– ACIDS & BASES IN AQUEOUS

SOLUTION –

WEEKS 6 AND 7: MODULES 15–20

Chapters 15 & 16 Practice Problems:
Chapter 15: 15.27, 15.28, 15.29, 15.31, 15.33, 15.35, 15.51, 15.53, 15.57, 15.59,
15.61, 15.67, 15.71, 15.85, 15.99, 15.107.
Chapter 16: 16.1, 16.9, 16.23, 16.25, 16.35, 16.39, 16.41, 16.45, 16.51, 16.53,
16.55, 16.57, 16.59, 16.63, 16.65, 16.101, 16.111, 16.115.

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 – ACIDS & BASES IN AQUEOUS
SOLUTION –
MODULE 15

1. ACID/BASE CONCEPTS AND DEFINITIONS

1.1. ARRHENIUS DEFINITION (15.1)

 Acid supplies H+

 Base supplies HO-

1.2. BRØNSTED–LOWRY DEFINITION (15.2)

 The Acid is a PROTON DONOR

 The Base is a PROTON ACCEPTOR

e.g.: NH3(aq) + H2O(l) ⇌ NH4+(aq) + OH-(aq)

H+
base acid

1.3. LEWIS CONCEPT DEFINITION (15.3)

 Lewis Acid is an ELECTRON PAIR ACCEPTOR

 Lewis Base is an ELECTRON PAIR DONOR

 H2O(l) + H+(aq) H3O+(aq)

H
O O
H H H
H H

 NH3(aq) + H+(aq) NH4+(aq)

NH3(aq) + H+(aq) NH 4+(aq)

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  NH3 + BF3  H3N·BF3

NH3 + BF3 H3N BF3

2. DEFINITIONS OF pH AND pOH AND pK

p(anything) = – log10(anything)

Simply produces an "ordinary looking number" from a "scientific number"

5.0×10–10 has 2 sig. figs.

For logarithms, sig. figs appear as digits AFTER the decimal point.
e.g., 5.0×10–10  – log10(5.0×10–10 ) = 9.30
5.0×10–12  – log10(5.0×10–12 ) = 11.30
5.0×10–1  – log10(5.0×10–1 ) = 0.30

Notice that

 the smallest the number the largest is the value of the corresponding log 10
 the largest the number the smallest the value of the corresponding log 10

2.1. pH and pOH (15.8)

Calculated on concentrations of hydronium and hydroxide ions

pH = –log[H3O+]
if [H3O+] = 5.0×10–10
pH = – log [H3O+] = – log 5.0×10–10 = 9.30

When we know the pH we can calculate the concentration in H3O+ [H3O+] = 10–pH
pOH = –log[OH–]
if [OH-] = 2.0×10–5
pOH = – log [OH-] = – log 2.0×10–5 = 4.70

When we know the pOH we can calculate the concentration in OH– [OH–] = 10–pOH

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2.2. pK for any equilibrium
Calculated on equilibrium constant
Let’s consider an equilibrium:
A+B⇌C+D [C] × [D]
K= = 5.2 × 10–4
[A] × [B]
pK = –logK = –log 5.2× 10–4 = 3.28

When we know the pK we can calculate the equilibrium constant K = 10–pK

3. SELF–IONIZATION OF WATER (15.6)

AMPHOTERIC: means that it can act as BOTH an acid or as a base

NH3(aq) + H2O(l) NH4+(aq) + OH–(aq)

Acid Donates H+

NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)

Base Accept H+

As a Result Water is able to SELF-IONIZE or DISSOCIATE

Pure water contains equal small amounts of both H 3O+ and OH– ions.

H2O(l) + H2O(l) H3O+(aq) + OH–(aq) Kw

H+

Kw = [H3O+][OH–] = 1.00×10–14 at 25C the ION PRODUCT for water

Since in PURE water the stoichiometry is 1:1 between H 3O+ and OH– (neutral solution):

We can write: [H3O+] = [OH–] = x ∴ Kw = [H3O+][OH–] = x2

and solve for x = Kw = 1.0×10–14 = 1.0×10–7 M (at 25 C)

Therefore in pure water or NEUTRAL solution: [H3O+] = [OH–] = 1.0×10–7 M (at 25C)
ACIDIC solution: [H3O+] > [OH–]
BASIC solution: [H3O+] < [OH–]

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IN ALL AQUEOUS SOLUTIONS THE FOLLOWING EQUILIBRIUM IS REACHED

This even if we have added a base or an acid and modified the concentration of either H3O+ or OH-

H2O(l) + H2O(l) H3O+(aq) + OH–(aq) Kw

Thus we can write for any solution of pH different from 7: K w = [H3O+][OH–] = 1.00×10–14

