EQUILIBRIA IN

SOLUTION
“It’s lunch time: how about a meal of citric and ascorbic acids (lemons
and oranges), oxalic acid (spinach), folic acid (broccoli),and lactic acid
(yogurt), all washed down with some phosphoric acid (soft drink)—if
you eat too much, you may need some magnesium or aluminum
hydroxide base(antacid)!”
---– Chemistry, the molecular nature of matter and change by Martin
Stuart Silberberg
• Acids and bases are in many common consumer products and are
indispensable in academic and industrial research
• Definitions:
➢ acids produce hydrogen ions in aqueous solution, and bases produce
hydroxide ions --- Arrhenius Svante
➢ an acid is a proton (H+) donor, and a base is a proton acceptor.---
Bronsted – Lowry
➢ An acid is an electron pair acceptor, and a base is an electron pair donor -
-- Lewis
• Consider the dissolution of gaseous HCl in water:
HCl ( g ) + H 2O ( l ) → H 3Oaq+ + Claq−

➢ each HCl molecule donates a proton to a water molecule, and so HCl

qualifies as a Brønsted–Lowry acid. The molecule that
accepts the proton—water in this case—is a Brønsted–Lowry base.
➢ The oxygen of the water molecule has two unshared electron pairs, either
of which can form a covalent (coordinate) bond with an H+ ion.

• Generally, the reaction for the dissolution of an acid in water can be represented as
HA ( aq ) + H 2O ( l ) H 3O + ( aq ) + A− ( aq )
Acid Base Conjugate Conjugate
acid base
• Variation in Acid Strength: The Acid-Dissociation
Constant (Ka)
• Acids (and bases) are classified by their strength,
– the amount of H3O+ (or OH-) produced per mole of substance
dissolved
– by the extent of their dissociation into ions.
• Because acids and bases are electrolytes, their strength
correlates with electrolyte strength:
– strong electrolytes dissociate completely, and
– weak electrolytes dissociate slightly.
• Strong acids dissociate completely into ions in water:
• In a dilute solution of a strong acid,

– HA molecules are no longer present:

– [H3O+] =[A-] ≈ [HA]init. In other words,
– [HA]eq ≈ 0,
– The value of Kc is extremely large:

– Example of such acids include HNO3, HCl, H2SO4, HOCl, HClO4 etc
• Weak acids dissociate slightly into ions in water

– In a dilute solution of a weak acid, the great majority of HA

molecules are undissociated.
– Thus, [H3O] << [HA]init, and [HA]eq ≈ [HA]init, so Kc is very small.
 Acid Dissociation Constant, Ka
• The reaction of a weak acid, HA, with water forms a dynamic
equilibrium involving H3O+ and a conjugate base, A-
• The equilibrium constant is called the ACID
DISSOCIATION/IONIZATION CONSTANT

• As earlier discussed the concentration terms for pure liquids and

solids are equal to 1 and do not appear in the equilibrium
expression. So the acid dissociation constant becomes:

– Where 𝐻 + 𝑎𝑞 = 𝐻3 𝑂+ 𝑎𝑞
• Acid-dissociation constants of weak acids range over many orders
of magnitude.
• Thus, for solutions of the same initial HA concentration, the
smaller the Ka, the lower the percent dissociation of HA:
– Weaker acid ⟹ lower % dissociation of HA ⟹ smaller Ka
• AUTO-IONIZATION OF WATER AND THE pH SCALE
– A substance is said to be amphoteric if it can behave either
as an acid or as a base.
– Water is the most common amphoteric substance.
– This behaviour can be seen in the auto-ionization of water, which
involve the transfer of proton from one water molecule to
another to produce hydroxonium (H3O+) and hydroxide (OH-) ions
•
• In this reaction one water molecule acts as an acid by furnishing a
proton, and the other acts as a base by accepting the proton.
H 2Ol + H 2Ol H 3Oaq+ + OH aq−
• The equilibrium constant for this auto-ionization reaction is

• Kw is called the ion – product of water (also known as the

dissociation constant of water). At 25 oC, experiment has shown that
for any aqueous system: 𝐻 + = 𝑂𝐻 − = 1.0 × 10−7 𝑀 ⟹
K w =  H +  OH −  = (1.0 10−7 M )(1.0 10−7 M ) = 1.0 10−14 M 2
– The unit is customarily omitted as in the case of equilibrium constant
• There are three possible situations all at 25 oC:

