General Chemistry II

Module 2
Chemical Equilibria and
Thermodynamics

Equilibrium Reaction

At equilibrium

rate of the forward reaction = rate of the reverse reaction

Rate of the forward reaction = k1[A]a[B]b

Rate of the reverse reaction = k2[C]c[D]d
2

The Equilibrium Constant

The equilibrium constant for a chemical
reaction can be written in terms of a ratio of
the concentrations of the products over the
reactants each raised to their stoichiometric
coefficients.
e.g. aA + bB cC + dD
K = [C]c[D]d/[A]a[B]b
For any of the reactants or products that
are gases, the concentrations are replaced
by partial pressures
PA, PB, PC, or PD.
K = PCcPDd/PAaPBb

The Equilibrium Constant

Equilibrium constants are dimensionless.
Each quantity in the equilibrium constant is
actually a ratio of that species divided by its
concentration in its standard state
Concentration of solutes are expressed in mol/L
Concentrations of gases are expressed in bar
(1bar = 105Pa)
Concentrations of pure solids, pure liquids, and
solvents are omitted because they are unity

Equilibrium Constant
Write an equilibrium constant for the reaction
BrO3- + 2Cr3+ + 4H2O Br- + Cr2O72- + 8H+
Water is the solvent as well as a reactant and is in its standard state
Always write the equilibrium constant with products as the numerator
and reactants as the denominator
K = [Br-][Cr2O72- ][H+]8
[BrO3- ][Cr3+]2

Equilibrium Constant
Write the equilibrium
following reactions.

constant

expressions

for

C2H4 (g) + 3 O2 (g) 2 CO2 (g) + H2O(g)

K = P2CO2PH

3
/
P
P
O
C2H
O2

HF (aq) + H2O (l) F- (aq) + H3O+ (aq)

K = [F-][H3O+]/[HF]
(H2O is in its standard state and has an activity of 1)
4 NH3 (g) + 5 O2 (g) 4 NO (g) + 6 H2O (g)
K = PNO4PH

6
O

/ PNH 4PO
3

the

Example:
Write
equilibrium
expressions
heterogeneous equilibria.

for

the

following

CaCO3(s) CaO(s) + CO2(g) (at 500C)

K = PCO2
SO2(g) + H2O(g) H2SO3(aq) (at 25C)
K = [H2SO3] / PH2OPSO2
CaF2(s) Ca2+(aq) + 2 F-(aq) (at 25C)
K = [Ca2+][F-]2
3 Fe(s) + 4 H2O(g) Fe3O4(s) + 4 H2(g)

(at 500C)

K = PH24 / PH2O4
7

The Direction of Change

The Reaction Quotient, Q
Q PCcPDd/PAaPBb
In the reaction quotient, the concentrations or partial
pressures do not necessarily have their
equilibrium values.
The equilibrium constant K is determined by the
concentrations or partial pressures of reactants
and products at equilibrium and is a constant
dependent only upon temperature.
8

The Direction of Change

Q varies with time or the extent of the reaction.
As equilibrium is approached, Q K.
Qo PCocPDod/PAoaPBob
the initial reaction quotient at t = 0
If Qo < K, the reaction proceeds from left to right and
leads to the formation of more product.
If Qo > K, the reaction proceeds from right to left and
leads to the formation of more reactant.
If Qo = K, the reaction has reached equilibrium, no
net reaction occurs.
9

Example:
The equilibrium constant for the following reaction is 49 at 450C.
H2 (g) + I2 (g) 2 HI (g)

K = 49

If 0.22 mole of I2, 0.22 mole of H2 and 0.66 mole of HI were put
into an evacuated 1.00-L container, would the system be at
equilibrium?
Qo = [HI]o2/[H2]o[I2]o = (0.66)2/(0.22)(0.22) = 9.0
Qo < K

The system is not at equilibrium.

If not, what must occur to establish equilibrium?