For water pKw = –log Kw = –log([H3O+][OH–]) = –log (1.00×10–14)

Recall: log ab = log a + log b

–log [H3O+] – log [OH–] = –logKw = –log (1.00×10–14 )

In any aqueous solution  pH + pOH = pKw = 14.00

What all this means is that given ANY ONE of [H3O+], [OH–], pH or pOH, we can find all four.
 Acidic, pH < 7, Basic pH > 7
 Very Acidic / low pH and high pOH
 Very Basic / high pH and low pOH

Question 1: If a solution has a pH of 4.74 what are [H 3O+], [OH–], and pOH?

pH = – log[H3O+], therefore, [H3O+] = 10–pH =

pOH = 14.00 – pH =

[OH–] = KW/[H3O+] = 10–pOH =

4. STRONG ACIDS (SA) AND STRONG BASES (SB)

We will only consider

 6 COMMON STRONG ACIDS (SA): HCl, HBr, HI, HNO 3, HClO4 & H2SO4 (1st H only)

We will only consider

 8 COMMON STRONG BASES (SB):

Alkali Metal (Group 1)Hydroxides: LiOH, NaOH, KOH, RbOH and ,CsOH,

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 Alkaline Earth Metal Hydroxides (Group 2): Ca(OH)2, Sr(OH)2 and Ba(OH)2

 ALL other acids and bases are considered WEAK!!

Strong Acids and Strong Bases are COMPLETELY DISSOCIATED in water

Stong acids give the hydronium ion: H3O+

HX(aq) + H2O(l)  H3O+(aq) + X–(aq)

Strong Bases give the hydroxide ion OH–

MOH(s)  M+(aq) + OH–(aq)

M(OH)2(s)  M2+(aq) + 2OH–(aq)

5 CALCULATING pH FOR SA AND SB SOLUTIONS

(15.8)
From the "stoichiometric" or "nominal" concentration of SA or SB we can calculate the concentration of
all ions, the pH and the pOH

5.1. Strong Acid

For a nominal concentration CHA, there is no strong acid HA that remains non-dissociated.

Thus [H3O+] = CHA then we calculate → pH → pOH (recall pH + pOH = 14.00 at all time)

Question 2: Determine the concentration of all the ions in a solution labelled "C HCl = 0.15 M” and calculate
the pH and pOH?

1. RECOGNITION: What type of species?

2. [H3O+] = [Cl–] =

3. Other ions in solution?

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5.2. Strong Base

For a nominal concentration of base from Alkali Metal Hydroxides group IA: MOH (LiOH, NaOH, KOH,
RbOH or ,CsOH,): CMOH there is no strong base MOH that remains non-dissociated.

Thus [OH–] = CMOH then we calculate → pOH → pH (recall pH + pOH = 14.00 at all time)

For a nominal concentration of base from Alkaline Earth Metal Hydroxides (Group 2): M(OH) 2 (Ca(OH)2,
Sr(OH)2 and Ba(OH)2): CM(OH)2 there is no strong base M(OH)2 that remains non-dissociated, each M(OH)2
molecules gives 2 Hydroxide ions.

Thus [OH–] = 2× CM(OH)2 then we calculate → pOH → pH (recall pH + pOH = 14.00 at all time)

Question 3: What are all the ION concentrations in a solution labelled as "C{Ca(OH) 2} = 0.15 M" and
calculate the pH and pOH?
1. RECOGNITION: What type of species?

2. [OH–] = [Ca2+] =

3. Other ions in solution?

END OF MODULE 15
PLEASE COMPLETE ACTIVITY 15

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 – ACIDS & BASES IN AQUEOUS
SOLUTION –
MODULE 16

6. WEAK ACIDS (WA) and WEAK BASE (WB)

Weak acids & weak bases – react ONLY partially with H 2O

6.1. Weak Acids (16.1)

HA(aq) + H2O(l) H3O+(aq) + A–(aq) Ka(HA)

[H3O+] × [A–]
Ka(HA) =
[HA]

Ka values are always small – WHY??

With Ka < 1, the equilibrium lies to the left hand side of the reaction, not many "products" are formed.
We have a range of Ka values for weak acids:
 the bigger Ka, the "stronger" the WA.
 the smaller Ka, the "weaker" the WA.

