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ACID-BASE EQUILIBRIA

1. Arrhenius theory of acids and bases is suitable for strong acids and bases only. Bronsted-
Lowry theory (BLT) is more general and can be applied to any acid and base. Lewis theory
of acids and bases are suitable for complex ions and compounds with electron pairs. [Lewis
theory is not in the syllabus]
2. Common acids and bases
a. 7 strong acids: HCl, HBr, HI, HNO3, H2SO4, HClO4 and HClO3
b. 6 strong bases: NaOH, KOH, LiOH, Ca(OH)2, Ba(OH)2 and Sr(OH)2
c. Common weak acids: HF, H3PO4, CH3COOH (all carboxylic acids), HCN, HNO2, HClO,
HClO2, H2CO3 and H2SO3
d. Common weak bases: ammonia and amines (methylamine, ethylamine etc)

3. BLT for weak acids and bases


a. Weak acids and bases always approach equilibrium as they do not completely
dissociate in soln. Thus, equilibrium constant of acids and bases can be written by using
the symbol Ka and Kb, respectively.

b. Properties of BL acids and bases:


i. An acid is a proton donor. A base is a proton acceptor. (H+ is also called proton)
ii. Every acid has a conjugate base. Every base has a conjugate acid.

c. i. Weak acid is represented by HA. The general equation for acid dissociation is
HA(aq) + H2O(l) H3O+(aq) + A-(aq)
Acid Base Hydronium ion related anion

ii. Weak base is represented by B. The general equation for base dissociation is
B(aq) + H2O(l) BH+(aq) + OH-(aq)
Base Acid related cation Hydroxide ion

iii. The acid dissociation constant, Ka and base dissociation constant, Kb can be
written for all acids and bases, in the same way that we write Kc and Kp for any
reaction.
Ka and Kb values are large for strong acids and bases. Logically, stronger
acids and bases dissociate better. Thus, equilibrium lies away from them,
producing more ions.
Ka and Kb values are small for weak acids and bases because less ions
are produced.

d. Example of acid dissociation and its conjugate acid-base pairs


i. HSO4- +H2O SO42-+ H3O+ ; HSO4-/ SO42- and H3O+/ H2O
ii. CH3COOH(aq) + H2O(l) H3O+(aq) + CH3COO-(aq) ; CH3COOH/ CH3COO- and
+
H3O / H2O
iii. Equilibrium lies towards the left in all of the above such that value of Ka is always
small

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e. Example of base dissociation and its conjugate acid-base pairs
i. NH3(aq) + H2O(l) NH4+(aq) + OH-(aq) ; NH4+/NH3 and H2O/OH-
ii. CH3NH2(aq) + H2O(l) CH3NH3+(aq) + OH-(aq) ;CH3NH3+/CH3NH2 and
-
H2O/OH
iii. Equilibrium lies towards the left in all of the above such that value of Kb is always
small

f. Polyprotic acids are acids that can donate more than one proton. Each proton is donated
in successive steps. E.g. H2SO4 and H3PO4

g. Amphiprotic acids are acids that can either behave as an acid or a base. Amphiprotic
acids arise from polyprotic acids. E.g HSO4- , H2PO4- , HPO42- , HSO3-

4. The strength of binary acids (HX, where X is a halogen) can be determined by:
a. anion radius: the smaller the anion radius, the weaker the acid because of greater
attraction b/w H+ and X-. Greater attraction means more difficult to rip off the proton
b. bond energy: the greater the bond energy, the weaker the acid because it takes more
energy (thus more difficult) to rip off the proton
therefore, in the order of increasing acid strength: HF < HCl< HBr < HI

5. Self-ionization of water
a. Water is amphiprotic. By definition, it self-ionizes such that for each water molecule that
loses a proton, another water molecule gains it.
H2O(l) + H2O(l) H3O+(aq) + OH-(aq)
Base Acid Conj acid Conj base

b. Equilibrium lies far to the left as H3O+ is a stronger acid than H2O. This is reflected by Kw
(25oC) = [H3O+ ][OH- ] = 1.0 x 10-14
c. This value of Kw applies to pure water and all dilute aqueous soln
d. In a neutral solution, we expect [H3O+ ] = [OH- ] = 1.0 x 10-7M
e. An acidic soln has [H3O+] > [OH-] while a basic soln has [H3O+] < [OH-]. Refer to Fig 18.6
in the textbook

6. The p-scale and what it represents


a. The most familiar p-scale is the pH scale. pH is the measure of the concentration of
H3O+ in a solution in the logarithmic form
pH = - log [H3O+]
OR in the index form [H3O+] = 10-pH

b. We can express the concentration of any quantity in this manner: pY = -log [Y], whatever
Y represents.
E.g. pOH = - log [OH-] pKa = - log Ka
pKb = - log Kb pKw = pH + pOH = 14.00 (how is this derived?)

