Ch.

6: Chemical Equilibrium
Outline:

• 6-1 The Equilibrium Constant

• 6-2 Equilibrium and Thermodynamics

• 6-3 Solubility Product

• 6-4 Complex Formation

• 6-5 Protic Acids and Bases

• 6-6 pH

• 6-7 Strengths of Acids and Bases

Updated Oct. 5, 2011: minor fix on slide 11, new slides 31-42
 The Equilibrium Constant
For the reaction:
aA + bB  cC + dD

the equilibrium constant K has the form

[C]c [D]d
K=
[A]a [B]b

By definition, a reaction is favoured whenever K > 1.

Each concentration above is expressed as the ratio of the concentration of a species to its
concentration in its standard state:
Solutes: the standard state is 1 M.
(e.g., [A] really means [A]/(1 M) if A is a solute)
Gases: the standard state is 1 bar (≡ 105 Pa; 1 atm ≡ 1.013 25 bar)
Solids and Liquids: the standard states are the pure solid or liquid.

All of the terms above are dimensionless; hence, all equilibrium constants are
dimensionless.
 The Equilibrium Constant, 2
For the various concentrations and pressures to be dimensionless:

Solutions: [A] must be in units of molarity (M or mol L-1)

Gases: pD must be in bar
Liquids or Solids: The ratio [C]/[C]std state must be unity (1), since the standard state is the
pure liquid or solid.
Solvents: If B is a solvent, [B]/[B]std state is essentially one, since the concentrations are so
close to one another.

Final summary: When one evaluates equilibrium constants:

1. Concentrations of solutes should be expressed as moles per liter.

2. Concentrations of gases should be expressed in bars.

3. Concentrations of pure solids, pure liquids, and solvents are omitted because they
are unity.
 The Equilibrium Constant, 3
For the reaction:
+ − [H + ][A − ]
HA  H + A ; K1 =
[HA]
and the reverse reaction:
[HA]
H + + A −  HA ; K1−1 = = 1 / K1
[H + ][A − ]

If two reactions are added, then K is the product of the two rate constants:

HA  H + + A − K1
H + + C  CH + K2
HA + C  A − + CH + K3

[H + ][A − ] [CH + ] [A − ][CH + ]

K 3 = K1 K 2 = • + =
[HA] [H ][C] [HA][C]

If n reactions are added, the overall equilibrium constant is the product of n individual
equilibrium constants.
 Equilibrium and Thermodynamics
Equilibrium is controlled by the thermodynamics of a chemical reaction. The heat absorbed
or released (enthalpy) and the degree of disorder of reactants and products (entropy)
independently contribute to the degree to which the reaction is favoured or disfavoured.

The enthalpy change, ΔH, for a reaction is the heat

absorbed or released when the reaction takes place
under constant applied pressure. The standard
enthalpy change, ΔH°, refers to the heat absorbed
when all reactants and products are in their
standard states. ΔH > 0 for endothermic processes,
and ΔH < 0 for exothermic processes.

The entropy, S, of a substance is a measure of its

“disorder.” ** The greater the disorder, the greater
the entropy. In general, Sgas > Sliquid > Ssolid. Ions in
aqueous solution are normally more disordered than
in their solid salts. ΔS > 0 if the products are more
ordered than the reactants, and ΔS < 0 if the
products are less ordered than the reactants.
** We will not discuss entropy in a rigorous
quantitative fashion as in intro thermodynamics
courses (e.g., 59-240 and 59-241).
 Gibbs Energy
When ΔH and ΔS are both positive or both negative, what decides whether a reaction will
be favoured? The change in Gibbs energy, ΔG, is the arbiter between opposing tendencies
of ΔH and ΔS. At constant temperature, T,
ΔG = ΔH − T ΔS
A reaction is favoured (i.e., said to be spontaneous or allowed for a given set of conditions)
if the change in Gibbs energy is negative, ΔG < 0. At 25 oC,