Question 4: Consider the Ka values for the following: Which is the strongest acid?
A) Cyanic acid, HOCN, 3.5  10–4
B) Formic acid, HCHO2, 1.7  10–4
C) Lactic acid, HC3H5O3, 1.3  10–4
D) Propionic acid, HC3H5O2, 1.3  10–5
E) Benzoic acid, HC7H5O2, 6.3  10–5

Recall then that pK = –logK

 Thus we define for an acid: pKa = – log Ka

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For example the Ka for acetic acid: Ka (HAc) = 1.8×10–5 ∴ pKa (HAc) = – log 1.8×10–5 = 4.77

 When given a pKa value (usually from table we will calculate the Ka = 10–pKa

Example pKa = 9.23 ∴ Ka = 5.9×10–10 Boric Acid)

pKa = 3.4 ∴ Ka = 3.5×10–4 (HCN)

If we look at Ka (equilibrium constant) and its corresponding pKa value in tables:

 the smallest the Ka, the weaker the acid, the larger the value of pKa
 the larger the Ka, the stonger the acid, the smaller the value of pKa

Question 5: Consider the pKa values for the following:

A) Propionic acid, HC3H5O2, 4.89
B) Benzoic acid, HC7H5O2, 4.20
C) Lactic acid, HC3H5O3, 3.89
D) Formic acid, HCHO2, 3.77
E) Cyanic acid, HOCN, 3.46

Which is the weakest acid?

6.2. Types of Weak Acids

(i) Organic Weak Acids:

 CARBOXYLIC ACIDS

R–COOH(aq) + H2O(l) H3O+(aq) + R–COO–(aq) Ka(RCOOH)

When R = CH3  acetic acid, i.e., CH3COOH (or ethanoic acid based on IUPAC rules)
R = C2H5  propanoic acid, CH3CH2COOH, etc.

 some alcohols, e.g., phenol C6H5OH

C6H5OH(aq) + H2O(l) H3O+(aq) + C6H5O–(aq) Ka(C6H5OH)

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(ii) Inorganic Weak Acids:

HF(aq) + H2O(l) H3O+(aq) + F–(aq) Ka(HF)

HCN(aq) + H2O(l) H3O+(aq) + CN–(aq) Ka(HCN)

B(OH)3(aq) + H2O(l) H3O+(aq) + H2BO3–(aq) Ka(B(OH)3)

HClO(aq) + H2O(l) H3O+(aq) + ClO–(aq) Ka(HClO)

(iii) Conjugate acids of weak bases:

NH4Cl(aq), CH3NH3Cl(aq) [or any “alkyl ammonium salt”: RNH3Cl(aq) with R = methyl, ethyl
etc…], C5H5NHCl(aq)

We will find them on the shelf as “salts”, strong electrolytes that dissolve and fully dissociate in water.
Example “Ammonium Chloride” dissolved in water it will give the following reaction.

NH4Cl(aq) + H2O(l) H3O+(aq) + Cl- (aq) + NH3(aq)

But since NH4Cl is soluble and a strong electrolyte, it is fully dissociated into ions and we can write the
complete ionic equation:

NH4+(aq) + Cl- (aq) + H2O(l) H3O+(aq) + Cl- (aq) + NH3(aq)

After cancelling the “spectator ion” Cl- we have the

NIE: NH4+(aq) + H2O(l) H3O+(aq) + NH3(aq) Ka(NH4+)

These WA follow the NIE for the equilibrium:

[H3O+] × [B]
BH+(aq) + H2O(l) H3O+(aq) + B(aq) Ka(BH+) =
[BH+]
Acid Base
CH3NH3+(aq) + H2O(l) H3O+(aq) + CH3NH2(aq) Ka(CH3NH3+ )

C5H5NH+(aq) + H2O(l) H3O+(aq) + C5H5N(aq) Ka(C5H5NH+ )

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6.3. Weak Bases (16.3)

B(aq) + H2O(l)  BH+(aq) + OH–(aq) Kb(B)

[OH–] × [BH+]
Kb(B) =
[B]

Kb values are always small – WHY??

With Kb < 1, the equilibrium lies to the left hand side of the reaction, not many "products" are formed.

We have a range of Kb values for weak bases:

 the bigger Kb, the "stronger" the WB
 the smaller Kb, the "weaker" the WB

Recall then that pK = –logK,

 Thus we define for a base: pKb = – log Kb

For example the Kb for Ammonia Kb (NH3) = 1.8×10–5 ∴ pKb (NH3) = – log 1.8×10–5 = 4.74

 When given a pKb value (usually from table we will calculate the Kb = 10–pKb

Example pKb = 9.30 ∴ Kb = 4.2×10–10 (Aniline)

pKb = 4.19 ∴ Kb = 6.5×10–5 (Triethylamine)

If we look at Kb (equilibrium constant) and its corresponding pK b value in tables:

 the smallest the Kb, the weaker the base, the larger the value of pK b
 the larger the Kb, the stonger the base, the smaller the value of pK b

6.4. Types of Weak Bases (16.3)

(i) Ammonia & its Organic Derivatives

NH3(aq) + H2O(l) NH4+(aq) + OH–(aq) Kb(NH3)
CH3NH2(aq) + H2O(l) CH3NH3+(aq) + OH–(aq) Kb(CH3NH2)

other weak bases e.g., (CH3)2NH & (CH3)3N

pyridine (C5H5N), aniline (C6H5NH2)
hydroxylamine (HONH2)

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(ii) Conjugate Bases of Weak Acids:

CH3COONa(aq), NaF(aq) , NaNO2(aq), NaClO(aq)

We will find them on the shelf as “salts”, strong electrolytes that dissolve and fully dissociate in water.

