Acid-Base Equilibria

Acid-Base Equilibria
Arrhenius Concept
Acid: A substance that produces hydronium ion, H30+, in aqueous solution.
Base: A substance that produces hydroxide ion, OH-, in aqueous solution.
H2O (l) + H2O (l) ↔ H3O+ (aq) + OH- (aq)
H2O (l) + HCl (aq)  H30+ (aq) + Cl- (aq)
H2O
NaOH (s)  Na+ (aq) + OH- (aq)
Acid and base can be classified as either strong or weak.
Strong acids completely ionize (or dissociate) in aqueous solution to give H 3O+ and
an anion. E.g. perchloric acid, HClO4 and hydrochloric acid, HCl.
H2O (l) + HClO4 (aq)  H30+ (aq) + ClO4- (aq)
H2O (l) + HCl (aq)  H30+ (aq) + Cl- (aq
Strong bases completely ionize in aqueous solution to give OH- and a cation. E.g
Sodium hydroxide, NaOH.
H2O
NaOH (s)  Na+ (aq) + OH- (aq)
• Hydroxides of Group IA and Group IIA elements (except Be) are strong bases.
• Weak acids and bases ionize only partially in aqueous solution, typically less than
5%.
• Most acids and bases we encounter in our daily lives are weak acids and bases.
E.g Acetic acid (vitamin C). These substances are not completely ionized and exist
in equilibrium with corresponding ions.
CH3COOH (aq)+ H2O (l) ↔ H3O+ (aq) + CH3COO- (aq)
Bronsted-Lowry Concept
Acid: proton (H+) donor; Base: proton acceptor.
In the Brosted-Lowry concept, acid-base reactions involve the transference of

protons from the acid to the base. In so doing, an acid becomes its conjugate base
and the base becomes its conjugate acid:
H2O (l) + HA (aq)  H30+(aq) + Cl-(aq)
acid base conjugate conjugate
acid base
E.g.
1. H30+ (aq) + NH3 (aq) ↔ H2O (l) + NH4+ (aq)
Acid base conjugate Conjugate
base acid
2. HCl (benzene) + NH3(benzene)  NH4Cl (s)
3. NH3 (aq) + H2O (l) ↔ NH4+(aq) + OH-(aq)
A conjugate acid-base pair consist of two species in an acid-base reaction, one an acid the
other a base, that differ by the loss or gain of a proton.
Note that in examples 1 and 3 above, water can act s either an acid or a base, depending
on whether it has lost or gained a proton. Such species are known as amphoteric species.
In 1 water acts as a base, accepting a proton to form H30+ (aq).
In 2 water acts as an acid, donating a proton to NH3 to form NH4+ and OH-.
Lewis Concept
Certain reactions have characteristics of acid-base reactions but do not fit the
Arrhenius or Bronsted-Lowry concepts.
E.g
BF3 + NH3  H3N-BF3
In this reaction, the NH3 molecule donates an lone pair of electrons while the B in
BF3 accepts the electron pair.
A Lewis acid is a species that cam form a covalent bond by accepting an electron
pair from another species. A Lewis base is a species that can form a covalent bind
by donating an electron pair to another species.
Acid Strength
The Bronsted-Lowry concept considers an acid-base reaction as a proton-transfer
reaction. It is useful to think of such acid-base reactions as a competition between
species for protons.
HA(aq) + H2O(l) ↔ H3O+(aq) + A-(aq)
If H2O is much stronger base than A- (i.e. if H2O has a much greater affinity for H+
that A- does) the equilibrium position will be far to the right (i.e. most of the acid
dissolved will be ionized).
If, on the other, if A- is a much stronger base than H2O the equilibrium position will
lie far to the left (i.e. most of the acid dissolved will ionized).
If, on the other hand, if A- is a much stronger base that H2O, the equilibrium
position will lie far to the left (I.e. most of the acid dissolved will be present at
equilibrium at HA).
The equilibrium expression for this reaction is:
+ − + −
𝐻30 [𝐴 ] 𝐻 [𝐴 ]
Ka = [𝐻𝐴]
= [𝐻𝐴]
Ka= acid dissociation constant.
The strength of an acid is defined by the equilibrium position of its dissociation
reaction:
HA(aq) + H2O(l) ↔ H3O+(aq) + A-(aq)
A strong acid is one for which this equilibrium lies far to the right (i.e. almost all
the original HA is dissociated at equilibrium). A strong acid yields a weak conjugate
base relative to water, i.e. one that has a low affinity for H+.
A weak acid is one for which the equilibrium lies far to the left. A weak acids yields
a strong conjugate base relative to H2O.
The common strong acids are sulphuric acids are sulphuric acid (H2SO4(aq)),
hydrochloric acid (HCl(aq)). Sulphuric acid is an example of a diprotic acid, an acid
with two acidic protons.