To establish equilibrium the reaction must proceed to the right,
that is the reaction must produce more HI product.
This will lead to an increase in Q. The reaction will proceed until
Q increases to K or becomes 49.
10

External Effects and Le Chateliers

Principle
In 1884, Henri LeChatelier stated what has become
known as LeChateliers Principle
A system in equilibrium that is subjected to a stress
will react in a way that tends to counteract the
stress.
Most industrial processes are designed in such a
way that products can be removed continuously
(pushing the reaction towards the right, leading to
the generation of more product) to achieve high
overall yields, even for reactions with small
equilibrium constants.
11

External Effects and Le Chateliers

Principle
An endothermic reaction absorbs heat from the
surroundings.
K for an endothermic reaction with T.
An exothermic reaction gives off heat to the
surroundings.
K for an exothermic reaction with T.

12

Example:
Given the reaction below at equilibrium in a closed container at
500C.
N2(g) + 3 H2(g) 2 NH3(g) + 92kJ
How would the following influence the equilibrium?
T

want to absorb heat, pushed to the left

want to produce heat, pushed to the right

want to decrease ngas, pushed to right

introducing a platinum catalyst

forcing more H2 into the system
to the right
removing NH3

no effect
want to react H2 away, pushed

want to produce NH3, pushed to the right

13

Equilibrium and Thermodynamics

The equilibrium constant is directly related
to 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 favored or disfavored.

14

Enthalpy
The enthalpy change, H, for a reaction is
the heat absorbed or released when the
reaction takes place under constant applied
pressure.
The standard enthalpy change, Ho, refers
to the heat absorbed when all reactants and
products are in their standard states.
when H is (+), heat is absorbed, the
reaction is endothermic
when H is (-), heat is released, the
reaction is exothermic
15

Entropy
The entropy, S, of a substance is a
measure of its disorder. The greater the
disorder, the greater the entropy.
In general
S (gas) > S (liquid) > S (solid)
S (ions in soln.) > S (salt)
So is the change in entropy when all
species are in their standard states.
when S is (+), disorder increases,
order decreases
when S is (-),disorder decreases,
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order increases

Free Energy
The change in Gibbs free energy, G,
balances the opposing tendencies of
enthalpy (to lower values) and entropy (to
higher values)
G = H - TS
* A reaction is favored if G is negative.
The equilibrium constant depends on Go
K = e-G/RT
The more (-) the value of Go, the larger is K
A chemical reaction is favored by the
liberation of heat (H negative) and/or an
increase in disorder (S positive).17

G vs K
The standard free energy change for a
reaction is G and corresponds to the free
energy change that accompanies complete
conversion of reactants, initially present in
their standard state, to products in their
standard state. G is the free energy
change for other concentrations and
pressures.
The relationship between G and G is
G = G + RTlnQ
When a system is at equilibrium, G = 0 and
Q=K
0 = G + RTlnK
18
Therefore, the standard free energy
change

G vs K
When
G < 0, K > 1, reaction is spontaneous,
products are favored over the reactants at
equilibrium
G > 0, K < 1, reaction is not
spontaneous, reactants are favored over
the products at equilibrium
G = 0, K = 1, system is at equilibrium
under standard conditions
19

Example:
Calculate the equilibrium constant, Kp, for the following
reaction at 25C from the given thermodynamic data.
N2O4(g) 2 NO2(g)
Gf(NO2) = 51.30 kJ/mol
Gf(N2O4) = 97.82 kJ/mol
Grxn = 2Gf(NO2) - Gf(N2O4)
= {2(51.30) - 97.82}kJ/mol = 4.78kJ/mol
Kp = e-G/RT = e{-(4.78kJ/mol)(1000J/kJ)/(8.314JK-1mol-1)(298.15K)} = 0.193
20

Equilibrium vs Kinetics
The equilibrium constant tells us about the
thermodynamics of the reaction, the
relative ratios of reactants and products at
equilibrium.
It tells us NOTHING of the kinetics of the
reaction,
i.e., how rapidly equilibrium is reached.

21

Solubility Product
Dissolution and precipitation reactions by
which solids pass into and out of solution
are of great practical importance
permit isolation of single products
from reaction mixtures
purification of impure solids
control
formation
of
mineral
deposits
affect ecologies of rivers, lakes
and oceans
22

The Nature of Solubility Equilibria

Recrystallization one of the most powerful
methods for purification of solids, relies on
differences between the solubilities of the
desired substance and its contaminants
An impure product is dissolved and reprecipitated, repeatedly if necessary, with
careful control of the factors that influence
solubility.

