm of the value ( p=−log ⁡¿ Therefore:
o pH=−log¿ ¿
o pOH =−log ¿ ¿
+¿¿
 The pH scale represents the concentration of H . The acidity of a solution is a measure of the
concentration of hydrogen ions present. Using pH + pOH=14:
 When pH<7, the solution is acidic as ¿
 When pH=7, the solution is neutral as ¿
 When pH>7, the solution is basic as ¿

 Log laws allow us to find ¿ and ¿:

o ¿
o ¿

 A solution that has [H+] = 0.1 mol dm–3 ⇒ [H+] = 10–1 mol dm–3 ⇒ pH = 1.
 A solution that has [H+] = 0.01 mol dm–3 ⇒ [H+] = 10–2 mol dm–3 ⇒ pH = 2.
 The pH scale is logarithmic, meaning that an increase or decreases of an integer value changes
the concentration by ten (= a change of one pH unit represents a 10-fold change in [H+]
 A two-unit change represents a one-hundred-fold change and so on
 pH values are usually positive and have no units
  [H+] and [OH-] is inverse in aqueous solutions, concentrations of H + and OH- are inversely
proportional in an aqueous solution
o Lower [H+] (higher pH) = higher [OH-]

Ionic Product of Water

 Pure water has a pH of 7 at 25 C
 Water will self-ionize, where it will exist in equilibrium
o Endothermic process

 In pure water, the concentration of H+ and OH- are equal

 K W is the ionization constant of water (ionic product constant of water)

o The concentration of water does not appear in the equilibrium constant expression 
present in too much excess it is essentially constant
 The product of the H+ and OH- concentrations in any aqueous solution at 298.15K is 1.0 x 10-14
K W =¿
 pKw = −log Kw

 There is an inverse relationship between the concentration of H+ and OH- ions in solution
 The pH value & Kw of pure water differs depending on the temperature
o Water dissociates more as temperature increases
 pOH
 pOH =−log ¿ ¿
 ¿
 pKw = −log Kw

Properties of Acids
 All Bronsted-Lowry acids must contain at least one exchangeable hydrogen atom that can detach
from the rest of the acid molecule
  Exchangeable hydrogen atoms example:

 Remaining part of the acid produces an anion a.k.a = acid residue

 Oxoacids = inorganic acids containing oxygen

 Depending on number of exchangeable hydrogen atoms acids can be classified:

o Monoprotic
o Diprotic
o Triprotic
 Organic acids often contain both exchangeable and non-exchangeable hydrogen atoms, while
inorganic acids usually only have exchangeable hydrogen atoms

Strong and Weak Acids/Bases

 All acids and bases do not dissociate to the same extent. Not all acids and bases are of equal
strength in producing ¿ and ¿ in solution. The terms “strong” and “weak” give an indication of the
strength of an acid/base

Strong acid Weak acid

Strong acids fully dissociate in solution (~100%) Weak acids partially dissociate in solution (<5%)

Form strong electrolytes when absorbed in water Form weak electrolytes when absorbed in water

At the same concentration, strong acids will produce more ¿ than weak acids

Examples: Examples

hydrochloric acid, HCl nitric acid, HNO3 Ethanoic acid, CH3COOH carbonic acid, H2CO3

sulphuric acid, H2SO4 Propanoic Acid phosphoric acid, H3PO4

Strong bases Weak bases

Strong bases fully ionize in solution (~100%) Weak bases partially ionize in solution (<5%)

At the same concentration, strong bases will produce more ¿ than weak acids

Examples: sodium hydroxide, Examples: ammonia, NH3

NaOH

potassium hydroxide, Amines

 KOH

barium hydroxide, Ethylamine, CH3CH2NH2

Ba(OH)2

 When dealing with strong acids/bases use a single arrow as it will ionize completely

 When dealing with weak acids/bases use a double arrow as it will not ionize completely and exists
in equilibrium

 A strong acid has a weak conjugate base while a

strong base has a weak conjugate acid
o Strong acids are good proton donors
o Weak acids are poor proton donors
 Weak acids and bases are much more common than
strong acids and bases

Ionization constants for Acids and Bases
 The dissociation of a weak acid characterized by an equilibrium constant
 Acids Dissociation constant (Ka): measure the extent to which an acid dissociates
−¿¿
+¿+ A ¿
 HA + H 2 O ⇌ H K a =¿ ¿
 The stronger the acid, the more it dissociates and the higher the value of Ka

 The dissociation of a weak base characterized by an equilibrium constant

 Base Dissociation constant (Kb): measure the extent to which a base dissociates
−¿¿
+¿+OH ¿
 B+ H 2 O ⇌ BH K b =¿ ¿