Take for example “Sodium Acetate” dissolved in water will give the following reaction on water

CH3COONa(aq) + H2O(l) OH–(aq) + Na+ (aq) + CH3COOH(aq)

But since CH3COONa is soluble and a strong electrolyte, it is fully dissociated into ions and we can write
the complete ionic equation:

CH3COO–(aq) + Na+ (aq) + H2O(l) OH–(aq) + Na+ (aq) + CH3COOH(aq)

After cancelling the “spectator ion” Na+ we have the

NIE: CH3COO–(aq) + H2O(l) OH– (aq) + CH3COOH(aq) Kb(CH3COO-)

These WB examples follow the NIE for the equilibrium:

A–(aq) + H2O(l) HA(aq) + OH–(aq) [OH–] × [HA]

Kb(A–) =
[A–]

F–(aq) + H2O(l) HO–(aq) + HF(aq) Kb(F-)

NO2–(aq) + H2O(l) OH–(aq) + HNO2(aq) Kb(NO2-)

ClO–(aq) + H2O(l) OH–(aq) + HClO(aq) Kb(ClO-)

END OF MODULE 16
PLEASE COMPLETE ACTIVITY 16

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 – ACIDS & BASES IN AQUEOUS
SOLUTION –
MODULE 17
6.5. Recognizing Conjugate Acid-Base Pairs (p 637)
To make a CONJUGATE BASE from its acid  REMOVE H+
To make a CONJUGATE ACID from its base  ADD H+

Question 5: Indicate conjugate acid/base pairs

NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)

CN–(aq) + H2O(l) HCN(aq) + OH–(aq)

6.6. Relating Ka/pKa and Kb/pKb of conjugate acid-base pairs (16.7)

Take for instance the Weak acid HA and it’s Conjugate Base A– (solution of the sodium salt for instance)

We can write the following equilibria and add them up

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HA(aq) + H2O(l) H3O+(aq) + A–(aq) [H3O+] × [A–]
Ka(HA) =
[HA]
A–(aq) + H2O(l) HA(aq) + OH–(aq) [OH–] × [HA]
Kb(A–) =
[A–]

HA(aq) + H2O(l) + A–(aq) + H2O(l) HA(aq) + OH–(aq) + H3O+(aq) + A–(aq)

There [H3O+] × [A–] [OH–] × [HA]

K= = Ka × Kb
[HA] [A–]

Then if we cancel species that are found on both side of the arrow we end up with:

H2O(l) + H2O(l) H3O+(aq) + OH–(aq) Kw = [H3O+] × [OH–]

Thus we can write the following relationship between K a and K for a conjugate acid-base pair:

Ka × Kb = Kw = 1.0×10–14

Kw and Kw
Ka = Kb =
Ka Ka

Recall: pK = –log K and log(ab) = loga + logb

We can then write : pKw = –log(Ka × Kb) = pKa + pKb = 14.00

This is true for any conjugate acid-base pairs: AH/A– or BH+/B

Question 6:

a. Given the Ka of Acetic Acid Ka (HAc) = 1.8×10–5 calculate the Kb of the Acetate ion Ac– given by
Sodium Acetate (AcNa)

b. Given the Kb of Methylamine Kb (CH3NH2) = 4.4×10–4 calculate the Ka of the weak acid CH3NH3+
(methyl ammonium ion) given by Methylammonium Chloride (CH 3NH3Cl)

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Question 7: Write realistic balanced net-ionic equations for HCO3– acting (a) as an acid & (b) as a base.
From tables: Ka(H2CO3) = 4.4510–7 (= Ka1)
Ka(HCO3–) = 4.6910–11 (= Ka2)

(a) Ka =

(b) Kb =

Here’s two more equations:

