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PART-D
IONIC EQUILLIBRIA
By :
S.K.Sinha
Arrhenius concept:
Acid a substance that produces hydrogen ion in aqueous solution.
Base a substance that produces hydroxide ion in aqueous solution.
Examples of Acids:
1. HCl(aq) H+(aq) + Cl-(aq); (a strong acid)
2. HNO3(aq) H+(aq) + NO3-(aq); (a strong acid)
3. CH3COOH(aq) ⇋ H+(aq) + CH3COO (aq); (a weak acid)
-
Examples of bases:
1. NaOH(aq) Na+(aq) + OH-(aq); (a strong base)
2. Ba(OH)2(aq) Ba2+(aq) + 2OH-(aq); (a moderately strong base)
8. NH3(aq) + H2O ⇋ NH4+(aq) + OH-(aq); (a weak base)
* All hydroxides and oxides of metal are bases.
(Oxides of metals in veryhigh O.N. is acidic. Ex CrO3 , Mn2O7 .
* Reactions that involve the transfer of protons (H+) are acid-base reactions.
In each reaction, a conjugate base is what remains of the acid molecule after it loses a
proton (H+), and a conjugate acid is what becomes of the base after it gains a proton.
acid1 - conjugate base1 and acid2 - conjugate base2 are called conjugate acid-base pairs;
they are a pair of species that are related to each other by the loss or gain of a single
For binary acids such as HF, HCl, HBr, and HI, HX bond strength decreases down
the group. The weaker the bond, the easier the molecule ionizes in aqueous solution.
Hence, the stronger will be the acid. Thus, for this group of acids, their strength increases
down the group:
HF < HCl < HBr < HI; H2O < H2S < H2Se < H2Te
Among the hydrohalic acids, HF is the only weak acid; the others are strong acids. The
relative strength of HCl, HBr, and HI cannot be differentiated in aqueous solution, because
each of them dissociates almost completely. Less polar solvents are used to determine their
relative strength. For example, HCl, HBr and HI ionize only partially in acetone or
methanol, which have a weaker ionizing strength than water. The ionization of HCl in
acetone can be represented by the following equilibrium:
(CH3)2CO(l) + HCl(acetone) ⇋ (CH3)2COH+(acetone) + Cl-(acetone)
The degree of ionization in acetone increases in the order of HCl < HBr < HI. Based on this
observation, it was determined that the acidity of hydrogen halides increases down the
For the same period hydrides, the relative acidity increases from left to right, such that:
CH4 < NH3 < H2O < HF; PH3 < H2S << HCl
Water is a stronger acid than ammonia, and in acid-base reaction, H2O acts as a BrØnsted-
Lowry acid, which donates a proton to NH3:
H2O(l) + NH3(aq) ⇋ NH4+(aq) + OH-(aq)
In reaction with HF, water acts as a BrØnsted-Lowry base, which accept a proton:
HF(aq) + H2O(l) ⇋ H3O+(aq) + F-(aq)
The Relative Strength of Oxo-acids
Oxo-acids are acids that contain one or more OH groups covalently bonded to a
central atom, which can be a metal or a nonmetal. The OH group ionizes completely or
partially in aqueous solution producing hydrogen ions. Some common examples of oxo-acids
are H2CO3, HNO3, H3PO4, H2SO4, HClO4, and HC2H3O2:
O O O
HOSOH HOPOH OClOH
O O O
H
For these type of acids, their relative strengths depend on the electronegativity of
the central atoms. The more electronegative the central atom, the more polarized the OH
bond and the more readily it ionizes in aqueous solution to release the H+ ion. For
example, N, S, and Cl are more electronegative than P, and HNO3, H2SO4, and HClO4 are
stronger acids compared to H3PO4. The relative acid strengths are: HNO3 > H2SO4 > H3PO4.
For oxo-acids with central atoms from the same group, their relative strength decreases
from top to bottom as the electronegativity of the central atom decreases:
HOCl > HOBr > HOI; HOClO > HOBrO > HOIO; HOClO2 > HOBrO2 > HOIO2
For oxo-acids containing identical central atom, acidity increases as more oxygen atoms are
bonded to it. For example, acidity increases in the following order:
HOCl < HOClO < HOClO2 < HOClO3; H2SO4 > H2SO3; HNO3 > HNO2
Oxygen is a very electronegative atom; when more oxygen atoms are bonded to the
central atom, the OH group in the molecule becomes more polarized (due to inductive
effect), and the more readily it ionizes to release H+ ion.
Acetic acid is an organic acid, which contains the acidic carboxyl group, -COOH.