The acid is a strong acid, dissociating virtually completely in water:
H2SO4 (aq) + H2O (l)  H3O+ (aq) + HSO4- (aq)
The HSO4- (aq) is a weak acid, only partially dissolving in water:
HSO4-(aq) + H2O(l) ↔ SO42-(aq) + H3O+(aq)
Example
1. Identify the conjugate acid-base pairs in these reactions:
(a) CH3COOH(aq) + H2O (l) ↔ H3O+ (aq) + CH3COO- (aq)
(b) NH4+(aq) + H2O(l) ↔ H3O+(aq) + NH3(aq)
(c) CO32-(aq) + H2O(l) ↔ HCO3-(aq) + OH-(aq)
2. Using Ka values from the above table, arrange the following species according to
their strength as bases:
H2O, F-, Cl-, NO2-, and CN-
Note that strong acids, such as HCl, H2SO4, etc., are not listed in the table. This is
because these acids are dissolved in water, the position of the equilibrium:
HCl (aq) + H2O (l) ↔ H3O+ (aq) + Cl- (aq)
Lies so far to the right that [HCl] can not be measured accurately. As a result,
+ −
𝐻30 [𝐶𝑙 ]
Ka =
𝐻𝐶𝑙
Can not be determined accurately.
Water as an Acid and a Base
Water is amphoteric, i.e. it can act as either an acid or a base. This means that
water undergoes self- or auto-ionization, which involves the transfer of a proton
from one water molecule to another water molecule to produce a hydronium ion
and hydroxide ion:
2. Another example of an amphoteric species is ammonia, NH3:

2NH3 (aq) ↔ NH4+(aq) + NH2-(aq)
The auto-ionization reaction of water leads to the equilibrium expression
Kw = [H30+][OH-]=[H+][OH-]
Kw = ion-product constant (or water dissociation constant).
Experimental data shows that at 25°C.

[H+]= [OH-] = 1.0 x 10-7 M
Which means that at 25°C.
Kw = [H+][OH-]= (1.0 x 10-7 M)(1.0 x 10-7 M) =1.0 x 10-14 M
The units are customarily omitted.
In any aqueous solution at 25°C, no matter what it contains, the product of [H+] and
[OH-] must always equal 1.0 x 10-14 . There are three possible solutions:
1. A neutral solution, where [H+]=[OH-]
2. An acidic solution, where [H+]> [OH-]
3. A basic solution, where [H+]< [OH-]
In each case, however, at 25°C
Kw = [H30+][OH-]=[H+][OH-]= 1.0 x 10-14
Example
1. At 60°C the value of Kw is 1.0 x 10-13.
Example
1. At 60°C the value of Kw is 1.0 x 10-13.
(a) Using Le Chatelier’s principle, predict whether the reaction
2H2O (l) ↔ H3O+ (aq) + OH- (aq)
Is endothermic or exothermic. Briefly justify your answer.
(b) Calculate [H+] and [OH-] in neutral solution at 60°C.
(b) @ 60°C [H+][OH-] = 1.0x10-13
For a neutral solution
[H+]=[OH-]=√1.0x10-13 = 3.0x10-7 M
2.A solution of barium hydroxide at 25°C is 0.125 M Ba(OH)2. What are the
concentrations of
(a) Hydroxide ion
(b) Hydronium ion
In this solution?
The pH of a solution
Because [H+] in an aqueous solution is typically very small, the pH scale is used to
present solution acidity, The pH is a log scale based on 10, where
pH = -log[H+]
Thus, for a solution in which [H+]= 1.0 x 10-7 M
Then
pH = -log(1.0 x 10-7)
= -(-7)
= 7.00
Concerning significant figures, the rule is that the number of decimal places in the
log is equal to the number of significant figures in the original number (i.e.
concentration).
Thus,
[H+] = 1.0 x 10-9 M (2 significant figures)
pH= -log(1.0 x 10-7 M)
= 9.00 (2 decimal places)
We can find the pH of solution of known hydroxide ion concentration by first
solving for the hydronium-ion concentration. Alternatively, we can also find the pH
simply from the pOH, a measure of hydroxide-ion concentration similar to the pH:
pOH = -log[OH-]
At 25°C:
Kw = [H+][OH-] = 1.0 x 10-14 -log on both sides
-logKw= (-log[H+]) + (-log[OH-]) = 14.00
pKw = pH + pOH = 14.00
Therefore, pH+ pOH =14.00
Example
1. What is the pH of a sample of gastric juice whose hydronium-ion concentration
is 0.045M?
2. A brand of carbonated beverage has a pH of 3.16. What is the hydronium-ion
concentration of this beverage?
3. A 0.010 M solution of ammonia, NH3, has a pH of 10.6 at 25°C. what is the concentration
of hydroxide ion?