In recrystallization, a solution begins to

23
deposit a compound when it is brought
to

The Nature of Solubility Equilibria

Saturated solution one in which a
dissolutionprecipitation equilibrium exists
between the solid substance and its
dissolved form.
Unsaturated solution one in which
solubility equilibrium ceases to exist and all
of the solid is dissolved
Supersaturated solutions condition in
which the concentration of dissolved solids
exceed their equilibrium value(s)
Dissolution-precipitation
reactions
24
frequently come to equilibrium very
slowly

The Solubility of Salts

Although all ionic compounds dissolve to
some extent in water, those having
solubilities (at 25C) of
< 0.1 g/L are referred to as insoluble.
> 10 g/L are soluble
0.1 g/L < S < 10 g/L are slightly soluble
25

Solubility Product, Ksp

AgCl(s) Ag+(aq ) + Cl-(aq)
Ksp = [Ag+][Cl-] = 1.6 x 10-10
If no solid is present, then the product of
the two ion concentrations is no longer
constrained by the solubility product
expression, and

[Ag+][Cl-] Ksp

molar solubility the # of moles of a solid

26
that will dissolve at a given temperature in

Solubility of a Sparingly Soluble Electrolyte

Calculate the solubility of silver oxalate (Ag2C2O4) in a
saturated solution Ksp = 1.3 x 10-14
Ag2C2O4 2 Ag+ + C2O42Let the solubility of Ag2C2O4 be x moles/liter
From the stoichiometry of the reaction
x 2x + x
[Ag+] = 2x and [C2O42-] = x
Ksp = [Ag+]2[C2O42-] = 1.3 x 10-14
Ksp = [2x]2[x] = 1.3 x 10-14
4x3 = 1.3 x 10-14
x = 1.48 x 10-4 moles/liter

[Ag] = 2x = 2.96 x 10-4

[C2O42-] = x = 1.48 x 10-4
27

Example:
At 25 C, in 1.00 L of solution, 0.5 mol of A2B salt is
soluble. What is the solubility product constant of A2B?
A2B(s)
Initial

2A+(aq ) + B2-(aq)

excess

Change

-0.5

Final

1.0

+2(0.5)

0.5

0.5

Ksp = [A+]2[B2-]
Ksp = [1]2[0.5]
Ksp = 0.5
28

Precipitation and the Solubility

Products
Computing Ksp from solubility, and solubility from Ksp
is valid if the solution is ideal, and if there are no
side reactions that reduce the concentrations of the
ions after they enter solution.
A solubility product is more general than
dissolving a single solid in solution.
Two solutions can be mixed to give a
precipitate, or when another salt is present
that contains an ion common to
the salt
29
under consideration.

Precipitation from Solution

Use the reaction quotient to determine
whether or not a precipitate will form
Qo = [Ag+]o[Cl-]o
if Qo < Ksp no precipitate
if Qo > Ksp a precipitate forms until Q = Ksp
The equilibrium concentrations of ions after
mixing two solutions to give a precipitate
are most easily calculated by assuming that
the reaction first goes to completion
(consuming
one
type
of
ion)
and
subsequent dissolution of the solid restores
30
some of that ionic species to solution.

The Common Ion Effect

*If a solution and the solid salt to be
dissolved in it have an ion in common, then
the solubility of the salt is depressed.

Example:
Calculate the solubility, S, of BaSO4
BaSO4(s) Ba2+(aq ) + SO42-(aq)
If S = the molar solubility of BaSO4, then S = [Ba2+] =
[SO42-]
Ksp = [Ba2+][SO42-] = [S][S] = S2 = 1.1 x 10-10 S = 1.0
x 10-5 M
31

Example:
Calculate the solubility, S, of BaSO4 in 1.0 x 10-2 M BaCl2.
BaSO4(s) Ba2+(aq ) + SO42-(aq)
mass balances:
Ba2+
Ion)

[Ba2+] = S + 1.0 x 10-2 (because of common Ba

SO42-

[SO42-] = S

Ksp = [Ba2+][SO42-] = 1.1 x 10-10 = S(S + 1.0 x 10-2)

S2 + 1.0 x 10-2S 1.1 x 10-10 = 0 (quadratic equation)
S = -1.0 x 10-2 [(1.0 x 10-2)2 + 4(1.1 x 10-10)]/2
= 1.1 x 10-8M
Solubility is decreased by almost a factor of 3210 3 compared
to pure water.