When acetic acid (CH3COOH) ionizes, only the OH bond of the carboxyl group breaks, but
not the CH bonds. However, if one or more of the hydrogen atoms in the methyl group (-
CH3) is substituted with a more electronegative atom, the OH of -COOH group becomes
more polarized and ionizes more readily, and increasing the acidity. The following Ka values
illustrate the effect on the acidity of COOH when one or more of the methyl hydrogen is
substituted with more electronegative atoms:
CH3COOH(aq) ⇋ CH3COO-(aq) + H+(aq); Ka = 1.8 x 10-5
The oxide ion, O2-, has a very strong affinity for protons and reacts with water to produce
hydroxide ions:
O2-(aq) + H2O(l) 2OH-(aq)
Some metal oxides are amphoteric; for example, Al2O3, Cr2O3, PbO, SnO, and ZnO. They
react with both strong acids and strong bases:
Al2O3(s) + 6HCl(aq) 2AlCl3(aq) + 3H2O(l);
Al2O3(s) + 2NaOH(aq) + 3H2O(l) 2Na[Al(OH)4](aq);
Oxides of nonmetals are acidic. They form acidic solution when dissolved in water.
CO2(g) + H2O(l) ⇋ H2CO3(aq) ⇋ H+(aq) + HCO3-(aq);
SO2(g) + H2O(l) ⇋ H2SO3(aq) ⇋ H+(aq) + HSO3-(aq);
P4O10(g) + 6H2O(l) ⇋ 4H3PO4(aq); H3PO4(aq) H+(aq) + H2PO4-(aq);
Strong acids, such as HClO4, HCl, HNO3, and H2SO4, are those that are considered to
completely ionize at 1 M concentration. The above equilibrium would lie far to the right.
Acids that are only partially ionized at this concentration, such as HC2H3O2, HF, HNO2,
H2SO3, H3PO4, and HClO, are considered weak acids. Their dissociation equilibria would lie
far to the left.
The equilibrium constant, Ka, for the acid ionization is given by the following expression:
[H3O+][A-] [H+][A-]
Ka = =
[HA] [HA]
Exercise-2:
1. What is [OH-] if [H+] = 0.0050 M? Is the solution acidic, basic or neutral?
2. What is the [H+] if [OH-] = 6.0 x 10-4 M? Is the solution acidic, basic or neutral?
________________________________________________________________________
The pH Scale
pH is a scale that measures the acidity of an aqueous solution where [H+] is very small.
pH = -log[H+],
We can also express basicity using the log scale for [OH-], such that pOH = -log[OH-]
That is, if a solution has [OH-] = 1.0 x 10-7 M, pOH = -log(1.0 x 10-7) = -(7.00) = 7.00
Since, at 25oC, Kw = [H+][OH-] = 1.0 x 10-14
pKw = -log Kw = -log[H+] + (-log[OH-]) = -log(1.0 x 10-14) = -(-14.00) = 14.00
pKw = pH + pOH = 14.00; and pOH = 14.00 – pH
Thus, in aqueous solutions, if pH > 7.00 pOH < 7.00, and vice versa;
In neutral solution, [H+] = [OH-] = 1.0 x 10-7 M, and pH = pOH = 7.00;
[H+] > 1.0 x 10-7 M, pH < 7.00, the solution is acidic.
[H+] < 1.0 x 10-7 M, pH > 7.00, the solution is basic.
_________________________________________________________________________.
Calculating the pH of Strong Acid and Strong Base Solutions
Strong acids are assumed to ionize completely in aqueous solution. For monoprotic
acids (that is, those acids with a single ionizable hydrogen atom), the concentration of
hydrogen ion in solution is the same as the molar concentration of the acid. That is
[H+] = [HA]
A strong base such as NaOH, contains OH- which concentration is equal to that of dissolved
NaOH. That is, a solution of 0.10 M NaOH(aq) contains [OH-] = 0.10 M
Weak acids do not ionize completely. At equilibrium, [H+] is much less than the
concentration of the acid. The concentration of H+ in a weak acid solution depends on the
initial acid concentration and the Ka of the acid. To determine [H+] of a weak acid we can
set up the “ICE” table as follows:
Consider a solution of 0.10 M acetic acid and its ionization products:
Concentration: HC3H3O2(aq) ⇋ H+(aq) + C2H3O2-(aq)
Initial [ ], M: 0.10 0.00 0.00
Change, [ ], M: -x +x +x
Equilibrium [ ], M : (0.10 - x) x x
The acid ionization constant, Ka, is given by the expression:
Ka = [H+][C2H3O2-] = x2 = 1.8 x 10-5
[HC2H3O2] (0.10 – x)
Since Ka << 0.10, we can use the approximation that x << 0.10, and (0.10 – x) ~ 0.10
Then, Ka = x2 ~ x2/0.10 = 1.8 x 10-5 ;
(0.10 – x)
x2 = (0.10)(1.8 x 10-5); x = (1.8 x 10-6) = 1.3 x 10-3
Note that, x = [H+] = 1.3 x 10-3 M; pH = - log(1.3 x 10-3) = 2.89
Percent Dissociation
The percent dissociation (or degree of ionization) of a weak acid is defined as
follows:
Percent dissociation = Amount of acid that dissociate (mol/L)
Initial concentration of acid (mol/L)
Ka or pKa is a measure of the acid strength. The stronger the acid, the more of it
ionizes, and the greater its Ka (or the lower its pKa). The percent dissociation of a weak acid
then depends on its Ka and also on the degree of dilution. In the more dilute acid, a higher
percentage of the molecules will ionize.