Solution
[NH3] = 0.010M , pH=10.6
pH = -log[H+]
10.6 = -log[H+]
[H+]=10-10.6
= 2.511886 x 10-11 M
Kw = [H+][OH-] −
𝐾𝑤 1.0×10 14
[OH-]= + = −
[𝐻 ] 2.511886×10 11
= 4 x 10 -4 M
Calculating the pH of strong acid solution
When dealing with acid-base equilibria, it is important to focus on the solution
components and their chemistry.
E.g What species are present in a 1.0M solution of HCl?
Since HCl is strong acid, we assume that it dissociated completely in solution. Thus
in solution HCl dissociates to H+ (aq) and Cl- (aq) ions.
Next we determine which species are significant and which can be ignored. The
major species are those which exist in relatively large amounts. In 1.0M HCl
solution, the major species are H+, Cl- and H2O. Since this solution is very acidic,
OH- is present in small amounts and can therefore be ignored.
Auto-ionization of water
2H2O (l) ↔ H3O+ (aq) + OH- (aq)
also contributes to the overall [H+] in the solution. However, compared to the [H+]
generated by dissociation of HCl, the [H+] contribution from auto-ionization of H2O
is insignificant, we can therefore assume that the pH of the solution is solely due to
the presence And dissociation of HCl in the solution.
Therefore; the pH of a 1.0M HCl solution is:
pH= -log[H+]
= -log(1.0)
= 0.00
Calculating the pH of weak acid solutions
Weak acids dissociated/ionize to a small extent in water. For the generic acid HA,
the equilibrium expression for the dissociation of the acid in the water is:
HA (aq) + H2O (l) ↔ H3O+ (aq) + A- (aq)
+ −
𝐻30 [𝐴 ]
Ka =
𝐻𝐴
To demonstrate how we calculate the pH of a weak acid, lets determine the pH of
1.00M solution of HF (Ka = 7.2 x 10 -4)
Step 1: Identify the major species in solution. From its small Ka value, we know that
hydrofluoric acid is a weak acid and will only dissociate to a small extent in aqueous
solution. Major species: HF (because it has dissociates to a small extent), H 2O.
Step 2: Decide which of the major species can furnish H3O+ ions:
HF (aq) + H2O (l) ↔ H3O+ (aq) + F- (aq)
2H2O (l) ↔ H3O+ (aq) + OH- (aq)
Therefore; In aqueous solution, both HF and H2O can produce H3O+. But by
comparing Ka (HF) and Kw (7.2 x 10-4 and 1.0 x 10-14, respectively) we see that even
though HF is a weak acid, it is still a much stronger acid than water. Therefore; the
H3O+ contribution from water is negligible compared to the contribution from HF.
We can therefore ignore the H30+ contribution from the auto-ionization of water.
Therefore; it is the dissociation of HF that will determine the equilibrium
concentration of H3O+ and hence the pH.
Step 3: Set up an ICE table for the reaction.
HF (aq) + H2O (l) ↔ H3O+ (aq) + F- (aq)
Initial 1.00 - 0 0
Change -x - +x +x
Equilibrium 1.00-x - +x +x
Step 4: The equilibrium constant equation for the reaction is:
+ −
𝐻30 [𝐹 ] -4
Ka = 𝐻𝐹
= 7.2 x 10
(𝑥)(𝑥)
= = 7.2 x 10-4
1.00−𝑥
Because Ka is so small, we expect the value of x to be negligible compared to 1.00M
, therefore; the denominator can be approximated as follows:
(1.00 – x) ≈ 1.00
Step 5: Solve for x
𝑥2
= 7.2 x 10-4 multiply by 1.00
1.00
x2 = (7.2 x 10-4)(1.00)
= 7.2 x 10-4 square root
x = √ 7.2 x 10-4
= 2.7 x 10-2
How valid is the approximation that [HF] at equilibrium ≈ 1.00M? Typically, the Ka
values for acids are known to an accuracy of about ±5%. We can therefore apply
this figure when determining the validity of the approximation.
[HA]o – x ≈ [HA]o
𝑥2 𝑥2
Ka = 𝐻𝐴 𝑜 −𝑥
≈ 𝐻𝐴 𝑜
Where
Ka[HA]o ≈ x2
x ≈ √Ka[HA]
𝑥
If the expression [𝐻𝐴]x 100% is less than or equal to 5%, the value of x is small
enough for the approximation
[HA]o – x ≈ [HA] to be considered valid.
Therefore in our example:
x = 2.7 x 10-2 M
[HF]o = 1.00M
−
2
2.7×10
x 100% = 2.7%
1.00
The approximation we made is considered valid.
x= [H3O+] = 2.7 x 10-2 M
Step 5: Calculate the pH of the solution
pH= -log[H+] = -log(2.7x 10-12) = 1.57
The pH of a mixture of weak acids
Example
(a) Calculate the ph of a solution that contains 1.00M HCN (Ka =6.2 x 10-10) and 5.00 M
HNO2 (Ka = 4.0 x 10-4).