HCl(g)  H + (aq) + Cl− (aq); ΔH = −74.85 kJ mol−1

ΔG 0 = ΔH 0 − T ΔS 0
= (−74.85 × 10 3 J mol−1 ) − (298.15 K)( − 130.4 J K mol−1 )
= −35.97 kJ mol−1

ΔG° is negative, so the reaction is favoured when species are in their standard states. The
favourable influence of ΔH° is greater than the unfavourable influence of ΔS° in this case.
 Gibbs Energy, 2
The equilibrium constant is dependent upon the Gibbs energy:
− ΔG 0 / RT
K=e
Hence, the more negative the value of ΔG°, the larger is the equilibrium constant. For the
dissociation of HCl (g):
−(−35.97 ×10 3 J mol−1 )/(8.1344 J K −1 mol−1 )(298.15 K)
K=e
= 2.00 × 10 6

The large K indicates that HCl (g) is very soluble in water and is nearly completely ionized
to H+ and Cl− when it dissolves.

To summarize, a chemical reaction is favoured by the liberation of heat (ΔH < 0) and by an
increase in disorder (ΔS > 0). ΔG takes both effects into account to determine whether or
not a reaction is favourable. We say that a reaction is spontaneous under standard
conditions if ΔG° < 0, or equivalently, if K > 1. The reaction is not spontaneous (i.e., will
not occur under a given set of conditions) if ΔG° is positive (K < 1).
 LeChatelier’s Principle
Suppose that a system at equilibrium is subjected to a change that disturbs the system.
Le Châtelierʼs principle states that the direction in which the system proceeds back to
equilibrium is such that the change is partially offset. For example:
BrO −3 + 2Cr 3+ + 4H 2O  Br − + Cr2O 27 − + 8H +

[Br − ][Cr2O 27 − ][H + ]8

K= − 3+ 2
= 1 × 1011
at 25 o
C
[BrO 3 ][Cr ]
Starting conditions:
[H + ] = 5.0 M, [Cr2O 27 − ] = 0.10 M, [Cr 3+ ] = 0.0030 M,
[Br − ] = 1.0 M and [BrO −3 ] = 0.043 M
If the concentration of the dichromate is increased from 0.10 M to 0.20 M, in what direction
will the reaction proceed to equilibrium?
The reaction should go back to the left to partially offset the increase in dichromate, which
appears on the right side of the reaction equation. To confirm this, we normally calculate
the reaction quotient, Q.
 LeChatelier’s Principle, 2
The form of Q is exactly that of K, except that Q is evaluated with whatever concentrations
currently exist in the system (say after addition or removal of a reagent).
[1.0][0.20][5.0]8
Q= 2
= 2 × 1011
>K
[0.043][0.0030]
Since Q > K, the reaction must go to the left in order to decrease the numerator and
increase the denominator until Q = K.
• If a reaction is at equilibrium and products are added (or reactants are removed), the
reaction goes to the left.

• If a reaction is at equilibrium and reactants are added (or products are removed), the
reaction goes to the right.
If the temperature of the system is changed, then K also changes, as predicted by
− ΔG 0 / RT −(ΔH 0 −T ΔS 0 )/ RT − ΔH 0 / RT ΔS 0 / R
K=e =e =e ie
The ΔS° term is independent of T; hence, the ΔH° term increases with increasing
temperature if ΔH° is positive (endothermic, K increases with increase in T) and decreases
if ΔH° is negative (exothermic, K decreases with increase in T).
 LeChatelier’s Principle, 3
These statements can be understood in terms of Le Châtelierʼs principle as follows.
Consider an endothermic reaction:
heat + reactants  products
If the temperature is raised, then heat is added to the system. The reaction proceeds to the
right to partially offset this change.