Now consider a solution of 0.010 M acetic acid and its ionization products:
Concentration: HC3H3O2(aq) ⇋ H+(aq) + C2H3O2-(aq)
Initial [ ], M: 0.010 0.00 0.00
Change, [ ], M: -x +x +x
Equilibrium [ ], M : (0.010 - x) x x
Ka << 0.010, we can still use the approximation that x << 0.010, and (0.010 – x) ~ 0.010
2. A 0.10 M aqueous solution of lactic acid, HC3H5O3, has a pH = 2.43. Determine [H+] in
this solution and the Ka of lactic acid. (Answer: [H+] = 3.7 x 10-3 M; Ka = 1.4 x 10-4)
3. If a 0.10 M benzoic acid, HC7H5O2 is 2.5% ionized, what is [H+] and pH of 0.10 M
benzoic acid? Calculate the Ka of benzoic acid.
(Answer: [H+] = 2.5 x 10-3 M; pH = 2.60; Ka = 6.4 x 10-5)
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Bases
Strong Bases:
Hydroxides of Group IA metals (LiOH, NaOH, KOH, RbOH, and CsOH) are strong
bases, but only NaOH and KOH are commercially important and are common
Among the hydroxides of the alkaline earth metals, Ca(OH)2, Sr(OH)2, and Ba(OH)2
are also relatively strong bases. When completely dissolved, these bases produce
two moles of OH- per mole of the base:
The hydroxides of other metals are only slightly soluble. Even in a saturated solution,
the concentration of OH- is still quite low. For example, a saturated solution of
Mg(OH)2 has [OH-] ~ 3.1 x 10-4 M.
Weak Bases
Ammonia is the only weak base that is of commercial importance. Ammonia is very
soluble in water and ionizes as follows:
NH3(aq) + H2O(l) ⇋ NH4+(aq) + OH-(aq)
The base dissociation constant, Kb, is given by the expression:
[NH ][OH - ]
Kb = 4 = 1.8 x 10-5
[ NH 3 ]
The concentration of OH- of a weak base solution, such as NH3(aq), depends on its Kb and
the initial concentration of the base. For example, to determine [OH-], pOH and pH of 0.10
M NH3(aq), we can set up the following “ICE” table:
Exercise:
1. What is [OH-] in 0.0055 M KOH and what is the pH of the solution?
Acid strength decreases in the order: H3PO4 >> H2PO4- >> HPO42-;
Sulfuric acid is a strong acid because the first hydrogen ionizes completely:
H2SO4(aq) H+(aq) + HSO4-(aq); Ka1 = very large
However, the second hydrogen does not dissociate complete. Thus, HSO4- is a weak acid,
which dissociates as follows:
HSO4-(aq) ⇋ H+(aq) + SO42-(aq); Ka2 = 1.2 x 10-2
Exercise:
1. What is [H+], [HSO4-], and [SO42-] in 0.10 M H2SO4(aq)? What is the pH of the
solution? (Ka1 is very large; Ka2 = 1.2 x 10-2) (Answer: pH = 0.96)
2. What is the pH of 0.10 M oxalic acid, H2C2O4, and what is [C2O42-] in this solution?
(Ka1 = 6.5 x 10-2; Ka2 = 6.1 x 10-5 )
(Answer: [H+] = 0.054 M; pH = 1.26; [C2O42-] = 6.1 x 10-5 M)
_________________________________________________________________________
Salts of Weak Acid-Strong Base Reactions: such as NaF, NaNO2, NaC2H3O2, etc.
A salt that is the product of a reaction between a weak acid and a strong base will
form an aqueous solution that is basic in nature.
When sodium acetate is dissolved in water, it dissociates into sodium and acetate ions:
NaC2H3O2(aq) Na+(aq) + C2H3O2-(aq)
For example, ammonium chloride, NH4Cl, is produced by the reaction of a strong acid HCl
and a weak base NH3.
HCl(aq) + NH3(aq) NH4Cl(aq) NH4+(aq) + Cl-(aq)
In an aqueous solution, ammonium ion (NH4+) establishes the following equilibrium that
increases [H3O+] and makes the solution acidic:
NH4+(aq) + H2O(l) ⇋ H3O+(aq) + NH3(aq); Ka = [H3O+][NH3]
[NH4+]
For the reaction of NH3 with water, the following equilibrium occurs:
[NH4+] [NH3]
Thus, the hydrolysis of ammonium ion has Ka = 5.6 x 10-10 (> Kw), which implies that
aqueous solution of ammonium chloride will be acidic (pH < 7).
Salts of Weak Acid-Weak Base Reactions: such as NH4C2H3O2, NH4CN, NH4NO2, etc..
Aqueous solutions of this type of salts can either be neutral, acidic, or basic,
depending on the relative magnitude of the Ka of the weak acid and the Kb of the
weak base.