(b) Calculate the concentration of cyanide ion (CN-) in this solution.
Solution
(a) Major species in solution: HCN, HNO2 and H2O
Species that produce H3O+:
HCN (aq) + H2O (l) ↔ H3O+ (aq) + CN- (aq) Ka= 6.2 x 10-10
HNO2 (aq) + H2O (l) ↔ H3O+ (aq) + NO2- (aq) Ka= 4.0 x 10-4
2H2O (l) ↔ H3O+ (aq) + OH- (aq) Kw = 1.0 x 10-14
HNO2 is weak acid, however it is a much stronger acid than both HCN and H 2O
(based on Ka values). The H3O+ contribution from HCN and H2O can therefore be
neglected as they are negligible compared to the H3O+ contribution from HNO2.
Thus the equilibrium constant expression is:
+
𝐻3𝑂 [𝑁𝑂2−]
Ka =4.0 x 10-4 = [𝐻𝑁𝑂2]
HNO2 (aq) + H2O (l) ↔ H3O+ (aq) + NO2- (aq)
Initial 5.00 - 0 0
Change -x - +x +x
Equilibrium 5.00-x - +x +x
𝑥2
Ka =4.0 x 10-4 = 5.00−𝑥
Assume (5.00 – x) ≈ 5.00
𝑥2
4.0 x 10-4 = 5.00−𝑥
x2 = (4.0 x 10-4 )(5.00)
x =√ 0.00200
x = 0.045
[H30+] = 0.045 M
Ph = -log [H+] =-log(0.045) = 1.35
(b) Although HCN contribution to [H3O+] can be ignored, it is the only source of CN-
To calculate [CN-] at equilibrium, we consider the process
HCN (aq) + H2O (l) ↔ H3O+ (aq) + CN- (aq) Ka= 6.2 x 10-10
Note that the solution at equilibrium has [H3O+] = 0.045M even though the H30+
was contributed by the dissociation Of HNO2.
Note also that [HCN]o = 1.00M , and since Ka for HCN is so small, a negligible
amount of HCN will dissociate:
[HCN]-[HCN]o – amount of HCN dissociated
Thus we can make the approximation
[HCN]≈ [HCN]o = 1.00M
Since [H3O+] and [HCN] are known, we can determine [CN-] from the equilibrium
expression:
+ −
𝐻3𝑂 [𝐶𝑁 ]
Ka =6.2 x 10-10 = [𝐻𝐶𝑁]
− −
4.5 ×10 2 [𝐶𝑁 ]
= 1.00
−
6.2×10 10 1.00) −8
[CN-] = − = 1.4 × 10 M
4.5 ×10 2
Percent Dissociation
𝐴𝑚𝑜𝑢𝑛𝑡 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑒
Percent dissociation = 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 (𝑀)
x100%
E.g in the HF example:
[H3O+] = 2.7 x 10-2 M
−
2.7 ×10 2𝑀
Therefore; percent dissociation = x 100%
1.00𝑀
= 2.7%
For a given weak acid, the % dissociation increases as the acid solution becomes
more dilute.
Example
1. Compare the % dissociation for 1.0M acetic acid solution and 0.10M acetic acid
solution. Ka =1.8 x 10-5.
2. Lactic acid (HC3H5O3) is a waste product that accumulates in the muscle tissue
during exertion, leading to pain and a feeling of fatigue. In a 0.100M aqueous
solution, lactic acid is 3.7% dissociated. Calculate that value of Ka for this acid.
Bases
The general reaction between a base (B) and water is given by
B (aq) + H2O (l) ↔ BH+ (aq) + OH- (aq)
Base acid conjugate conjugate
acid base
The equilibrium
+ −
constant expression for this reaction is
𝐵𝐻 [𝑂𝐻 ]
Kb =
[𝐵]
Kb = base-ionization constant
Typically, pH calculations for solutions of weak bases are very similar to those for
weak acids.
Example
Calculate the pH of a 1.0M solution of methylamine (Kb =4.38 x 10-4).