Precipitation
A precipitate will form when the ion product
concentration exceeds the Ksp
How many mL of 0.10 M K2CrO4 solution would have to
be added to 50 mL of 1.00 mM Cu(NO3)2 to begin to
precipitate CuCrO4. Ksp = 3.6 x 10-6 for CuCrO4

Cu(NO3)2 + K2CrO4 CuCrO4 + 2 KNO3

After addition of x mL of K2CrO4 solution
[Cu2+] = 1 x 10-3(50/ 50 + x)
[CrO42-] = 0.1(x / 50 + x)
Ksp = [Cu2+] [CrO42-] = 3.6 x 10-6

33

Precipitation
After substitution of concentration terms into Ksp
and rearrangement
3.6 x 10-6 x2 4.64 x 10-3 x + 9 x 10-3 = 0
a = 3.6 x 10-6, b = 4.64 x 10-3, and c = 9 x 10-3
x = {-b (b2 4ac)}/2a
x = 1.94 mL
1.94 ml of K2CrO4 solution is the minimum volume
required to just form a permanent precipitate
34

Separations
Precipitation reactions can sometimes be used to
separate ions from each other
A solution contains 0.01 M Ca2+ and 0.01 M Ce3+. Is it possible to
selectively precipitate 99.9% of Ce3+ from this solution by adding
oxalate without precipitating any Ca2+ ?
Ca(C2O4) Ca2+ + C2O42Ksp = 1.3 x 10-8
Ce2(C2O4)3 2 Ce3+ + 3 C2O42-

Ksp = 3.0 x 10-29

Original [Ce3+] = 0.01 M

If 99.9% is to be precipitated then [Ce3+] = 0.01 (0.01/100) = 1 x 10-5 M
Let x = [C2O42-] in equilibrium with Ca2+ with the required [Ce3+]
Ksp = [Ce3+] 2 [C2O42-] 3 = 3.0 x 10-29
[Ce3+] = 1 x 10-5 and [C2O42-] = x
x3 = (3.0 x 10-29 / 1 x 10-10) and x = 6.69 x 10-7
35

Separations- Part 2
Will the 6.69 x 10-7 M of C2O42- cause precipitation with a
0.01 M solution of Ca2+?
[Ca2+] = 0.01 M
[C2O42-] = 6.69 x 10-7 M
Q = [Ca2+][C2O42-] = [0.01][6.69 x 10-7] = 6.69 x 10-9
Since Q (=6.69 x 10-9) is less than Ksp (= 1.3 x 10-8) it is
possible to precipitate 99.9% cerium from this solution
36

Complex Ions and Solubility

Coordination
Complexes

metal
ion
surrounded by a group of anions or neutral
molecules called ligands.
Bonding interaction involves the sharing of
a lone pair of electrons on each ligand with
the metal providing a partially covalent
bond.

Overall reaction
M(H2O)n + nL MLn + n H2O
37

Coordination Complexes
NH 3
Complexes formed in a series of H3 N Cu 2+ NH 3
Sequential stepwise equilibrium reactions
NH 3
Cu2+(aq) + NH3(aq) Cu(NH3)2+(aq)
K1 = [Cu(NH3)2+] / [Cu2+][NH3] = 1.0 x 104
Cu(NH3)2+(aq) + NH3(aq) Cu(NH3)22+(aq)
K2 = [Cu(NH3)22+] / [Cu(NH3)2+][NH3] = 2.0 x
103
Cu(NH3)22+(aq) + NH3(aq) Cu(NH3)32+(aq)
38
K3 = [Cu(NH3)32+] / [Cu(NH3)22+][NH
] = 5.0 x
3

Coordination Complexes
Cu(NH3)32+(aq) + NH3(aq) Cu(NH3)42+(aq)
K4 = [Cu(NH3)42+] / [Cu(NH3)32+][NH3] = 90.
Overall reaction:
Cu2+(aq) + 4 NH3(aq) Cu(NH3)42+(aq)
Kf = [Cu(NH3)42+] / [Cu2+][NH3]4
= K1K2K3K4 = 1.1 x 1012
Kf is the formation constant of the fully
complexed ion.
The larger Kf is, the more stable the
39
corresponding complex ion is (for ions with

Common Ion Effect versus Formation of

Coordination Complexes
Complex ion formation affects solubility in the
opposite direction from the common ion effect.
Common ion effect reduces solubility by
increasing the concentration of one of the ions in
solution.
Complex ion formation increases solubility by
decreasing the concentration of one of the ions in
solution.