If Ka ~ Kb, the salt solution will be approximately neutral;
If Ka > Kb, the salt solution will be acidic, and
If Ka < Kb, the salt solution will be basic.
For example, Ka of HC2H3O2 = 1.8 x 10-5, Kb of NH3 = 1.8 x 10-5, and aqueous solution of
ammonium acetate, NH4C2H3O2, is approximately neutral.
NH4C2H3O2(aq) NH4+(aq) + C2H3CO2-(aq)
NH4+(aq) + H2O(l) ⇋ H3O+(aq) + NH3(aq); Ka = 5.6 x 10-10;
C2H3O2-(aq) + H2O(l) ⇋ HC2H3O2(aq) + OH-(aq); Kb = 5.6 x 10-10;
Ka=Kb a neutral solution, because the hydrolyses result in a solution with [H3O+] = [OH-].
For NH4CN, Ka(HCN) = 6.2 x 10-10, Kb(NH3) = 1.8 x 10-5, and aqueous solution of NH4CN
will be basic.
NH4CN(aq) NH4+(aq) + CN-(aq)
NH4+(aq) + H2O(l) ⇋ H3O+(aq) + NH3(aq); Ka = 5.6 x 10-10;
CN-(aq) + H2O(l) ⇋ HCN(aq) + OH-(aq); Kb = 1.6 x 10-5; Ka < Kb basic
solution, because the hydrolyses result in a solution in which [H3O+] < [OH-].
For NH4NO2, Ka(HNO2) = 4.0 x 10-4, Kb(NH3) = 1.8 x 10-5, and aqueous solution of NH4NO2
will be acidic.
NH4NO2(aq) NH4+(aq) + NO2-(aq)
NH4+(aq) + H2O(l) ⇋ H3O+(aq) + NH3(aq); Ka = 5.6 x 10-10;
NO2-(aq) + H2O(l) ⇋ HNO2(aq) + OH-(aq); Kb = 2.5 x 10-11;
Ka > Kb acidic solution, because the hydrolyses result in a solution with [H3O+] > [OH-].
Common ions are ions produced by more than one solute in the same solution. For
example, in a solution containing sodium acetate and acetic acid, the acetate ion (C2H3O2-)
is the common ion. According to the Le Chatelier's principle, the following equilibrium for
acetic acid:
HC2H3O2(aq) + H2O(l) ⇌ H3O+(aq) + C2H3O2-(aq)
will shift to the left if C2H3O2- (from another source) is added to the solution. This will reduce
the acid dissociation, which lowers [H3O+] and increases the pH of the solution.
Addition of ammonium chloride, NH4Cl, to ammonia solution will cause the following
equilibrium to shift to the left:
NH3(aq) + H2O(l) ⇌ NH4+(aq) + OH-(aq)
NH4Cl dissociates to produce NH4+ and Cl- ions, where NH4+ is a common ion in the
equilibrium of ammonia solution. The introduction of NH4+ ion reduces the ionization of NH3,
which decreases [OH-] and lowers the pH of the solution.
Calculating [H+] and pH of a solution containing weak acid and the salt of its
conjugate base.
Consider a solution containing 0.10 M HNO2 and 0.050 M NaNO2, where the latter
dissociates completely as follows:
NaNO2(aq) Na+(aq) + NO2-(aq)
[H ][NO -2 ] ( x)(0.050 x)
Ka = = = 4.0 x 10-4
[HNO 2 ] (0.10 - x)
Since Ka << 0.10, x is assumed to very small, and by approximation,
( x)(0.050 x) (x)(0.050)
~ = 4.0 x 10-4; x = 8.0 x 10-4
(0.10 - x) (0.10)
where x = [H+] = 8.0 x 10-4 M, and pH = -log(8.0 x 10-4) = 3.10
In general, for a solution containing a weak acid HX, with an dissociation constant Ka, and
the salt NaX, [H+] can be calculated by approximation, such that,
[ HX ]
[H+] = Ka x
[X ]
Exercises:
1. What are [H+] and pH of a solution containing 4.0 g of sodium acetate (NaC2H3O2) in
1.0 L of 0.050 M HC2H3O2(aq)? (Ka = 1.8 x 10-5 for acetic acid)
2. What are [OH-], [H+], and pH of a solution containing 2.5 g of NH4Cl dissolved in 1.0 L
of 0.050 M NH3(aq)? (Kb = 1.8 x 10-5 for NH3)
Buffered Solutions
A buffered solution is one that has the ability to maintain its pH relatively constant even
when a small amount of strong acid or strong base is added.
Buffered solutions contain a comparable amount of weak acid and its conjugate base (or a
weak base and its conjugate acid).
Consider a buffer made up of acetic acid and sodium acetate, in which the major species
present in solution are HC2H3O2 and C2H3O2-.
If a little HCl is added to this solution, most of H+ (from HCl) is absorbed by the conjugate
base, C2H3O2-, in the following reaction:
H+(aq) + C2H3O2-(aq) HC2H3O2-(aq)
Since C2H3O2- is present in a much larger quantity than the added H+, the above reaction is
considered to go almost completely to the right. This buffering reaction prevents a
significant increase in [H+] and minimizes the change in its pH.