H2CO3(aq) +H2O(l) H3O+(aq) + HCO3–(aq) Ka =

CO32–(aq) + H2O(l) HCO3–(aq) + OH–(aq) Kb =

7. CALCULATIONS WITH WEAK ACIDS (16.1)

How do weak acids (WAs) differ from strong acids (SAs)?
 Conductivity: SAs have many more ions thus the conductivity of SA solutions is much greater than
that of WA
 Concentrations of H3O+ for SA is much greater than that in WA: For similar concentrations pH (SA)
<< pH (WA)
Question 8: Match the solutions below with their appropriate pH values.
SOLUTION pH
1) 0.010 M HCl(aq) A) 2.0
2) 0.010 M H2SO4(aq) B) 4.0 – 5.0
3) 0.010 M HF(aq) C) 10.0 – 11.0
4) 0.010 M HClO(aq) D) 1.0 – 2.0
5) 0.010 M NH3(aq) E) 8.0 – 9.0
6) 0.010 M C6H5NH2(aq) F) 2.0 – 3.0

From Appendix E From Appendix F

Ka(HF) = 6.810–4 Kb(NH3) = 1.810–5
Ka(HClO) = 3.510–8 Kb(C6H5NH2) = 4.210–10

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7.1. Weak Acid Equilibrium

Let us consider a solution of Weak Acid “HA” in aqueous solution of initial concentration C HA. Remember
that it is NOT FULLY DISSOCIATED, thus in solution we will have: HA(aq) and a little bit of H3O+(aq)
and A– (aq) which will be produced once the equilibrium is established.

We can write the following equilibrium and an ICE table to do the calculation

HA(aq) + H2O(l) H3O+(aq) + A–(aq)

[Initial] CHA 0 0
[Change] -x +x +x
[Equil.] CHA – x +x +x

AT EQUILIBRIUM we can write

[H3O+]eq × [A–]eq +x × +x (x)2
Ka(HA) = = =
[HA]eq CHA – x CHA – x

With x = [H3O+]eq = [A–]eq

We will then encounter 3 types of problems:

(i) Given [H3O+]eq (or pH) and the nominal concentration (initial) C HA, find Ka
(ii) Given Ka and [H3O+]eq (or pH), find the nominal concentration (initial) CHA
(iii) Given Ka and the nominal concentration (initial) CHA, find [H3O+]eq or pH

END OF MODULE 17
PLEASE COMPLETE ACTIVITY 17

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 – ACIDS & BASES IN AQUEOUS
SOLUTION –
MODULE 18
7.2. Calculating Ka for a Weak Acid (i) (p 665)

Question 9: The pH of 0.100 M lactic acid is 2.06. What is K a for lactic acid? (Ans: 8.3×10–4)

LacH(aq) + H2O(l) H3O+(aq) + Lac–(aq)

[Initial] 0.100 0 0
[Change] -x +x +x
[Equil.] 0.100– x +x +x

[H3O+]2
Ka(LacH) =
0.100 – [H3O+

The pH is given thus:

pH = 2.06  [H3O+] = 10–2.06 = 8.710–3 M = x

7.3. Calculating a nominal concentration or initial concentration (ii)

Question 10: What concentration of formic acid (HCOOH, Ka = 2.1×10–4) will yield a solution of pH 2.42?
(Ans: CHA = 7.3×10–2 M)

HCOOH(aq) + H2O(l) H3O+(aq) + HCOO–(aq)

[Initial] CHA 0 0
[Change] -x +x +x
[Equil.] CHA – x +x +x

(x)2
Ka =
CHA – x

(x)2
∴ CHA – x =
Ka
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 (x)2
∴ CHA = +x
Ka
Given are Ka = 2.1×10–4

pH = 2.42 → x = [H3O+]eq = 10–pH

CHA =

7.4. Calculating the pH of a weak acid solution (iii) (p 667–670)

Question 11: Find the pH of an 0.10 M solution of acetic acid, Ka(HAc) = 1.8×10–5 (Ans: pH = 2.87)

HAc(aq) + H2O(l) H3O+(aq) + Ac–(aq)

[Initial] 0.10 0 0
[Change –x +x +x
[Equil.] 0.10– x x x

(x)2
Ka =
CHA – x

We know Ka and we know CHA we are looking to solve on x therefore we may have to solve a quadratic
equation  !
Ka(CHA – x) = x 2 ⇒ x2 + Ka x – CHA×Ka = 0

Luckily we can often make the “approximation” that x is very small compared to CHA: remember that for a
weak acid the equilibrium Ka is usually small and the equilibrium is largely in favor of HA(aq)

Then (CHA – x)  CHA and we can say:

(x)2
Ka = then x = √Ka × CHA
CHA

We can assess whether or not we can safely make this assumption by looking at the ratio CHA/Ka:
(i) If CHA/Ka  100, it is safe to assume that x <<< CHA thus (CHA – x)  CHA 
(ii) If CHA/Ka  100, then x cannot be ignored in front of CHA and one can only solve for x through
solving the quadratic equation 
(iii) If in doubt we will make the approximation, calculate x then assess if x is less than 5% of CHA,
if x/CHA × 100 < 5% the approximation was valid 

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 if x/CHA × 100 > 5% then the approximation was not valid and we must solve the quadratic
equation. 