= 
• In each case, w   
K H +
  OH −

 = 1.0  10 −14
• Illustrations
– A research chemist adds a measured amount of HCl gas to pure
water at 25°C and obtains a solution with [H3O+] = 3.0×10-4 M.
Calculate the [OH-]. Is the solution neutral, acidic, or basic?
• SOLUTION
K w =  H +  OH −  = 1.0 10−14

𝐾𝑤 1.0 × 10−14
⇒ 𝑂𝐻 − = + = = 3.3 × 10 −11
𝐻 3.0 × 10−4
– Since 𝐻+ > 𝑂𝐻− , the solution is acidic
– It makes sense that adding an acid to water results in an acidic
solution.
– Also, since [H3O+] is greater than 10-7 M, [OH-] must be less than
10-7 M to give a constant Kw
• Can you try this?
– Calculate [H3O+] in a solution that has [OH-] = 6.7×10-2 M at
25°C. Is the solution neutral, acidic, or basic?
• To handle numbers with negative exponents more conveniently in
calculations, we convert them to positive numbers using a
numerical system called a p-scale, the negative of the common
(base-10) logarithm of the number. Applying this numerical system
to [H3O+] gives pH, the negative of the common logarithm of [H+]
(or [H3O+]):
pH = − log10  H + 
• A p-scale is used to express other quantities as well:
– Hydroxide ion concentration can be expressed as pOH:

– Acidic solutions have a higher pOH (lower [OH-]) than basic

solutions.
– Equilibrium constants can be expressed as pK:
• pK = –log K
– Specifically for weak acids:

• A low pK corresponds to a high K. So

• a reaction that reaches equilibrium with mostly products
present (proceeds far to the right) has a low pK (high K);
• a reaction that has mostly reactants present at equilibrium
has a high pK (low K).
• An important relationship:

• pH for Strong Acids and Bases:

– The equilibrium concentration of H3O+ is equal to the
initial concentration of a strong acid:
– 0.200 M HCl dissociates to produce 0.200 M H3O+.
– The equilibrium concentration of OH- is equal to the initial
concentration of an alkali metal hydroxide:
– 0.200 M KOH dissociates to produce 0.200 M OH- .
• Example:
• Calculate [H3O+], pH, [OH-], and pOH for each solution at
25°C:
– (a) 0.20 M HCl
– (b) 0.0012 M Mg(OH)2, used as an antacid in the treatment of
heartburns
• SOLUTION
• For 0.20 M HCl:
– [H3O+] = 0.20 M
– 𝑝𝐻 = −𝑙𝑜𝑔10 𝐻3 𝑂+ = −𝑙𝑜𝑔10 0.20 = 0.70
− 𝐾𝑤 1.0×10−14
– 𝑂𝐻 = = = 5 × 10−14 𝑀
[𝐻 + ] 0.20
– 𝑝𝑂𝐻 = −𝑙𝑜𝑔10 [𝑂𝐻 − ] = −𝑙𝑜𝑔10 5 × 10−14 = 13.3
• For 0.0012 M 𝑴𝒈 𝑶𝑯 𝟐
• 𝑴𝒈 𝑶𝑯 𝟐 ⟶ 𝑴𝒈𝟐+ + 𝟐𝑶𝑯−
– [OH-] = 2 × 0.0012 M = 0.0024 M
– 𝑝𝐻 = −𝑙𝑜𝑔10 𝑂𝐻 − = −𝑙𝑜𝑔10 0.0024 = 2.62
𝐾𝑤 1.0×10−14
– 𝐻+ = = = 4.17 × 10−12 𝑀
[𝑂𝐻 − ] 0.0024
– 𝑝𝐻 = −𝑙𝑜𝑔10 [𝐻 ] = −𝑙𝑜𝑔10 4.17 × 10−12 = 11.38
+

• The strong acid has pH < 7 and the strong base has a pH
> 7, as expected. In each case, pH + pOH = 14, so the
arithmetic seems correct.
• TRY THIS!!!
– Sodium hydroxide is used to clear clogged drains. A solution of
NaOH has a pOH of 4.48 at 25°C. What are its pH, [OH-], and
[H3O+]?
 SOLVING PROBLEMS ON ACID-BASE EQUILIBRIA
• Problem Phenylacetic acid (C6H5CH2COOH, simplified
here to HPAc) builds up in the blood of persons with
phenylketonuria, an inherited disorder that, if untreated,
causes mental retardation and death. A study of the acid
shows that the pH of 0.12 M HPAc is 2.62. What is the Ka
of phenylacetic acid?
• SOLUTION
• Given that pH = 2.62⟹ 𝑯+ = 𝟏𝟎−𝟐.𝟔𝟐 = 𝟎. 𝟎𝟎𝟐𝟒 𝑴
• Equation for the dissociation of HPAc is