Note: We are making thermodynamic

predictions, not kinetic ones. In
other words, we look at what it takes
for a system to reach equilibrium, or
to drive a reaction in a particular
direction. We do not know how
long the reaction will take! (i.e., a
large K does not necessarily indicate
a fast reaction).
 Solubility Product
The solubility product is the equilibrium constant for the reaction in which a solid salt
dissolves to give its constituent ions in solution. Solid is omitted from the equilibrium
constant because it is in its standard state.
Consider the dissolution of mercurous chloride in water:
Hg 2Cl2 (s)  Hg 22 + + 2Cl−
The solubility product, Ksp, is

K sp = [Hg 22 + ][Cl− ]2 = 1.2 × 10 −18

A solution containing excess, undissolved solid is said to be

saturated with that solid. The solution contains all the solid
capable of being dissolved under the prevailing conditions.
If an aqueous solution is left in contact with excess solid
Hg2Cl2, the solid will dissolve until the condition above is
satisfied. Thereafter, the amount of undissolved solid
remains constant. Unless excess solid remains, there is no
guarantee that [Hg22+][Cl-]2 = Ksp. On the other hand, if Hg2+
and Cl- are mixed such that [Hg22+][Cl-]2 > Ksp, then Hg2Cl2
will precipitate!
In chemical analysis, we encounter
solubility in precipitation titrations,
electrochemical reference cells, and
gravimetric analysis
e.g., The effect of acid on the
solubility of minerals and the effect of
atmospheric CO2 on the solubility
(and death) of coral reefs are
important in environmental science.
 Solubility Product, 2
Most often, the solubility product is used to find the concentration of one ion when the
concentration of the other is known or fixed by some means.

e.g., What is the concentration of Hg22+ in equilibrium with 0.10 M Cl− in a solution of KCl
containing excess, undissolved Hg2Cl2(s)?

2+
K sp 1.2 × 10 −18 −16
[Hg ] =
2 − 2
= 2
= 1.2 × 10 M
[Cl ] 0.10
Because Hg2Cl2 is so slightly soluble, additional Cl− obtained from Hg2Cl2 is negligible
compared with 0.10 M Cl−.

Note: The solubility product does not tell the entire story of solubility. Many salts form
soluble ion pairs to some extent, i.e., MX(s) can give MX(aq) as well as M+(aq) and X−(aq).

e.g., In a saturated solution of CaSO4, two-thirds of the dissolved calcium is Ca2+ and one
third is CaSO4 (aq). The CaSO4 (aq) ion pair is a closely associated pair of ions that
behaves as one species in solution (see Appendix J of the 8th edition for more information).
 Common Ion Effect
For the ionic solubility reaction:

CaSO 4 (s)  Ca 2 + + SO 24 − , K sp = 2.4 × 10 −5

The product [Ca2+][SO42-] is constant at

equilibrium in the presence of excess solid
CaSO4. If the concentration of Ca2+ were
increased by adding another source of Ca2+,
such as CaCl2, then [SO42-] must decrease so
that [Ca2+] remains constant. i.e., less CaSO4
will dissolve if Ca2+ or SO42- is present from
another source.

This application of Le Chatelierʼs principle is

called the common ion effect: A salt will be less
soluble if one of its constituent ions is already
present in the solution.
Solubility of CaSO4 in solutions
containing dissolved CaCl2. Solubility
is expressed as total dissolved sulfate,
which is present as free SO42- and as
the ion pair, CaSO4 (aq).
 Separation by Precipitation
Precipitation can sometimes be used to separate ions from each other. For example,
consider a solution containing lead(II) (Pb2+) and mercury(I) (Hg22+) ions, each at a
concentration of 0.010 M. Each forms an insoluble iodide, but the mercury(I) iodide is
considerably less soluble, as indicated by the smaller value of Ksp:

PbI2 (s)  Pb 2 + + 2I− , K sp = 7.9 × 10 −9 The smaller Ksp implies a lower solubility for Hg2I2 because
the stoichiometries of the two reactions are the same. If
the stoichiometries were different, it does not follow that
Hg 2 I2 (s)  Hg 22 + + 2I− , K sp = 4.6 × 10 −29 the smaller Ksp would imply lower solubility.