Solution
Methylamine (CH3NH2) is a weak base, therefore major species in solution are:
CH3NH2, H2O
Both are bases, but since water is a much weaker base that CH3NH2, auto-ionization
of water can be neglected as a source of OH- The dominant equilibrium is :
CH3NH2 (aq) + H2O (l) ↔ CH3NH3+ (aq) + OH- (aq)
+ −
𝐶𝐻3𝑁𝐻3 [𝑂𝐻 ]
Kb =4.38 x 10-4 = [𝐶𝐻3𝑁𝐻2]
CH3NH2 (aq) + H2O (l) ↔ CH3NH3+ (aq) + OH- (aq)
Initial 1.0 - 0 0
Change -x - +x +x
Equilibrium 1.0-x + −
- x x
𝐶𝐻3𝑁𝐻3 [𝑂𝐻 ] 𝑥2 𝑥2
Kb =4.38 x 10-4 = = =
[𝐶𝐻3𝑁𝐻2] 1.0 −𝑥 1.0
x= 2.1 x 10 -2
x = [OH-] = 2.1 x 10-2 M
Note that since [H3O+][OH-] = 1.0 x 10-14, pH + pOH =14
pOH =-log[OH-] =-log(2.1 x 10-2) = 1.68
pH =14.00-1.68 =12.32
Note that for a conjugate acid-base pair, HA and A-:
HA (aq) + H2O (l) ↔ H3O+ (aq) + A- (aq)
+ −
𝐻30 [𝐴 ]
Ka =
[𝐻𝐴]
A- (aq) + H2O (l) ↔ HA (aq) + OH- (aq)
−
𝐻𝐴 [𝑂𝐻 ]
Kb = −
[𝐴 ]
+ − −
𝐻 0 [𝐴 ] 𝐻𝐴 [𝑂𝐻 ]
Ka x kb = 3 x −
[𝐻𝐴] [𝐴 ]
Ka x kb = [H3O+] [OH-] = Kw= 1.0 x 10-14
Polyprotic Acids
Some important acids, such as sulphuric acid (H2SO4), phosphoric acid( H3PO4) and
carbonic acid (H2CO3) can furnish more than one proton per molecule and called
polyprotic acids.
Carbonic Acid
Carbonic acid is a diprotic acid that dissociates as follows:
H2CO3 (aq) + H2O (l) ↔ H3O+ (aq) + HCO3- (aq)
+ −
𝐻30 [𝐻𝐶𝑂3 ]
Ka1 = = 4.3 x 10-7
[𝐻2𝐶𝑂3 ]
HCO3-(aq) + H2O (l) ↔ H3O+ (aq) + CO32-(aq)
+ −
𝐻30 [𝐶𝑂32
]
Ka2 = [𝐻𝐶𝑂3 ]
− = 4.8 x 10-11
Example
Calculate the fractions Of H2CO3, HCO3- and CO32- at pH 9.00.
Solution
The fraction of each species present is the concentration of that of all three
species.
E.g for HCO3-:
−
[𝐻𝐶𝑂3 ]
𝑓𝐻𝐶𝑂3 −= − −
𝐻2𝐶𝑂3 + 𝐻𝐶𝑂3 +[𝐶𝑂32 ]
Dividing the numerator and the denominator by [HCO3-] gives:
1
𝑓𝐻𝐶𝑂3 −= 𝐻 𝐶𝑂 2
−
[𝐶𝑂3 −]
2 −
3
+1+
[𝐻𝐶𝑂3 ] [𝐻𝐶𝑂3 ]
𝐻2𝐶𝑂3
− can be calculated from Ka1:
[𝐻𝐶𝑂3 ]
+ −
𝐻30 [𝐻𝐶𝑂3 ]
Ka1 = [𝐻 𝐶𝑂 ] inverse
2 3
[𝐻 𝐶𝑂3]
1/Ka1= 𝐻 0 +2[𝐻𝐶𝑂 − multiply by [H3O+]
3 3 ]
+
[𝐻2𝐶𝑂3 ] 𝐻30
− =
[𝐻𝐶𝑂3 ] 𝐾𝑎1
Since ka1 = 4.3 x 10-7 and pH = 9.00 [H3O+] = 1.00 x 10-9,
+ −
[𝐻2𝐶𝑂3 ] 𝐻30 1.00×10 9
[𝐻𝐶𝑂3 ]
− =
𝐾𝑎1
= − = 2.3 x 10-3
4.3×10 7
−
2
[𝐶𝑂3 ]
[𝐻𝐶𝑂3−]
can be calculated from Ka2:
+ −
2
𝐻30 [𝐶𝑂3 ]
Ka2 = [𝐻𝐶𝑂3−] = 4.8 x 10-11
− −
[𝐶𝑂32 ] 𝐾 𝑎2 4.8×10 11
So = + = − = 4.8x10-2
[𝐻𝐶𝑂3−] [𝐻3𝑂 ] 1.00×10 9
1 1
Therefore 𝑓𝐻𝐶𝑂3 −= 𝐻2𝐶𝑂−3 2
−
[𝐶𝑂3 −] = −
3
−
2 =0.95
+1+ 2.3×10 +1+4.8×10
[𝐻𝐶𝑂3 ] [𝐻𝐶𝑂3 ]
Example
1. Calculate the pH of a 5.0M H3PO4 solution and determine the equilibrium
concentrations of the species H3PO4,H2PO4-,HPO42- and PO43-.