This is the "5 % Rule".

For Question 11: 

CHA 0.10
= =
Ka 1.8 × 10-5

Then we can say: x = √Ka × CHA = √ (1.8 × 10-5)× 0.10 =

Recall that x = [H3O+ ] = then pH = –log [H3O+ ] =

Let see if the 5% rule is indeed true

x
× 100 = × 100 =
CHA 0.10 M

Question 12: Let us do the same question with an acid ‘HA’ of K a is 4.0 × 10–3 , CHA = 0.10 M

CHA 0.10
= = 25 < 100 !!! NO APPROXIMATION ! 
Ka 4.0 × 10-3

We cannot ignore x

(x)2
Ka =
CHA – x

To find the correct value, we need to solve the quadratic equation

⇒ Ka(CHA – x) = x 2 ⇒ x2 + Ka x – CHA×Ka = 0

Remember the Equilbrium Lecture notes

Quadratic equation: ax2 + bx + c = 0
 b  b 2  4ac
Quadratic equation solution: x 
2a
–Ka ± √ (Ka)2 + 4 CHA × Ka
x=
2

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For Question 12,

–4.0 × 10–3 ± √ (4.0 × 10–3)2 + 4 × 0.10 × 4.0 × 10–3

x=
2
Only “+” gives a valid number here x = 0.018 M = [H3O+]eq

Then pH = –log[H3O+]eq = 1.74

Let’s check that indeed:

x 0.018 M
× 100 > 5 % ⇒ × 100 = 18 %
CHA 0.10 M
It means that 18% of the acid HA is dissociated in solution

7.5. Percent dissociation

x
× 100 is the Percent Dissociation (this is just the 5% Rule!!)
CHA

It tells us how much the Equilibrium is leaning towards the right = dissociation
HA(aq) + H2O(l) H3O+(aq) + A–(aq)
[Equil.] CHA – x x x

[H3O+]
× 100 is the Percent Dissociation remember that x = [H3O+]
CHA
We call this ratio % dissociation
% ionization
% deprotonation

It depends on BOTH KHA and CHA

Question 13: Ka (HAc) = 1.8×10–5 Calculate % dissociation of (a) 0.10 M HAc

(b) 0.0010 M HAc

CHA = 0.10 M CHA = 0.0010 M

CHA 0.10 CHA 0.0010

= = =
Ka 1.8 × 10-5 Ka 1.8 × 10-5
–Ka ± √ (Ka)2 + 4 CHA × Ka
x = √Ka × CHA
x=
2

x= x=

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 x
% Dissociation is × 100
CHA
1.310–3 1.310–4
× 100 × 100
CHA CHA

= =

The % Dissociation of a Weak Acid INCREASES with dilution

Question 14: Cacodylic acid is used as a cotton defoliant. Cacodylic acid is 0.77% deprotonated in a 0.011
M aqueous solution.
a. What is the pH of the solution?

A) 0.11 B) 1.96 C) 2.07 D) 4.07 E) Not enough data

HA(aq) + H2O(l) H3O+(aq) + A–(aq)

[Equil.] CHA – x x x

[H3O+] % Deprot
+
% Deprotonation is × 100 ⇒ [H3O ] = × CHA
CHA 100

[H3O+] =

pH = –log [H3O+] =

b. What is the Ka of this acid?

A) 6.6 × 10–7 B) 1.8 × 10–5 C) 2.8 × 10–2 D) 4.07 E) Not enough data

[H3O+]2
Ka =
0.011 – [H3O+]

END OF MODULE 18
PLEASE COMPLETE ACTIVITY 18

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 – ACIDS & BASES IN AQUEOUS
SOLUTION –
MODULE 19

8. CALCULATIONS WITH WEAK BASES

8.1. Weak Base Equilibrium (16.3)

B(aq) + H2O(l) BH+(aq) + OH–(aq)

[Initial] CB 0 0
[Change] –y +y +y
[Equil.] CB – y y y

AT EQUILIBRIUM we can write

[OH–]eq × [BH+]eq +y × +y (y)2
Kb(B) = = =
[B]eq CB – y CB – y

With y = [OH–]eq = [BH+]eq

We will treat these questions in a similar fashion that we treated solutions of weak acid, the major
differences are that we will be solving for [OH–] and using Kb, but remember that pH + pOH = 14.00
thus we may be given a pH that we will need to convert to a pOH and [OH –]!