Is it possible to lower the

concentration of Hg22+ by
99.990% by selective precipitation A yellow solid, lead(II) iodide
with I−, without precipitating Pb2+? (PbI2), precipitates when a
colourless solution of lead
nitrate (Pb(NO3)2) is added to
a colourless solution of
In other words, can we lower potassium iodide (KI).
[Hg22+] to 0.010% of 0.010 M (1.0
× 10-6 M) without precipitating any
Pb2+?
 Complex Formation
If anion X− precipitates metal M+, it is often observed that a high concentration of X− causes
solid MX to redissolve. The increased solubility arises from formation of complex ions, such
as MX2, which consist of two or more simple ions bonded to one another.
A ligand is any atom or group of atoms attached to the species of interest.
e.g., In complex ions such as PbI+, PbI3- and PbI42-, iodide, I-, is said to be a ligand of Pb2+.
Pb2+ is said to act as a Lewis acid, and I- is said to act as a Lewis base.

The product of the reaction between a Lewis acid and a Lewis base is called an adduct,
and the bond between them is called a dative or coordinate covalent bond.
 Complex Formation, 2
If Pb2+ and I− only reacted to form solid PbI2, then the solubility of Pb2+ would always be
very low in the presence of excess I−:

High concentrations of I− cause solid PbI2 to dissolve. We explain this by the formation of a
series of complex ions:

The species PbI2(aq) is dissolved PbI2, containing two iodine atoms bound to a lead atom.
Complex Formation, 3
 Complex Formation, 4
At low I− concentrations, the solubility of lead is governed by precipitation of PbI2(s). At high
I− concentrations, all of the reactions are driven to the right (Le Châtelierʼs principle), and
the total concentration of dissolved lead is considerably greater than that of Pb2+ alone.

All equilibria are satisfied simultaneously.

If we know [I−], we can calculate [Pb2+] by
substituting the value of [I−] into the equilibrium
constant expression for the main reaction,
regardless of whether there are other reactions
involving Pb2+. The concentration of Pb2+ that
satisfies any one equilibrium must satisfy all
equilibria, i.e., there can be only one concentration
of Pb2+ in the solution.

Total solubility of lead(II) (curve with circles) and solubilities of individual

species (straight lines) as a function of the concentration of free iodide. To
the left of the minimum, [Pb]total is governed by the solubility product for
PbI2(s). As [I−] increases, [Pb]total decreases because of the common ion
effect. At high values of [I−], PbI2(s) redissolves because it reacts with I− to
form soluble complex ions, such as PbI42-. Note the logarithmic scales. The
solution is made slightly acidic so that [PbOH+] is negligible.
 Protic Acids and Bases
Acids and bases are of paramount importance in analytical chemistry, since they influence:

- general chemical reactivity

- complex formation
- redox chemistry
- molecular charge and shape
- analytical separation processes

In aqueous chemistry, an acid is a substance that increases the concentration of H3O+

(hydronium ions) when added to water. Conversely, a base decreases the concentration of
H3O+. A decrease in H3O+ concentration requires an increase in OH− concentration.
(Therefore, a base increases the concentration of OH− in aqueous solution).

Protic refers to chemistry involving transfer of H+ from one molecule to another. The species
H+ is also called a proton because it is what remains when a hydrogen atom loses its
electron. The hydronium ion, H3O+, is a combination of H+ with H2O. Although H3O+ is a
more accurate representation than H+ for the hydrogen ion in aqueous solution, H3O+ and
H+ are used interchangeably.
 Brønsted-Lowry Acids and Bases
Brønsted and Lowry classified acids as proton donors and bases as proton acceptors.
e.g., HCl is an acid (a proton donor), and it increases the concentration of H3O+ in water:

HCl + H 2O  H 3O + + Cl−
Brønsted and Lowry classifications do not require the formation of the hydronium cation,
making these definitions useful for non-aqueous situations (e.g., gas phase, solvents, etc.).