2. Calculate the pH of a 1.0M H2SO4 solution.
Note that for weak polyprotic acids:
1.Typically, successive Ka values are so much smaller than Ka1 that only the first
dissociation step makes a significant contribution to the calculation of the pH for a
solution of a weak polyprotic acid is identical to that for a solution of weak
monoprotic acid.
2. Sulfuric acid is unique in being a strong acid in its first dissociation step and a
weak acid in its second dissociation. For relatively concentrated solutions of H 2SO4
(1.0M and higher), the larger [H3O+] from the first dissociation step represses the
second dissociation step, which can be ignored as a contributor of H 3O+ IONS. For
filute solutions, the second step is a significant contributer of H3O+ and must be
considered in obtaining the overall [H3O+].
Acid-Base PROPERTIES OF SALT Solutions
Salt: an ionic compound obtained by a neutralization reaction in aqueous solution.
Salts that produce Neutral solutions
Salts composed of the cations of strong bases and the anions of strong acids have
no effect on [H3O+] when dissolved in water. Therefore; aqueous solutions of salts
like KCl, NaCl, NaNO3 and KNO3 are neutral.
Salts that produce Basic Solutions
For any salt whose cation has neutral properties (i.e has no effect on [H3O+]) such
as Na+,K+ and whose anion is the conjugate base of a weak acid, the aqueous
solution will be basic.
Example
Calculate the pH of a 0.30M NaF solution. (Ka for HF=7.2x10-4).
Solution
1. Major species in solution: Na+, F-, H2O because:
H2O
NaF(s) Na+ (aq) + F- (aq)
2. HF is a weak acid therefore F- must have a significant for H+ and the dominant
reaction will be:
F-(aq) + H2O(l)HF
−
(aq) + OH - (aq)
𝐻𝐹 [𝑂𝐻 ]
Kb = −
[𝐹 ]
Recall that for a conjugate acid-base pair, HA and A-,
𝐾𝑤
Kw= Ka x Kb= Kb = 𝐾𝑎
Therefore for the conjugate acid-base pair HF and F-.
−
14
1.0×10
Kb (F-)= 7.2×10−4 = 1.4x10-11
3. Set up ICE table for the dominant equilibrium:
F-(aq) + H2O(l)HF (aq) + OH- (aq)
Initial 0.30 - 0 0
Change -x - +x +x
Equilibrium 0.30-x - x x
4.Solve for x =[HF]=[OH-]
−
𝐻𝐹 [𝑂𝐻 ] 𝑥 (𝑥) 𝑥2
Kb (F-)=1.4x10-11= −
[𝐹 ]
=0.30−𝑥≈ 0.30
x≈2.0x10-6= [OH-]
This approximation is valid by the 5% rule.
Therefore pOH= -log[OH-]
=-log(2.0x10-6)
=5.69
pH=14.00-pOH
14.00-5.60=8.31
Salts that produce acidic solutions
In general, a salt whose cation is a conjugate acid of a weak base. A second type of
salt that produces acidic solutions is one that contains a highly charged metal ion.
Example
1. Calculate the pH of a 0.10M NH4Cl solution. Kb(NH3)= 1.8 x 10-5
2. Calculate the pH of a 0.010M AlCl3 solution. Ka(Al(H20)63+) = 1.4 x 10-5
Solution
H2O
1. NH4Cl(s) NH4+ (aq) + Cl- (aq)
Therefore major species in solution: NH4+, Cl-, H2O.
The dominant equilibrium is:
NH4+(aq) + H2O(l)NH3 (aq) + H3O+ (aq)
For which
+
𝑁𝐻3 [𝐻3𝑂 ]
Ka= +
[𝑁𝐻4 ] −
14
𝐾𝑤 1.0×10
Therefore Ka= = − = 5.6x10-10
𝐾𝑏(𝑁𝐻3) 1.8×10 5
3.ICE table for the dominant equilibrium:
NH4+(aq) + H2O(l)NH3 (aq) + H3O+ (aq)
Initial 0.10 - 0 0
Change -x - +x +x
+
𝑁𝐻3 [𝐻3𝑂 ] 𝑥 (𝑥) 𝑥2
Ka (NH4+)=5.6x10-10= = ≈
[𝑁𝐻4+] 0.10−𝑥 0.10
x≈7.5x10-6= [H3O+]
Approximation valid by5% rule, therefore
x= [H3O+]=7.5x10-6M
pH=-log[H3O+]=-log(7.5x10-6)=5.13
2.AlCl3 dissociates in aqueous solution to give
H2O
AlCl3(s) Al3+ (aq) + 3Cl- (aq)
Al3+ exists in aqueous solution as the hydrated ion(Al(H2O)63+. This ion In water is
weak acid:
Al(H2O)63+ (aq) ↔ Al(OH)(H2O)52+ (aq) + H+ (aq)
Major species in solution are:
Al(H2O)63+, Cl-, and H2O
Al(H2O)63+(aq) + H2O (l) ↔ Al(OH)(H2O)52+ (aq) + H+ (aq)
Initial 0.010 - 0 0
Change -x - +x +x
+
Al(OH)(H 2O)52+ [𝐻3𝑂 ] 𝑥 (𝑥) 𝑥 2
Ka (Al(H2O)63+)=1.4x10-5= = ≈
[Al(H2O)63+] 0.010−𝑥 0.010
x≈3.7x10-4= [H3O+]
The approximation is valid by the 5% rule, therefore
x= [H3O+]=3.7x10-4M
pH=-log[H3O+]=-log(3.8x10-4)=3.43
For salt solutions where the salt is composed of the cation that is a conjugate acid
od weak base, and the anion is a conjugate base of a weak base, and the anion is a
conjugate base of a weak acid, both components of the salt have an effect on the
pH of the solution. To determine whether the resulting solution is acidic, basic or
neutral, we compare the ka and kb values of the involved cation and anion,
respectively.