We will then encounter 3 types of problems:

(i) Given [OH–]eq (or pH) and the nominal concentration (initial) C B, find Kb
(ii) Given Kb and [OH–]eq (or pH), find the nominal concentration (initial) CB
(iii) Given Kb and the nominal concentration (initial) CB, find [OH–] or pH which we will solve by finding
[OH–] then pOH then pH. For these types of question we will also often make the “approximation” that y is

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very small compared to CB: remember that for a weak base the equilibrium Kb is usually small and the
equilibrium is largely in favor of B(aq)

Then (CB – y)  CB and we can say

(y)2
Kb = then y = √Kb × CB
CB

We will assess whether or not we can safely make this assumption by looking at the ratio CB/Kb and using the
same rule as above for the weak acid.

8.2. Calculating Kb for a Weak Base (i)

Question 15: For dimethylamine, (CH3)2NH, the pH of a 2.610–2 M solution is 11.56. What is Kb for
dimethylamine?

Recognize we have a Weak Base (WB) problem and define the reaction

B(aq) + H2O(l) BH+(aq) + OH–(aq) Kb

[Equil.] CB - y y y

[OH–]eq × [BH+]eq +y × +y (y)2

Kb(B) = = =
[B]eq CB – y CB – y

We are given pH = 11.56, and we need [OH–] to solve on Kb  calculate pOH

Recall: pH + pOH = 14 → pOH =  [OH–] = y = 3.610–3 M

Calculate Kb:

(y)2
Kb(B) =
CB – y

8.3. Calculating pH of Weak Base solutions (iii) (p 676)

Question 16: Calculate the pH of a solution that is 0.500 M (CH 3)2NH (aq) (Kb = 5.410–4)
(Ans: pH = 12.22).

Recognize we have a weak base and define the reaction:

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 B(aq) + H2O(l) BH+(aq) + OH–(aq) Kb = 5.410–4
[Equil.] CB - y y y

(y)2
Kb(B) =
CB – y

We are looking to solve for y. Can we make the assumption that

y <<< CB and that therefore CB – y ≈ CB ?

Let’s calculate :

CB 0.500 M >>> 100 

= -4
Kb 5.4 × 10

(y)2
 Kb = then y = √Kb × CB =
CB

Remember that y = [OH–] =  pOH = –log[OH–] =

pH = 14.00 – pOH =
Let’s check that the approximation was allowed: Rule of 5%

y × 100 ⇒ × 100 = this is the %Protonation

CB 0.500 M

Question 17: What is the pH of a 0.050 M sodium acetate solution? K a(acetic acid) = 1.810-5

We are now looking at a solution of AcNa: Sodium Acetate. It is a fully soluble salt (Na + Group IA), thus
we have a solution of: Na+(aq ) and Ac–(aq)

Recognize that Na+ is spectator ion and that Ac– is the CONJUGATE BASE OF AcH (Acetic Acid) ,
therefore the solution is weakly Basic. We have a solution of a weak base (Ac –) in water
Ac–(aq) + H2O(l) AcH(aq) + OH–(aq) Kb(Ac–)

[Equil.] CB - y y y

–
(y)2
Kb(Ac ) =
CB – y
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What is the value of Kb(Ac–) ?
Kw
Recall (6.6 above) Kb (Ac–) =
Ka (AcH)

Thus 1.010-14
Kb (Ac–) =
1.810-5

Let’s calculate :

CB 0.050 M >>> 100 

=
Kb(Ac–)

y = √Kb × CB = [OH–] =  pOH =  pH = 14.00 – =

Let’s check that the approximation was allowed: Rule of 5%

y × 100 ⇒ × 100 = this is the %Protonation

CB 0.050 M

Question 18: Place the following 0.010 M solutions in order of most acidic (lowest pH) to most basic
(highest pH):

Ca(OH)2, HClO, LiOH, HNO2, CH3NH2, HNO3, C5H5N, C6H5OH.

Given: pKa(HClO) = 7.46
pKa(HNO2) = 3.35
pKb(C5H5N) = 8.85
pKb(CH3NH2) = 3.36
pKa(C6H5OH) = 9.96

(Ans: HNO3 < HNO2< HClO < C6H5OH< C5H5N < CH3NH2 < LiOH < Ca(OH)2 )

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 AQUEOUS SALT SOLUTIONS And
MORE PRACTICE CALCULATIONS

1. STRONG ELECTROLYTES AND IONS

Remember that if a salt is soluble in water, it is a strong electrolyte that fully dissociates into ions: Cations
and Anions.

We have already encountered ions which were:

Spectator ions: they did not do anything (i.e. did not participate in NIE)

Conjugate acids of weak bases: they were themselves weak acids

Conjugate bases of weak acids: they were themselves weak bases

So we can characterize ions by looking at them and assessing if they are neutral (i.e. spectator), acidic or
basic.