HCl (g) + NH 3 (g)  NH +4 Cl−

Unless otherwise noted, these classifications are used for all acids and bases.

J. N. Brønsted (1879–1947) of the University of

Copenhagen and T. M. Lowry (1874–1936) of
Cambridge University independently published
their definitions of acids and bases in 1923.
 Salts
Any ionic solid is called a salt. In a formal sense, a salt can be thought of as the product of
an acid-base reaction. When an acid and a base react, they are said to neutralize each
other. Most salts containing cations and anions with single positive and negative charges
are strong electrolytes—they dissociate nearly completely into ions in dilute aqueous
solution.
NH +4 Cl− (s) → NH +4 (aq) + Cl− (aq)
 Conjugate Acids & Bases
The products of a reaction between an acid and a base may also be classified as acids and
bases in some instances.
e.g., Consider the reaction of acetic acid and methylamine (base). Acetate is a base
because it can accept a proton to make acetic acid, whereas the methylammonium ion is
an acid because it can donate a proton and become methylamine.

Acetic acid and the acetate ion are said to be a conjugate acid-base pair. Methylamine and
methylammonium ion are likewise conjugate. Conjugate acids and bases are related to
each other by the gain or loss of one H+, respectively.
 The Nature of H+ and OH-
The proton does not exist by itself in water. The simplest formula found in some crystalline
salts is H3O+. For example, crystals of perchloric acid monohydrate contain pyramidal
hydronium (also called hydroxonium) ions:

Structure of hydronium ion, H3O+, proposed by M.

Eigen and found in many crystals. The bond
enthalpy (heat needed to break the OH bond) of
H3O+ is 544 kJ/mol, about 84 kJ/mol greater than
the bond enthalpy in H2O.
 Other H3O+ structures
In the gas phase, H3O+ can be surrounded by 20 molecules of H2O in a regular
dodecahedron held together by 30 hydrogen bonds. There are numerous solid structures:

Environment of aqueous H3O+. Three H2O

The Zundel structure of H3O+ ⋅ H2O.
molecules are bound to H3O+ by strong
hydrogen bonds (dotted lines), and one
H2O (at the top) is held by weaker ion-
dipole attraction (dashed line). The
OH...O hydrogen-bonded distance of 252
pm (picometers, 10−12 m) compares with
an OH...O distance of 283 pm between
hydrogen-bonded water molecules.

H3O+·3C6H6 cation found in the crystal structure

of [(C6H6)3H3O+] [CHB11Cl11−].
[From E. S. Stoyanov, K.-C. Kim, and C. A. Reed,
“The Nature of the H3O+ Hydronium Ion in
Benzene and Chlorinated Hydrocarbon Solvents,”
J. Am. Chem. Soc. 2006, 128, 1948.]
 The Nature of H+ and OH-, 2
We normally write H+ in most chemical equations, although we really mean H3O+. To
emphasize the chemistry of water, we write H3O+. For example, water can be either an acid
or a base. Water is an acid with respect to methoxide:

But with respect to hydrogen bromide, water is a base:

 Autoprotolysis
Water undergoes self-ionization, called autoprotolysis, in which it acts as both an acid and a
base:

or equivalently:

Protic solvents have a reactive H+, and all protic solvents undergo autoprotolysis.
e.g., acetic acid:

The extent of these reactions is very small. The autoprotolysis constants (equilibrium
constants) for the reactions above are 1.0 × 10−14 and 3.5 × 10−15, respectively, at 25°C.
 pH
The reason we discuss autoprotolysis is its relation to pH. The autoprotolysis constant for
H2O has the special symbol Kw, where “w” stands for water:

Table 6-1 shows how Kw varies with temperature. Its value at 25.0 °C is 1.01 × 10−14.
 pH, 2
An approximate definition of pH is the negative logarithm of the H+ concentration.