• Let us set up a ICE Table

 Concentration 𝑯𝑷𝑨𝒄𝒂𝒒 ⇌ 𝑯+ 𝒂𝒒 + 𝑷𝑨𝒄− 𝒂𝒒
Initial 0.12 0 0
Change -x +x +x
Equilibrium 0.12 – x x x

• But 𝐻 + = 0.0024 𝑀 = 𝑃𝐴𝑐 − = 𝑥

Ka =
 H +   PAc − 
=
( x )( x )
=
0.00242
= 4.84  10−5
 HPAc  ( 0.12 − x ) 0.12 − 0.0012

Example 2:
• Propanoic acid (CH3CH2COOH, which we simplify to HPr) is a
carboxylic acid whose salts are used to retard mold growth in foods.
What are the [H3O+] and the pH of 0.10 M HPr (Ka = 1.3×10-5)
• The equation for the dissociation and the dissociation constant is:
 Concentration 𝑯𝑷𝒓𝒂𝒒 ⇌ 𝑯+ 𝒂𝒒 + 𝑷𝒓− 𝒂𝒒
Initial 0.10 0 0
Change -x +x +x
Equilibrium 0.10 – x x x

Ka =
 H +   Pr − 
=
( x )( x )
=
x2
 
H Pr ( 0.10 − x ) 0.10 − x

• A trick to avoid solving a quadratic equation for this kind of

problem is to assume that since the acid is a weak acid (from the
value of the Ka) and also that the initial concentration is very
high(0.10 M, relatively), the amount of it dissociated is negligibly
small compared to the initial concentration such that 0.10 − 𝑥 ≈
0.10.
• This assumption will be reasonable if the % dissociation < 5%,
otherwise, the quadratic equation will need to be solved to find x
• Using the assumption above

Ka =
 H +   Pr − 
=
( x )( x )
=
x2

x2
 H Pr  ( 0.10 − x ) 0.10 − x 0.10

 x 2 = 0.10  K a = 0.10  1.3  10−5 = 1.3  10 −6

 x =  H +  =  Pr −  = (1.3 10 ) = 1.14 10
−6 −3
M

• Is our assumption reasonable? Let us find out

amount dissociated
Percent dissociation = ×100%
intial amount
1.14 10−3
= 100%
0.10
= 1.14%
• Since this is less than 5%, it is a reasonable one
pH = − log10  H +  = − log10 (1.14  10−3 ) = 2.94
• Base Dissociation Constant
– Many compounds are bases even though they do not contain the
hydroxide ion.
– These compounds increase the concentration of hydroxide ions
in aqueous solution because of their reaction with water.

– In other words, these bases are Brønsted–Lowry bases.

• For example, according to the Brønsted–Lowry theory, ammonia,
NH3(aq), is a base because it reacts with water to form aqueous
hydroxide ions:

– The equilibrium position of this reaction is far to the left, ammonia is

considered to be a weak base.
– Compounds that react with water as ammonia does are generally weak
bases.
• However, since the concentration (density) of water is a constant, it
can be incorporated into the value of K (just as it was in the
equilibrium law equation for Ka). This yields a new constant, Kb,
called the base ionization constant:

• For the ammonia – water equilibrium; the Kb for the reaction is:
• Problem Dimethylamine, (CH3)2NH, a key intermediate in detergent
manufacture, has a Kb of 5.9×10-4. What is the pH of 1.5 M
(CH3)2NH?
• SOLUTION:

• Setting up the ICE table as usual

• Making similar assumption as we did under acid dissociation (

assuming x is negligibly small as compared to the initial
concentration of the base) i. e. 1.5 − 𝑥 ≈ 1.5. Substituting into the
Kb expression to have
• How reasonable is our assumption? Let us check
amount dissociated
Percent dissociation = ×100%
intial amount
3.0 10−2
= 100%
1.5
= 2.00% < 5%; assumption justified
ACID-BASE PROPERTIES
OF SALT SOLUTIONS

NEUTRALIZATION AND HYDROLYSIS

• When a strong acid reacts with a strong base to produce salts that consist of the cations of
strong bases and the anions of strong acids. These conjugate acids and bases have no effect

This reaction is known as

on [H+] when dissolved in water.