1. Cations
Acidic Examples
- conjugate acids of weak bases C5H5NH+, C6H5NH3+, NH4+, CH3NH3+, etc.

- small, highly charged metal ions Fe3+, Cr3+, Al3+, Fe2+, Cu2+, Ni2+
Neutral
- group 1 & 2 cations; Li+, Na+, …; Mg2+, Ca2+, …;
- +1 metals Ag+, Cu+, etc.

2. Anions:
Acidic Examples
- very few HSO4–, H2PO4–
Neutral
- anions of strong acids Cl–, Br–, I–, NO3–, ClO4–
Basic
- conjugate bases of weak acids F–, O2–, OH–, S2–, HS–, CN–, CO32–, HCO3–,
HPO4–, etc.

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Question 1: Classify the following as acidic (A), basic (B), or neutral (N).
If acidic or basic write the relevant equation (DIY) to prove this.

i) LiBr

ii) KCN

iii) NH4NO3

iv) KHS (DIY)

v) NaHCO3 (DIY)

Question 2: Which of the following pairs of ions CANNOT exist in large concentrations?
simultaneously in aqueous solution?

A. K+ and CH3COO–
B. H3O+ and ClO4–
C. H3O+ and F–
D. Na+ and CN–
E. Li+ and OH–

END OF MODULE 19
PLEASE COMPLETE ACTIVITY 19

27
 – ACIDS & BASES IN AQUEOUS
SOLUTION –
MODULE 20
2. RECAP ON WA/WB AND SA/SB

Weak Acids:

Molecular: HA(aq) + H2O(l) H3O+(aq) + A–(aq) Ka (HA)

Conjugate Acid: BH+(aq) + H2O(l)  H3O+(aq) + B(aq) Ka (BH+) = Kw/Kb (B)

Weak Bases:

Molecular: B(aq) + H2O(l) BH+(aq) + OH–(aq) Kb(B)

Conjugate Base: A–(aq) + H2O(l) HA(aq) + OH–(aq) Kb= Kw/ Ka(HA)

Water Dissociation: Kw = [H3O+] × [OH-] = Ka × Kb

H2O(l) + H2O(l) H3O+(aq) + OH–(aq); Kw

YOU must be able to RECOGNIZE what kind of solution (i.e., SA, SB, N, WA or WB), then produce
the correct equations and K value.

Question 3: Calculate the pH of each of the following if the solution is 0.10 M:

(a) HCl, 0.10 M

(b) HCN, 0.10 M [Ka(HCN) = 4.910–10]

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(c) NH4Cl, 0.10 M [Kb(NH3) = 1.8 x 10-5]

(d) NaCN, 0.10 M

(e) NaOH, 0.10 M

Range of pH Scale:
What do you think the range of the pH scale actually is,
A) 1 to 14,
B) 0 to 14,
C) something else - if so, what?

Case 1: [H3O+] = 5 M

pH =

Case 2: [OH–] = 5 M

pH =

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Question 4: You have access to Ka or Kb values.
Determine Keq for the following:
(i) H3O+(aq) + OH–(aq) 2H2O(l) Keq ?

What does it meant? H3O+(aq) + OH–(aq) → 2H2O(l)

(ii) F–(aq) + H3O+(aq)  HF(aq) + H2O(l) Keq ?

What does that mean? F–(aq) + H3O+(aq) → HF(aq) + H2O(l)

(iii) HCN(aq) + OH–(aq) H2O(l) + CN–(aq) Keq ?

What does that mean? HCN(aq) + OH–(aq) → H2O(l) + CN–(aq)

What do we conclude from the question above ?

As we can see for the Keq calculated in (i)-(iii),
 a Strong Acid: H3O+ and a strong Base: OH– cannot co-exist in solution, they react with one another
immediately
 a Strong Acid: H3O+ and a Weak Base (B or A–) cannot co-exist in solution, they react with one
another immediately
 a Strong Base OH– and a weak acid (AH or BH+) cannot co-exist in solution, they react with one
another immediately

Question 5: A volume 10.0 mL of 1 M aqueous NaOH is added to 10.0 mL of a 5 M solution of Acetic

Acid.
What is the reaction that takes place?

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CIE:
NIE:
Calculate the Keq for this NIE.

What does that mean for the NIE?

What are the species present in solution, what are the concentrations of these species?

HCOOH(aq) + OH–(aq) → H2O(l) + HCOO–(aq)

[Initial] 0

[Change]

Final

What is the limiting reagent?

Initial moles AcH =
Initial moles OH– =
Stoichiometry is 1/1
How much Acetate ion is formed ?

Final moles of Acetate Ac– =

C(Ac–) =
How much acetic acid is left?
Final moles of AcH left n(AcH)f =
C(AcH)f =

END OF MODULE 20
PLEASE COMPLETE ACTIVITY 20

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