(In chapter 7 we will look at a more accurate definition in terms of activities).

In pure water at 25°C with [H+] = 1.0 × 10−7 M, the pH is −log(1.0 × 10−7) = 7.00. If [OH−] =
1.0 × 10−3 M, then [H+] = 1.0 × 10−11 M and the pH is 11.00. A useful relation between [H+]
and [OH−] is

This equation is equivalent to saying, for instance, that if pH = 3.58, then pOH = 14.00 –
3.58 = 10.42, or [OH−] = 10−10.42 = 3.8 × 10−11 M.

A solution is acidic if [H+] > [OH−]. A solution is basic if [H+] < [OH−]. At 25°C, an acidic
solution has a pH below 7 and a basic solution has a pH above 7. Although pH generally
falls in the range 0 to 14, these are not the limits of pH. A pH of −1, for example, means
−log[H+] = −1 or [H+] = 10 M. This concentration is attained in a concentrated solution of a
strong acid such as HCl.
 pH, 3

pH of various substances. [From Chem. Eng. News, 14 September 1981.] The most acidic rainfall is a
stronger acid than lemon juice. The most acidic natural waters known are mine waters, with total
dissolved metal concentrations of 200 g/L and sulfate concentrations of 760 g/L. The pH of this water, –
3.6, does not mean that [H+] = 103.6 M = 4 000 M! It means that the activity of H+ (discussed in Chapter
7) is 103.6. The surface of water or ice is ~2 pH units more acidic than the bulk because H3O+ is more
stable on the surface. Surface acidity could be important to the chemistry of atmospheric clouds.
 Pure water?
Is there such a thing as pure water? (i.e., pH of 7.00 at 25 oC?) Of course! But in practice,
in most daily situations (kitchen, lab, bathroom, etc.) water from the tap is acidic because it
contains CO2 from the atmosphere, which is an acid by virtue of the reaction

CO2 can be largely removed by boiling water and then protecting it from the atmosphere.
Again, the effects of increasing CO2 levels in our atmosphere, and their influence on ocean
pH, fish populations, coral reefs, etc. must be stressed!

More than a century ago, careful

measurements of the
conductivity of water were made
What about other constituents, by F. Kohlrausch and his
such as commonly found students. To remove impurities,
metal and halogen ions? they found it necessary to distill
water 42 consecutive times
under vacuum to reduce
conductivity to a limiting value!
 Strengths of Acids and Bases
Acids and bases are classified as strong or weak, depending upon whether they react
“completely” or “partially” to produce H+ or OH-, respectively.

A strong acid or base is completely dissociated (or almost completely) in an aqueous

solution (i.e., the values of K associated with such reactions are very large).

HCl(aq)  H + + Cl−
KOH(aq)  K + + OH −

You should be familiar with most of

the strong acids and bases in this
list (note the absence of HF, due to
the formation of an H3O+⋄⋄⋄F- ion
pair in solution).

In most cases, hydroxides of

alkaline earth metals are
considered to be strong bases.
 Strengths of Acids and Bases, 2
Weak acids and bases are only partially dissociated with water. For instance, a weak acid
denoted as HA reacts with water:
Ka Ka
HA + H 2O  H 3O + + A − or equivalently HA  H + + A −

Ka is the acid dissociation constant; for a weak acid, Ka must be “small.”

[H + ][A − ]
Ka =
[HA]

A weak base, B, abstracts a proton from water:

Kb
[BH][OH − ]
B + H 2O  BH + + OH − Kb =
[B]

Kb is the base hydrolysis constant, which is “small” for a weak base.

 Classes of Acids and Bases
Acetic acid (and most carboxylic acids) are weak acids; their anions (in this case the
carboxylate anion) are weak bases.