 Ka & Kb can be used to compare the relative strengths of different acids and bases
 Can be expressed as p-numbers:
o pK a=−logK a
o pK b=−logK b
 Larger values of pK a and pK b correspond to weaker acids and bases
o relationship between Ka and pKa and between Kb and pKb is inverse

 K a∧K b , pK a & pK b are better measures of acid & base strength than pH because their values
do not depend on the concentration of the acid
 pK a & and pKb must be quoted at a specified temperature
Relationship between Ka and Kb

 K a x K b=Kw ❑
o Works only for a conjugate acid-base pair
 pK a + pK b = pKw

 The weaker the acid or base the stronger its conjugates

pH of Salt Solutions (Salt Hydrolysis)

 Solutions of salts can be acidic, neutral or alkaline
o Can be predicted by looking at whether the acid, base used to make salt are strong or
weak
 Ions produced by the salt in an aqueous solution can react with water and form conjugate acids
and/or bases affecting pH
 Hydrolysis reaction: reaction between salts and water
o Ions of salt react with water which ionizes the water molecule into H+ and OH-
o Extent depends on the strengths of the acid and base that form the salt

o Anion Hydrolysis (pH > 7 at 298K)

 Conjugate base of the weak acid is strong enough to hydrolyze the water
molecule to produce OH-
−¿( aq)¿

A−¿ (aq )+ H O (l) ⇌ HA (aq)+OH

2 ¿

o Cation Hydrolysis (pH < 7 at 298K)

 Conjugate acid of a weak base is strong enough to hydrolyze the water molecule
to produce H+
+¿ ( aq ) ¿

M +¿ ( aq)+ H 2 O ( l ) ⇌ MOH ( aq ) + H ¿

Strong Acids & Strong Bases

 Both fully dissociated in aqueous solutions so do not undergo hydrolysis
 Ex) NaCl(aq)  Na+ (aq) + Cl- (aq)
 o Df

o
o Neither ion is involved in acid-base equilibria
o Only equilibrium in solution:
 H and OH- produced in equal amounts therefore solution remains neutral
+

 Solutions of salts of strong acids with strong bases have a pH = 7 at 298K

v Sulfuric acid (diprotic) is only a strong acid for the first dissociation
 solution will be slight alkaline

Strong Acids & Weak Bases

 Hydrolysis involves cations only
 Ex) NH4Cl  ‘Cl’ part from HCl (SA), NH4 part from NH3 (WB)
 Conjugate of Cl- ion (HCl) is strong acid  does not undergo hydrolysis
o \
 Conjugate of NH4+ is weak base (NH3)  conjugate acid is strong enough to cause hydrolysis
 Ex)


 Solutions of salts of strong acids with weak bases have a pH < 7 at 298K

Weak Acids & Strong Bases

 Hydrolysis involves anions only
 Ex) CH3COONa (sodium ethanoate)
o Sodium hydroxide (S.B) + ethanoic acid (W.A)
o D
 Conjugate of CH3COO- is weak acid  conjugate base is strong enough to cause hydrolysis
o D
o OH- ions produced
 Conjugate of Na+ ion (NaOH) is strong base  does not undergo hydrolysis
o

Other examples of W.A + S.B

o Sodium carbonate, sodium hydrogencarbonate
o Potassium carbonate, potassium hydrogen carbonate

 Solutions of salts of weak acids with strong bases have a pH > 7 at 298K

Weak Acids & Weak Bases

 Both cation and anion undergo hydrolysis
 The acidity/basicity depends on the relative strengths of the parent acid and base
o Conjugate acid > conjugate base  slightly acidic
o Conjugate acid < conjugate base  slightly basic
 Ex) ammonium methanoate HCOO-NH4+
 o Salt of methanoic acid ( pK a=3.75 ¿ & ammonia ( pK b=4.75 ¿
o pH < 7
 Ex) Ethylammonium ethanoate C2H5NH3+CH3COO-
o Salt of ethylamine ( pK b=3.35 ¿ & ethanoic acid ( pK a=4.76 ¿
o pH > 7

 ‘Hydrolysis is for the weak’

 ‘the stronger wins’

Acid-Base Titrations
 Titration is a technique used in analytical chemistry to determine the
concentration of an unknown acid or base
 Titration involves the slow addition of one solution where the
concentration is known to a known volume of another solution where the
concentration is unknown until the reaction reaches the equivalence point /
stoichiometric point
o Burette and pipette used
o Equivalence point occurs when stoichiometrically equivalent
amounts of acid and base have reacted together
 For Acid/base titrations, a color change from a pH indicator is reached or
by using a pH meter
 A titration curve is a graph of the pH vs the amount of reagent progressively added to the original
sample
 Equivalence point (point of inflexion, stoichiometric point): point at which the number of moles
of acid exactly neutralizes the equivalent number of moles of base  reaction over
 o The point at which equivalent amounts (in mol) of acid and base have been added