If Ka > Kb then the solution is acidic.
If Kb > Ka then the solution is basic.
If Ka = Kb then the solution is neutral.
Example
Predict whether an aqueous solution of each of the following salts will be acidic,
basic or neutral:
(a) NH4CH3COO
(b) NH4CN
(c) Al2(SO4)3
Common-Ion Effect
The common-ion effect is the shift in an ionic equilibrium caused by the addition of
a solute that provides an ion that takes part in the equilibrium.
Suppose we have a solution containing the weak acid HF (Ka=7.2x10-4) and its salt,
sodium fluoride (NaF). The salt NaF is a strong electrolyte.
Therefore:
H2O
NaF(s) Na+ (aq) + F- (aq)
HF is a weak acid and will therefore dissociate only to a small extent in solution:
HF(aq) + H2O (l)↔ H3O+ (aq) + F- (aq)
Therefore major species in this solution are:
HF, Na+, F-, and H2O and F- is the common-ion since it is produced by both HF and
NaF.
According to Le chatelier’s principle, the dissociation equilibrium for HF will be
driven to the left by the presence of the F- ions from the NaF:
HF(aq) + H2O (l)↔ H3O+ (aq) + F- (aq)
↑Added F- from NaF
←Equilibrium shifts away from the added
component. Net result is that [H3O+] is reduced.
This effect makes the solution of HF + NaF to be less acidic than the solution of HF.
Example
In an earlier example we found that the equilibrium concentration of H3O+ in a
1.0M HF solution is 2.7x10-2 M and the percent dissociation of HF is 2.7%. Claculate
[H3O+] and the % dissociation of HF in a solution containing both 1.0M HF (Ka = 7.2
x 10-4) and 1.0M NaF.
Solution
1. Major species: HF, F-, Na+ and H2O.
2. Na+ ions have neither acidic nor basic properties.
Water is a very weak acid/base.
Therefore HF and F- are the important species participating in the equilibrium that
determines [H3O+] and hence the pH of the solution:
HF(aq) + H2O (l)↔ H O + (aq) + F- (aq)
−
3
+
-4 𝐹 [𝐻3𝑂 ]
Ka =7.2x10 = [𝐻𝐹]
3. Ice table:
HF(aq) + H2O (l)↔ H3O+ (aq) + F- (aq)
Initial 1.0 - 0 0
Change -x - +x +x
− +
𝐹 [𝐻3𝑂 ] 𝑥 (𝑥) 𝑥 2
Ka (NH4+)=7.2x10-4= = ≈
[𝐻𝐹] 1.0−𝑥 1.0
x≈7.2x10-4= [H3O+]
thus
𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡
% dissociation = 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛x 100%
+
𝐻30 𝐸𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚
= 𝐻𝐹 𝑂
x 100%
−
7.2×10 4𝑀
= x 100%
1.0𝑀
= 0.072%
Buffers
A buffer is a solution that is characterized by the ability to resits changes in pH
when limited amounts of acids or base are added to it.
Buffers are composed of either a weak acid and its conjugate base (e,g HF and NaF)
or a weak base and its conjugate acid (e.g NH3 and NH4Cl).
Example
1. A buffered solution contains 0.50M acetic acid (CH3COOH, Ka = 1.8 x 10-5) and
0.5M sodium acetate (NaCH3COO).
(a) Calculate the pH of this solution.
(b) Calculate the charge in pH that occurs when 0.010 mole of solid NaOH is added
to 1.0L of the buffered solution.
(c ) Compare this pH change to the change that occurs when 0.010 mole of NaOH
(s) is added to 1.0L of water.
2. A buffered solution contains 0.25M NH3 (Ka =1.8 x 10-5) and 0.40M NH4Cl.
(a) Calculate the pH of this solution.