If a strong base such as NaOH is added, most of the OH- ions (from NaOH) are reacted by
the acid component of the buffer as follows:
OH-(aq) + HC2H3O2(aq) H2O + C2H3O2-(aq).
Again, because of the larger concentration of HC2H3O2 compared to OH-, this reaction also
goes almost to completion. This buffering reaction prevents a large increase in the [OH-]
and minimizes any change in the pH of the solution.
; pH = pKa + log(
[ HX ] [ HX ]
Re-arranging, we obtain, [H+] = Ka x
)
[X ] [X ]
The last expression is called the Henderson-Hasselbalch equation, which is useful for
calculation the pH of solutions when the ratio [X-]/[HX] is known. For a given buffer
system, [H ] and pH varies with the ratio: [Base]/[Acid].
+
Exercise:
1. A 100.0 mL buffer solution contains 5.0 g of 0.038 mol acetic acid and 0.061 mol of
sodium acetate. Calculate the pH of the buffer? (Ka = 1.8 x 10-5 for acetic acid)
If 0.0050 mol of HCl is added to the buffer, what is the final pH of the solution?
(Assume that the volume of buffer does not change when HCl(aq) is added.)
3. (a) Suppose you want to prepare a 100-mL buffer solution with pH = 7.30, which
buffer system would you consider? [Hint: look for acids that have pKa close to the
buffer pH.] (b) Calculate the ratio [Base]/[Acid] that the buffer should have. (c) If the
concentration of the acid is 0.50 M, what should be the base concentration?
(d) Assuming your starting materials are solids, how many grams of each must be
dissolved to make the 100. mL buffer solution? (Both acid and its conjugate base may
be in the form of sodium or potassium salts)
Buffering Capacity
The buffering capacity of a solution represents the amount of H+ and/or OH- the
buffer solution can absorb without significantly altering its pH. A buffer that contains large
concentrations of buffering components and able to absorb significant quantities of strong
acid or strong base with little change in its pH is said to have a large buffering capacity.
When 0.010 mol HCl is added to Buffer-A, the following reaction takes place:
H+(aq) + C2H3O2-(aq) ( HC2H3O2(aq)
The new pH = 4.74 + log(0.99/1.01) = 4.74 - 0.010 = 4.73 (pH is hardly changed ~ 0.21%)
When 0.010 mol HCl is added to Buffer-B, the following reaction takes place:
H+(aq) + C2H3O2-(aq) ( HC2H3O2(aq)
[ ] before reaction: 0.010 M 0.020 M 0.020 M
[ ] after reaction: 0 0.010 M 0.030 M
New pH = 4.74 + log(0.010/0.030) = 4.74 – 0.48 = 4.26 (pH decreases by 0.48 unit or 10%)
This shows that Buffer-A, which contains larger quantities of buffering components, has a much
higher buffering capacity that Buffer-B. For the Buffer-A to decrease its pH by 0.48 unit (or
10%), it would have to absorb the equivalent of 0.50 mol of HCl.
Exercise
1. An acetate buffer solution is prepared by mixing 35.0 mL of 1.0 M HC2H3O2 and 65.0 mL
of 1.0 M NaC2H3O2. Calculate the pH of this buffer. If 1.0 mL of 6.0 M HCl is added to the
buffer solution, what will be the new pH of the buffer.
2. A 100-mL buffer solution contains 0.20 M KH2PO4 and 0.32 M K2HPO4. What is the pH
of the buffer? If 0.0050 mol of HCl is added to the buffer without changing its volume,
what is the final pH of the buffer? (Ka = 6.2 x 10-8 for H2PO4-)
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There are four types of pH curves for the different types of acid-base titration:
1. strong acid - strong base titration.
2. strong acid - weak base titration.
At this point, the solution contains only water and salt (NaCl) and [H+] = [OH-] = 1.0 x 10-7 M,
which is due to water ionization. The pH of the solution will be 7.00 (pH of neutral solution)
(e) When 21.0 mL of 0.100 M NaOH has been added, there will be excess OH-:
H+(aq) + OH-(aq) ( H2O
[ ] after mixing, but
before reaction: 0.049 M 0.051 M
[ ] after reaction: 0.000 0.002 M
[OH-] = 0.002 M, ( pOH = 2.70, and pH = 11.30
1. Consider the titration of 20.0 mL of 0.100 M HC2H3O2 with 0.100 M NaOH solution.
Calculate the pH of the solution: (a) before any of the NaOH is added; (b) after 10.0 mL
of NaOH is added; (c) after 15.0 mL of NaOH is added; (d) after 20.0 mL of NaOH is
added; (e) after 25.0 mL of NaOH is added.