Methylamine is a weak base, and the corresponding methylammonium ion is a weak acid
(and also the conjugate acid of methylamine); this is the case for most amine and
ammonium compounds.
 Classes of Acids and Bases, 2
Methylammonium chloride dissociates in aqueous solution to give methylammonium cation
and chloride:

Methylammonium chloride is a weak acid because:

1. It dissociates into CH3NH3+ and Cl−
2. It is a weak acid, being conjugate to CH3NH2, a weak base.
3. Cl− has no basic properties, and is conjugate to HCl, a strong acid (i.e., HCl
dissociates completely). (i.e., in other words, Cl− has virtually no tendency to associate with
H+, otherwise HCl would not be a strong acid).

Metal cations, Mn+, form weak acids by acid hydrolysis to form M(OH)(n−1)+. Monovalent
metal ions form weak acids which are weaker than divalent cations, which in turn form weak
acids that are weaker than those of trivalent cations (i.e., Kmonov < Kdiv < Ktriv). We also note
that metal ions are sometimes hydrated by several H2O molecules, where the acid
dissociation reaction is:
Kb
n −1
M(H 2O)n+
x  M(H 2O)x-1 (OH) + H
+
 Classes of Acids and Bases, 3
Acid dissociation constants (−log Ka) for aqueous metal ions: e.g., for Li+, Ka = 10−13.64.
Later, we will learn that the numbers in this table are called pKa. Darkest shades are
strongest acids. [Data from R. M. Smith, A. E. Martell, and R. J. Motekaitis, NIST Critical
Stability Constants of Metal Complexes Database 46 (Gaithersburg, MD: National Institute
of Standards and Technology, 2001).]
 Polyprotic Acids and Bases
Polyprotic acids and bases are compounds that can donate or accept more than one
proton. For example, oxalic acid is a diprotic acid:

Notation for acid and base equilibrium constants: Standard notation for successive
acid dissociation constants of a polyprotic acid is K1, K2, K3, etc. Ka1 refers to the acidic
species with the most protons and Kb1 (see next slide) refers to the basic species with the
least protons. The subscript “a” in acid dissociation constants is usually omitted.
 Polyprotic Acids and Bases, 2
Phosphate is said to be tribasic:
 Polyprotic Acids and Bases, 3
The reaction of CO2 with water produces carbonic acid:

In comparing the Ka values for carbonic acid to other carboxylic acids, it may seem
surprising that the acid is classified as diprotic (i.e., Ka1 is 102 to 104 times smaller).
 Polyprotic Acids and Bases, 4
The reason for this apparent anomaly is because the value of for Ka1 is calculated from:

Only about 0.2% of dissolved CO2 is in the form H2CO3. When the true value of [H2CO3] is
used instead of the value [H2CO3 + CO2(aq)], the value of the equilibrium constant is:

Living cells utilize the enzyme carbonic

anhydrase to speed the rate at which H2CO3
and CO2 equilibrate in order to process this
key metabolite. The enzyme provides an
environment just right for the reaction of
CO2 with OH−, lowering the activation
energy (the energy barrier for the reaction)
from 50 to 26 kJ/mol and increasing the rate
of reaction by more than a factor of 106.
 Relation between Ka and Kb
A most important relation exists between Ka and Kb of a conjugate acid-base pair in
aqueous solution.

If the reactions are added, their equilibrium constants can be multiplied to yield:

K a iK b = K w
where Kw is 1.0 × 10-14.
e.g., If the Ka for acetic acid is 1.75 × 10-5, what is Kb for the acetate ion?
 Relation between Ka and Kb, 2
For a diprotic acid:

Since these sum up to yield the autoprotolysis equation for water, we get:

K a1 iK b2 = K w and K a2 iK b1 = K w
 Relation between Ka and Kb, 2
For a diprotic acid:

Since these sum up to yield the autoprotolysis equation for water, we get:

K a1 iK b2 = K w and K a2 iK b1 = K w