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c. Looking back at Kw
Kw = [H3O+ ][OH- ]
pKw = pH + pOH
- log Kw = - log [H3O+] log [OH-]
14.00 = - log10 (10-7) log10 (10-7)
= 7.00 + 7.00
= 14.00

d. In summary, you will need to be familiar with the following equations:


Kw (25oC) = [H3O+ ][OH- ] = 1.0 x 10-14
pH = - log [H3O+] OR [H3O+] = 10-pH
pKw = pH + pOH = 14.00
pKa = - log Ka and pKb = - log Kb
Kw = Ka x Kb (derivation is shown in textbook)
pKw = pKa + pKb

7. Acid-base equilibrium calculation


a. pH calculation for strong acids & bases are straightforward as they completely ionize in
water.
b. Weak acids & bases approach equilibrium, thus involve a multistep calculation
c. To calculate the pH of a weak acid or a weak base, we will make use of the tabulated Ka
and Kb values
d. Just like before, equilibrium calculation consists of 3 types:
i. Find K from given equilibrium concentration of all species
ii. Find K from given equilibrium concentration of some species
iii. Find equilibrium concentration for all species from given K value and initial
concentrations

e. To perform the calculations, just like before, a step-by-step approach is best.


i. Write equilibrium equation
ii. Set up ICE table (if necessary)
iii. Write the K expression
iv. Check for simplification ([A]o/K > 400) and solve for x
v. Solve for what is required in the question

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8. Salts and salt hydrolysis
a. A salt is just an ionic compound. Salts completely ionize when dissolved in water. Thus,
ions are produced.

b. Most ions are capable of demonstrating acidic or basic properties when dissolved in
water. An acidic ion donates a proton while a basic ion accepts a proton. This is what we
call salt hydrolysis, the reaction of salt or ions in water.

c. Cations can exhibit either neutral or weakly acidic properties


i. There are only 6 neutral cations derived from the strong bases. i.e. Li+, Na+, K+,
Ca2+, Sr2+, Ba2+
ii. Other cations are considered weakly acidic. E.g. NH4+, Al3+, Zn2+, Mg2+

d. Anions can exhibit either neutral or weakly basic properties


i. There are only 7 neutral anions derived from the strong acids. i.e. Cl-, Br-, I-, NO3-,
ClO4-, ClO3-, SO42- or HSO4-
ii. Other anions are considered weakly basic. E.g. NO2-, F-, ClO-

e. How to predict whether a salt is neutral, acidic or basic?


i. Check if either cation or anion is neutral
NaCl is neutral because both ions are neutral
ZnBr2 is acidic because cation is acidic while anion is neutral
KNO2 is basic because cation is neutral while anion is basic

ii. Compare the Ka and Kb values, the greater value is the prevailing property
If Ka > Kb , the salt is acidic. If Ka < Kb , the salt is basic
E.g. The salt NH4ClO has Ka (NH4+) = 5.6 E-10 & Kb (ClO-) = 3.6 E-7.
Therefore, this salt is basic
The salt NH4F has Ka (NH4+) = 5.6 E-10 & Kb (F-) = 1.4 E-11. Therefore,
this salt is acidic

9. The common ion effect


a. Based on Le Chateliers Principle, we can predict the equilibrium shift of a soln when a
common ion is introduced into the solution.
b. The addition of a conj acid or base of the dissolved species, will change the conc of the
dissolved species as equilibrium is reestablished
c. For each of the following, write the relevant acid-base equilibrium eqn and predict if pH
inc or dec w/ each change
i. NH4Cl added into NH3 soln ; pH dec w fewer amounts of OH-
ii. CH3COONa added into CH3COOH soln ; pH inc w fewer amounts of H3O+

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10. Buffers
a. Buffers are solutions of weak acid and its salt (e.g. HF and F-) or weak base and its salt
(e.g. NH3 and NH4+)
b. Buffers resist changes in pH when small amounts of either acids (H+) or bases (OH-) are
added e.g. human blood. It can takes up acid and base w/o much change in pH
c. Therefore, the use of buffer is most useful when conducting experiments which require a
strict range of pH
d. A good buffer is such that the conj acid-base pairs are present in equal amounts
(equimolar). E.g. a soln of 0.5 M HF and 0.5 M F-
e. Buffer capacity: the amount of acid or base a buffer can neutralize before the pH begins
to change appreciably. Increased component amounts increases the buffer capacity.
f. How does a buffer work? All added H+ ions will react w/ A- to form HA. All added OH-
ions will react w/ HA to form A-
H+(aq) + A-(aq) HA(aq)

OH-aq) + HA(aq) A-(aq)

g. Thus, the formation of weaker conj pairs is able to maintain the pH of a soln
h. The pH of a buffer can be determined by applying the Henderson-Hasselbach eqn. This
eqn can be used for both types of buffer.
pH = pKa + log [A-]
[HA]

i. The pOH of a buffer soln can be determined by using the following eqn. This eqn can be
used for both types of buffer.
pOH = pKb + log [BH+]
[B]
j. Acid-base equilibrium calculation involving buffered solutions
Common questions are: What is the pH after the addition of strong acid/base and
change in pH of the buffered soln
To perform the calculations:
i. Keep in mind that small amounts of strong acid or base will completely
react with the buffer.
ii. Keep track of the new conc of buffer components
iii. Apply the Henderson-Hasselbach eqn to find the new pH
iv. Calculate the change in pH = pHfinal pHini

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11. Acid-base indicator
a. An acid-base indicator is a soln of weak acid and its conj base that exhibit different
colors at different pH
b. Used in titration of acids and bases to signal the endpoint. The endpoint occur a few
drops after the equivalence point. Equivalence point is usually not accompanied by color
changes.
c. Need only to be familiar with phenolphthalein (best pH range 8-10) and methyl red (best
pH range 4-6).
d. Can choose any indicator for strong acid-strong base titrations, phenolphthalein for weak
acid-strong base titrations and methyl red for weak base-strong acid titrations.

12. Titration plots and calculations


Can be found in the textbook for each type: strong acid-strong base, weak acid-strong
base and weak base-strong acid, vice versa.

13. In summary of the chapter, you must be able to:


a. Identify BL conj acid-base pairs
b. Predict acidic/basic prop of soluble salts
c. Predict common ion effect
d. Understand how titration takes place w/ the addition of every drop of titrant
e. Do calculations involving:
i. Strong acid and base ionization
ii. Weak acid and base ionization
iii. Buffered soln
iv. Titration