(b) Claculate the pH of the solution that results when 0.10 mole of gaseous HCl is
added to 1.0L of the buffered solution from part (a).
Solution
1.(a) Major species: CH3COOH, Na+ , CH3COO-, H2O.
2. Dominant equilibrium:
CH3COOH(aq) + H2O (l)↔ H3O+ (aq) + CH3COO- (aq)
3. Ice table:
Initial 0.50 - 0 0
Change -x - +x +x
− +
𝐶𝐻3𝐶𝑂𝑂 [𝐻3𝑂 ] 𝑥 (0.50+𝑥) (𝑥)(0.50)
Ka =1.8x10-5= [𝐶𝐻3𝐶𝑂𝑂𝐻]
= 0.50−𝑥 ≈ 0.50
x≈1.8x10-5= [H3O+]
The approximation is valid by the 5% rule
pH=-log[H3O+]=-log(1.8x10-5)=4.74
(b) Change in PH
Major species before any reaction occurs:
CH3COOH, Na+ ,CH3COO-, OH- and H2O.
The solution contains a relatively large amount of OH-, which is a strong base. In
this solution, the best source of H+ is CH3COOH, since it is a much stronger base
than H2O.
CH3COOH(aq) + OH- (aq)↔ H2O (l) + CH3COO- (aq)
So In this solution we have a stoichiometry problem and an equilibrium problem:
CH3COOH(aq) + OH- (aq)↔ H2O (l) + CH3COO- (aq)
Before reaction 1.0Lx0.5M 0.010mole - 1.0L x 0.50M
=0.5mole =0.50mole
After reaction 0.50-0.010 0.010-0.010 - 0.50+0.010
=0.49mole =0 mole - 0.51mole
Equilibrium problem
After the reaction between OH- and CH3COOH has run to completion, the major
species in solution are: CH3COOH, Na+, CH3COO- and H2O.
The dominant equilibrium is:
Initial 0.49 - 0 0
Change -x - +x +x
Equilibrium 0.49-x
− +
- x 0.51+x
𝐶𝐻3𝐶𝑂𝑂 [𝐻3𝑂 ] 𝑥 (0.51+𝑥) (𝑥)(0.51)
Ka =1.8x10-5= = ≈
[𝐶𝐻3𝐶𝑂𝑂𝐻] 0.49−𝑥 0.49
x≈1.7x10-5= [H3O+]
pH=-log[H3O+]=-log(1.7x10-5)=4.76
(c) ΔpH=4.76-4.74= 0.02
Therefore ph has increased by 0.02 pH units.
Henderson-Hasselbalch Eqaution
A buffer solution can be prepared from a conjugate acid-base pair in which the acid
dissociation constant, Ka, is approximately equal to [H3O+] desired for the solution.
HA (aq) ++ H2−O (l) ↔ H3O+ (aq) + A- (aq)
𝐻30 [𝐴 ] 𝐻𝐴
Ka = multiply by −
[𝐻𝐴] [𝐴 ]
+ 𝐻𝐴
[H3O ]= Kax [𝐴−] -log
𝐻𝐴
-log[H3 O+ ]= -logKax-log( [𝐴−] )
−
[𝐴 ]
pH= pKa + log( )
[𝐻𝐴]
[𝒄𝑶𝑵𝑱𝑼𝑮𝑨𝑻𝑬 𝑩𝑨𝑺𝑬]
pH= pKa + log( [𝑨𝑪𝑰𝑫]
)
The Henderson-Hasselbalch equation for bases is as follows:
B(aq) + H2O (l) ↔ BH+ (aq) + OH- (aq)
+ −
𝐵𝐻 [𝑂𝐻 ] 𝐵
Kb = [𝐵]
multiply by [𝐵𝐻+]
𝐵
[OH- ]= Kbx + -log
[𝐵𝐻 ]
𝐵
-log[OH- ]= -logKbx-log([𝐵𝐻+])
+
[𝐵𝐻 ]
pOH= pKb + log( [𝐵] )
Therefore; for a buffer solution composed of a weak base and its conjugate acid(i.e its salt),
the pOH of the solution is given by:
[𝑪𝒐𝒏𝒋𝒖𝒈𝒂𝒕𝒆 𝒂𝒄𝒊𝒅)]
pOH= pKb + log( )
[𝑩𝒂𝒔𝒆]
The ph of the solution can be determined from the relationship:
pOH= 14.00 – pH
Note, also, that since Kw =Ka x Kb
pKw = pKa + pKb
Example
Attempt Question 2 in the last example using the Henderson-Hasselbalch quation
for basic buffers.

Acid-Base Equilibria

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Acid-Base Equilibria

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Acid-Base Equilibria

In the Brosted-Lowry concept, acid-base reactions involve the transference of

2. Another example of an amphoteric species is ammonia, NH3:

Experimental data shows that at 25°C.

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