Strong Acid + Strong Base

 Ex) Addition of 0.100 M NaOH solution to 25 cm3 of 0.1M HCl

 Initial pH = 1
o There’s 0.1M of HCl that dissociates completely

 Shape of pH curve
o Reaction: HCl (aq) + NaOH (aq)  NaCl (aq) + H2O (l)
o Ionic equation: H+ (aq) + OH- (aq)  H2O (l)
1. pH initially changes very little  [H+] is reasonably high, proportionate effect of
adding certain amount of NaOH is reasonably small
2. pH increases rapidly  adding a certain amount of NaOH has a proportionately
larger effect on [H+]
3. pH changes very little  proportionate effect of adding more NaOH is relatively
small

 Calculating pH for different points on the pH curve

o pH when 5.0cm3 of 0.100 mol dm-3 NaOH is added

to 25.0 cm3 of 0.100 mol dm-3 HCl

o pH when 25.0cm3 of 0.100 mol dm-3 NaOH is

added to 25.0 cm3 of 0.100 mol dm-3 HCl

o pH when 30.0cm3 of 0.100 mol dm-3 NaOH is added to 25.0 cm3 of 0.100 mol dm-3 HCl

 Features
o Y-axis intercept at pH approximately 1 (analyte is acid) or 13 (analyte is base)
 o Gradual rise or fall in pH at the beginning of the titration
o Sharp rise or drop in pH near the equivalence point
o Equivalence at pH =7 (no hydrolysis of salt)
o Flattening out at the end of the titration to pH approx..13 (titrant base) or 1 (titrant acid)

Weak Acid + Strong Base

1. Initial pH fairly high (pH of weak acid)

 Curve intercepts y-axis at a higher pH (partial dissociation of weak acid)
2. pH stays relatively constant until equivalence
 Reaches a zone where the solution seems to be buffered, the slope levels out
 Buffer region
o Solution contains both components of a weak conjugate acid-base pair
3. Jump in pH at equivalence: from pH 7 to pH 11
4. Curve flattens out a high value
5. pH at equivalence > 7
 Strong base will neutralize the weak acid more compared to neutralizing a strong acid

 Half equivalence point

o Represents where exactly half of the acid has been neutralized by base and converted into
the salt, the other half of the acid has been unreacted
o Occurs halfway through a buffered region where the pH barely changes for a lot of base
added
 equal quantities of weak acid and its salt = buffer
o Calculating pKa
 [acid] = [salt]
 [acid] = [HA] [salt] = [A-]  [HA] = [A-]

o pH= p K a
o pH at the half-equivalence point in a weak acid-strong base titration is equal to pK a of the
weak acid
 Weak acid – strong base titration curve vs strong acid-strong base curve
 Strong Acid and Weak Base Titration Curves

1. Initial pH = 1
2. No buffer region
3. jump in pH at equivalence: from pH 3 to pH 7
4. Curve flattens out a fairly low value
5. pH at equivalence < 7

Starting with weak base

 Can be used to determine the p K b
 pOH = p K b at half equivalence point
 p K b = 14 – pH at the half-equivalence point when a
strong acid is added to a weak base

Weak Acid and Weak Base Titration Curves

1. Initial pH fairly high

2. Addition of base causes pH to rise steadily
3. Difficult to identify equivalence point
4. Buffer region before the equivalence point, second buffer region
after the equivalence point
5. No sharp change in pH near the equivalence point

Indicators
 Needed to determine when equivalent amounts of acid and base have been mixed
 Weak acids or bases that differ in color from their conjugates where HIn and ¿−¿¿(undissociated
and dissociated forms) are different colors:
 −¿¿
+¿+¿ ¿
HIn ⇌ H
K ¿ =¿

 Increasing [H+] : equilibrium shift to left, favor HIn

 Decreasing [H+] : equilibrium shift to right, favor ¿−¿¿
 pH range of the indicator: the pH values between which the indicator has intermediate colors
because comparable amounts of the un-ionized and ionized forms are present
o Region where we can see the indicator changing color
o ex)

 pKa value of an indicator

 the pH range of an indicator is pKa plus or minus 1

Choosing an Indicator
 The equivalence point of a titration: point at which equivalent numbers of moles of acid and
alkali have been added
 End point of a titration: point at which the indicator changes color
 A suitable indicator should have its end point be close as possible to the equivalence point of the
titration
o pKa of the indicator should be close to the pH of the equivalence point
 Indicators cannot be used for a weak acid & weak base titration  no steep part on the curve