NEUTRALIZATION.
• Reaction between a strong acid and a weak base will yield a salt in which the conjugate acid of
the weak base becomes a stronger acid than water - water becomes a proton acceptor to yield
hydroxonium ion. Consequently, the pH of the solution is reduced because the solution is acidic
and not neutral (not a neutralization reaction):
HCl (aq ) + NH 3 ( aq ) → NH 4+ (aq ) + Cl − (aq )
acid ( strong ) base ( weak ) conjugate conjugate
acid base
NH +4 ( aq ) + H 2O ( l ) NH 3 ( aq ) + H 3O +
K a or K h

• The equilibrium constant for the hydrolysis of the cation of the weak base is:

 NH 3   H 3O + 
Ka =
 NH 4+ 
• Recall that for the base dissociation of NH3,
NH 3 ( aq ) + H 2O ( l ) NH 4+ ( aq ) + OH − ( aq )
Kb

• the base dissociation constant is:

 NH 4+  OH − 
Kb =
 NH 3 
 NH 4+  OH −   NH 3   H 3O + 
Kb  K a = 
 NH 3   NH 4+ 

• It is obvious that: =  H O  OH  3

+ −

=K
•  K K = K = 1.0  10
a b
w

w
−14
• Reaction between a weak acid and a strong base will yield a salt in which the
conjugate base of the weak acid becomes a stronger base than water - water
becomes a proton donor to yield hydroxide ion. Consequently, the pH of the
solution is increased because the solution is basic and not neutral (not a
neutralization reaction):
CH 3COOH (aq ) + NaOH ( aq ) −
→ +
CH 3COO ( aq ) + Na (aq ) + H 2O (l )
acid ( weak ) base ( strong ) conjugate conjugate
base acid
CH 3COO − ( aq ) + H 2O ( l ) CH 3COOH ( aq ) + OH − ( aq )
Kb or K h

• The base (the conjugate base) dissociation constant is given as:

CH 3COOH  OH − 
Kb =
CH 3COO − 
• The dissociation constant of the weak acid (that gives the conjugate base) is:
CH 3COOH + H 2O CH 3COO − + H 3O +
Ka

CH 3COO −   H 3O + 
Ka =
CH 3COOH
• Just as in the case for the dissociation of a weak base (producing a
conjugate acid). We can see that:
CH 3 COOH  OH −  CH 3 COO −   H 3O + 
Kb  K a = 
CH 3 COO −
CH 3 COOH 
= OH −   H 3O + 
=K w = 110−14
• In summary:
– For a weak acid(HA) and it’s conjugate base(A-), the relationship
between Ka and Kb (of the conjugate base) is established as:

– The equilibrium constants for each reaction can be expressed and

the equilibrium expression for the overall reaction will be the
product of the individual reactions that make the overall, that is:

–
K a ( HA )  K b ( A− ) = K w
 PRACTICE QUESTIONS
• In humans, blood pH is maintained within a narrow range: acidosis occurs if
the blood pH is below 7.35, and alkalosis occurs if the pH is above 7.45. Given
that the pKw of blood is 13.63 at 37°C (body temperature), what is the normal
range of [H3O+] and of [OH-] in blood?
• Putrescine [NH2(CH2)4NH2], found in rotting animal tissue, is now known to be
in all cells and essential for normal and abnormal (cancerous) growth. It also
plays a key role in the formation of GABA, a neurotransmitter. A 0.10 M
aqueous solution of putrescine has [OH-] = 2.1×10-3. What is the Kb?
• Sodium stearate (C17H35COONa) is a major component of bar soap. The Ka of
the stearic acid is 1.3×10-5. What is the pH of 10.0 mL of a solution containing
0.42 g of sodium stearate?
• Tris(hydroxymethyl)aminomethane, known as TRIS or THAM, is a water-
soluble base used in synthesizing surfactants and pharmaceuticals, as an
emulsifying agent in cosmetics, and in cleaning mixtures for textiles and
leather. In biomedical research, solutions of TRIS are used to maintain nearly
constant pH for the study of enzymes and other cellular components. Given
that the pKb is 5.91, calculate the pH of 0.075 M TRIS.