Solution:
(a) Before titration, [H+] = {(0.100 M)(1.8 x 10-5)} = 1.34 x 10-3 M,
pH = -log(1.34 x 10-3) = 2.873
[HC 2 H 3 O 2 ] (0.033 M)
[H+] = Ka x -
= 1.8 x 10-5 x = 1.8 x 10-5 M
[C 2 H 3 O 2 ] (0.033 M)
[C 2 H 3 O -2 ]
pH = pKa + log( = 4.74 + log(1) = 4.74
[C 2 H 3 O 2 ]
When a weak acid is half-neutralized, 50% of the acid is converted to its conjugate base.
That is, at half-way to the equivalent point of the titration, [C2H3O2-] = [HC2H3O2]. Under
this condition, [H+] = Ka, and pH = pKa.
(c) At the equivalent point (when 20.0 mL of 0.100 M NaOH has been added), all of the acid
is converted to its conjugate base. The latter undergoes hydrolysis as follows:
C2H3O2-(aq) + H2O(l) ⇌ HC2H3O2(aq) + OH-(aq)
———————————————————————————————————
Initial [ ], M: 0.0500 0.000 0.000
Change, [ ], M: -x +x +x
Equilibrium [ ], M: (0.0500 – x) x x
the equivalent point. In the case of acetic-NaOH titration, the pH at the equivalent point is
about 8.72. The larger the Ka of the weak acid, the closer the pH to 7 at equivalent point.
The smaller Ka, the higher the pH than 7 at equivalent point.
Exercise
1. In a titration of 20.00 mL of 0.100 M formic acid, HCHO2, with 0.100 M NaOH,
calculate the pH: (a) before NaOH was added; (b) after 15.00 mL of NaOH is added;
(b) after 20.00 mL of NaOH is added. (Ka = 1.8 x 10-4 for HCHO2)
2. In a titration of 20.00 mL of 0.100 M NH3(aq) with 0.100 M HCl(aq), calculate the pH:
(a) before titration begins; (b) after 10.0 mL of HCl(aq) is added; (c) at equivalent
point, that is after 20.0 mL of HCl(aq) is added. (Kb = 1.8 x 10-5 for NH3)
_________________________________________________________________________
Like a weak acid, an indicator exhibits the following equilibrium in aqueous solution:
[H ][In - ]
Ka = ;
[HIn]
[In - ]
Re-arranging, we obtain [H+] = Ka x ([HIn]/[In-]); pH = pKa + log( )
[HIn]
When [HIn] = 10 x [In-],
[In - ]
pH = pKa + log( ) = pKa - 1; indicator assumes the color of acid form
[HIn]
[In - ]
pH = pKa + log( ) = pKa + 1; indicator assumes the color of base.
[HIn]
Phenolphthalein, which is the most common acid-base indicator, has Ka ~ 10-9. Its acid form
(HIn) is colorless and the conjugate base form (In-) is pink. It is colorless when the solution
pH < 8, that is when 90% or more of the species are in the acid form (HIn), and pink at pH
> 10, when 90% or more of the species are in the conjugate base form (In-). The pH range
at which an indicator changes depends on the Ka. For phenolphthalein with Ka ~ 10-9, its
color changes at pH = 8 – 10. It is suitable for strong acid-strong base titration and weak
Ksp = [Mb+]a[Xa-]b
A. For ionic equilibria of the type: MX(s) ⇌ Mn+(aq) + Xn-(aq); Ksp = [Mn+][Xn-]
B. For ionic equilibria of the type: MX2(s) ⇌ M2+(aq) + 2X-(aq), Ksp = [M2+][X-]2 ;
The solubility of calcium fluoride is S = (Ksp/4)1/3 = (4.0 x 10-11/4)1/3 = 2.2 x 10-4 mol/L
C. For solubility equilibria of the type: MX3(s) ⇌ M3+(aq) + 3X-(aq), Ksp = [M3+][X-]3
If the solubility of the compound (MX3 or M3X) is S mol/L, Ksp = 27S4; S = 4 ( K sp / 27)
S= 4 ( K sp / 27) = 4
(1.8 x 10 -18 )/27 = 1.6 x 10-5 mol/L
If the solubility of the compound M3X2 is S mol/L, then [M2+] = 3S, and [X3-] = 2S;
Solution:
Solubility of PbSO4 in mol/L = 4.3 x 10-3 g x 1000 mL/L = 1.40 x 10-4 mol/L
100. mL 303.26 g/mol
That is, a saturated solution of PbSO4, contains [Pb2+] = [SO42-] = 1.4 x 10-4 mol/L
For the equilibrium: PbSO4(s) ⇌ Pb2+(aq) + SO42-(aq);
Exercise
1. If the solubility of MgF2 is 7.3 x 10-3 g/100 mL solution at 25oC, what is the Ksp of
MgF2?
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Determining Solubility from Ksp
Solubility of Mg(OH)2: S = 3 K sp / 4 = 3
(6.3 x 10 -10 )/4 = 5.4 x 10-4 mol/L
If some NaCl is added to a saturated solution of PbCl2, the [Cl-] will increase, and according
to Le Chateliler’s principle, the equilibrium will shift in the direction that tends to reduce [Cl-
]. In this case, the equilibrium will shift left, to form more PbCl2 solid, hence decreasing the
amount of PbCl2 that dissolves into solution.
Sample Problem
The Ksp of BaSO4 is 1.5 x 10-9 at 25 oC. (a) What is its solubility in water at 25oC? (b)
What is the solubility in 0.10 M Na2SO4 at 25 oC?
Solubility equilibrium for BaSO4: BaSO4(s) ⇌ Ba2+(aq) + SO42-(aq);
When a strong acid is added to the saturated solution, the following reaction occurs:
H+(aq) + F-(aq) HF(aq)
This reaction has the net effect of reducing the concentration of F- ions, which causes the
equilibrium to shift to the right and resulting in more of CaF2 to dissolve.
Exercise
1. Calculate the solubility of PbCl2 (Ksp = 1.6 x 10-5) and AgCl (Ksp = 1.6 x 10-10) in 0.010
M NaCl solution.
2. What is the solubility of CuS (Ksp = 4 x 10-37) and ZnS (Ksp = 2 x 10-25), respectively,
in solution buffered at pH = 8.00? (For H2S, Ka1 = 1 x 10-7; Ka2 = 1 x 10-19)
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Precipitation and Qualitative Analysis
For solubility equilibrium: MaXb(s) ⇌ aM+(aq) + bX-(aq),
Sample problem:
If 20.0 mL of 0.050 M Pb(NO3)2 is mixed with 30.0 mL of 0.10 M NaCl, will PbCl2
precipitate form? Ksp of PbCl2 = 1.6 x 10-5.
Pb2+(aq) + 2Cl-(aq) ⇌ PbCl2(s)
[ ] after mixing 0.020 M 0.060 M
Qsp = [Pb ][Cl-]2 = (0.020)(0.060)2 = 7.2 x 10-5 > Ksp
2+
Exercise:
1. At what pH a solution containg 0.10 M Ca2+ ions will form a precipitate of Ca(OH)2?
(Ksp = 1.3 x 10-6 at 25 oC for Ca(OH)2)
2. Will Ag2SO4 precipitate if 30.0 mL of 0.050 M AgNO3 is added to 20.0 mL of 0.10 M of
Na2SO4 solution? Ksp = 1.2 x 10-5 for Ag2SO4 at 25oC.
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Practical Application of Ionic Equilibria
Qualitative Analysis
The presence of certain ions, such as Cl-, I-, SO42-, Ag+, etc. in water can be
determined qualitatively and quantitatively by precipitation method. Cl- and I- can be
precipitated as AgCl and AgI, respectively, by adding AgNO3 solution.
Synthesis
Certain industrial chemicals, such as AgCl, AgBr, AgI, that are needed in
photographic industries are prepared by precipitation.
Selective Precipitation
Because of the different solubility of compounds, the separation of ions from a
mixture of solution can be accomplished by selectively precipitation. This selective
precipitation is carried out by adding the precipitating ion until the ion product, Q, of the
more soluble compound is almost equal to its Ksp, but the Ksp of the less soluble compound
is exceeded as much as possible. For example, because of the different solubility of CaSO4
(Ksp = 6.1 x 10-5), and BaSO4 (Ksp = 1.5 x 10-9), Ca2+ and Ba2+ can be separated from a
solution by selectively precipitating BaSO4 using Na2SO4 or H2SO4 solution.
Sample problem-3:
An aqueous solution contains Ca2+ and Ba2+ ions at concentrations 0.10 M and 0.010
M, respectively. What concentration of SO42- must be present so that the maximum amount
of Ba2+ ion precipitates as BaSO4, but Ca2+ remains in solution ? Ksp of CaSO4 = 6.1 x 10-5;
Ksp of BaSO4 = 1.5 x 10-9.
Exercise-9:
1. How many grams of AgCl will precipitate out when 50.0 mL of 0.050 M AgNO3 is added
to 50.0 mL of 0.10 M NaCl? What is the concentration of Ag+ that remains in solution
after the precipitation? Ksp = 1.6 x 10-10 at 25 oC for AgCl.
2. A solution contains 0.10 M in Cl- and 0.010 M in I-. At what concentration of Ag+
would (a) AgI begin to precipitate; (b) AgCl begins to precipitate? What is the
concentration of I- when AgCl begins to precipitate? (Ksp[AgCl] = 1.6 x 10-10 and
Ksp[AgI] = 1.5 x 10-16)
Ion group 1: Insoluble chlorides. Treating the mixture with 6 M HCl will precipitate Ag+,
Hg22+, and Pb2+ ions as chlorides, leaving other cations in solution. The formation of a white
precipitate indicates the presence of at least one of these cations in the mixture.
Ion group 2: Acid-insoluble sulfides. The supernatant from the above treatment with HCl is
adjusted to pH ~ 0.5 and then treated with aqueous H2S. The high [H3O+] in solution keeps
Sn2+, and Bi3+. Centrifuging and decanting gives the next solution.
Ion group 3: Base-insoluble sulfides. The supernatant from acidic sulfide treatment is
treated with NH3/NH4+ buffer to make the solution slightly basic (pH~8). The excess OH- in
solution increases [HS-], which causes the precipitation of the more soluble sulfides and
some hydroxides. The cations that precipitate under this condition are: Zn2+, Mn2+, Ni2+,
Fe2+, Co2+, as sulfides, and Al3+, Cr3+, and Fe3+ as hydroxides. The precipitate is centrifuged
and the supernatant decanted to give the next solution.
Ion group 4: Insoluble phosphates. The slightly basic supernatant separated from the
group 3 ions is treated with (NH4)2HPO4, which precipitates Mg3(PO4)2, Ca3(PO4)2, and
Ba3(PO4)2.
Ion group 5: Alkali metal and ammonium ions. The final solution contains any of the
following ions: Na+, K+, and NH4+.
add 6 M NaOH,
centrifuge
Precipitate Supernatant
Fe(OH)3 Cu(NH3)42+
(dark brown) (dark blue)
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All complex ions are Lewis adducts; the metal ions act as Lewis acids (electron-pair
acceptors) and the ligands are Lewis bases (electron-pair donors). Only species with at least
one lone-pair electrons can be a ligand.
[Cu(NH 3 ) 24 ]
Kf =
[Cu(H 2 O) 62 ][NH 3 ] 4
At molecular level, the ligand exchange process occurs in stepwise manner; water
molecule is replace with NH3 molecule one at a time to give a series of intermediate species,
each with its own formation constant. For convenience, the water molecules can be omitted
from the equation.
1. Cu2+(aq) + NH3(aq) ⇌ Cu(NH3)2+(aq);
[Cu(NH 3 ) 2 ]
Kf1 =
[Cu 2 ][NH 3 ]
2. Cu(NH3)2+(aq) + NH3(aq) ⇌ Cu(NH3)22+(aq);
[Cu(NH 3 ) 22 ]
Kf2 =
[Cu(NH 3 ) 2 ][NH 3 ]
3. Cu(NH3)32+(aq) + NH3(aq) ⇌ Cu(NH3)42+(aq);
[Cu(NH 3 ) 24 ]
Kf4 =
[Cu(NH 3 ) 32 ][NH 3 ]
The overall formation constant is the product of all intermediate formation constants:
[Cu(NH 3 ) 24 ]
Kf = Kf1 x Kf2 x Kf3 x Kf4 =
[Cu 2 ][NH 3 ]4
Sample problem-4:
If a 30.0-mL solution containing 0.020 M Cu2+ is mixed with 20.0 mL of 0.20 M NH3
solution, what is the concentration of Cu2+ in solution? Kf = 5.0 x 1012
Since Kf is very large, we can assume that all of Cu2+ is converted to Cu(NH3)42+.
Then, [Cu(NH3)42+] = 0.012 M and [NH3] = 0.080 M – (4 x 0.012 M) = 0.032 M
Next, consider the following (reverse) equilibrium:
Cu(NH3)42+(aq) ⇌ Cu2+(aq) + 4NH3(aq)
[Cu 2 ][NH 3 ]4
Kc = = 1/Kf = 1/(5.0 x 1012) = 2.0 x 10-13
[Cu(NH 3 ) 24 ]
Set up the following equilibrium table:
Concentration (M) Cu(NH3)42+(aq) ⇌ Cu2+(aq) + 4 NH3(aq)
Initial: 0.012 M 0.000 0.032 M
Change: -x +x +x
Equilibrium: (0.012 – x) x (0.032 + x)
Since Kc is very small, we assume that x << 0.012 M,
Then, (0.012 – x) ~ 0.012, and (0.032 + x) ~ 0.032
( x)(0.032) 4
Kc = = 2.0 x 10-13;
(0.012)
2. Will AgCl precipitates form if 5.0 mL of 0.10 M AgNO3 is added to 5.0 mL of solution
containing 0.10 NaCl and 2.0 M NH3? (b) Will precipitate form if [NH3] = 1.0 M?
(a) Label the two points where the solution has the maximum buffer capacity and label
first and second equivalence points as .
(b) Estimate the formal concentration of H2A from the graph.
(c) There are simple expressions for the pH at points A, B, and C. Give the equations
below.
(d) Estimate Ka1 and Ka2 for this acid from your estimate of pH at points A, B, and C.
(e) At what indicator pH would you want your color-change indicator to have in order to
titrate to the second equivalence point?
Ans (a) Buffer capacity at A & C
1st equivalence point at B 2nd at D.
(b) 0.1 M
©
(D)
(e)At pH=10
PROBLEM. 3.Calomel, Hg2Cl2, (MW 472.09) dissolves to form Hg22+ and chloride with
a Ksp=1.2 10-18. Calculate the mass of calomel that will dissolve in...
A. 1.00 L pure water Ans. 3.16 x 10-4 gram
The equilibrium equation is Hg2Cl2 s)<=>Hg2+ -
2 (aq) + 2Cl (aq)