Protic Acids and Bases

In aqueous solutions, an acid is a substance that
increases the concentration of H+ (or more
accurately H3O+, the hydronium ion) when added to
the solution.
A base decreases the concentration of H+ (or more
accurately, H3O+) or increases the concentration of
OHThe word protic refers to chemistry involving the
transfer of protons between species.

Brnsted-Lowry Acids and Bases

A Brnsted-Lowry acid is a proton donor
HCl (aq) + H2O () H3O+ (aq) + Cl- (aq)
A Bronsted-Lowry base is a proton acceptor.
The Bronsted-Lowry definition of acids and bases
does not require an aqueous solution, and applies to
nonaqueous solutions and to the gas phase as well.

42

Salts
HCl(g) + NH3(g) NH4+Cl-(s)
acid
base
salt
An ionic solid is called a salt. It can be thought of as
a product of an acid base reaction.
When an acid and a base react, they are said to
neutralize each other and produce a salt.
Most salts composed of singly charged cations and
anions such has Na+Cl- and NH4+Cl- are strong
electrolytes and dissociate completely in dilute
43
aqueous solution.

Conjugate Acids and Bases

The products of a reaction between an acid and a
base are also classified as acids and bases
HA + B
A+
HB+
acid + base conjugate base + conjugate acid

44

The Nature of H+ (H3O+) and OHThe proton H+ does not exist on its own, it is tightly
associated with at least one (H3O+) or maybe even
multiple H2O molecules in solution (H5O2+, H7O3+,
H9O4+, etc.) and with other molecules in crystals.
Most often H+ in solution is designated as H3O+
rather than H+ because the first H2O molecule is very
strongly bound, (while the strength of binding of
additional H2O molecules falls of rapidly with the
extent of solvation).

46

Autoprotolysis
Water undergoes self-ionization, a reacton called
autoprotolysis, in which it acts as both an acid and a
base
2 H2O () H3O+ + OHProtic solvents (water, methanol, ethanol, acetic
acid, etc.) have a reactive H+ and all protic solvents
undergo autoprotolysis to some extent.
2 CH3CO2H () CH3CO2H2+ (aq) + CH3CO2- (aq)
47

pH
The autoprotolysis constant for H2O has a special
designation Kw
2 H2O () H3O+ (aq) + OH- (aq)
Kw = [H3O+][OH-] = 1.0 x 10-14 at 25C
In general equilibrium constants depend upon
temperature, Kw increases with T because this
reaction is endothermic.
48

pH
An approximate definition of pH
pH = -log [H3O+].
The exact definition depends upon activities (Chapter 7). pH
generally lies between 0 and 14 but can extend beyond these
ranges in very strongly acidic and basic solutions.

pOH = -log [OH-]

pH + pOH = 14.00
A solution is acidic if [H3O+] > [OH-], and pH < 7.00
A solution is basic if [H3O+] < [OH-] and pH > 7.00
49

Strengths of Acids and Bases

The strength of an acid or base is a measure of how
completely it dissociates to produce H3O+ or OH-.
Strong acids dissociate completely or nearly
completely in water
HA(aq) + H2O() H3O+(aq) + A-(aq)
Weak acids dissociate only partially and thus
their reactivity is described by an equilibrium
constant.
HA(aq) + H2O() H3O+(aq) + A-(aq)
50

Common Strong Acids and Bases

Strong Acids
HCl, HBr, HI, H2SO4, HNO3, HClO4
For H2SO4, only the first proton ionization is
complete. Dissociation of a second proton has an
equilibrium constant of 1.0x10-2
Strong Bases
LiOH, NaOH, KOH, RbOH, CsOH, R4NOH
(where R = H, CH3, C2H5, or any organic group)
51

pH of Various Substances

52

Weak Acids and Bases

Dissociation of a weak acid
HA (aq) + H2O () H3O+ (aq) + A- (aq)
Acid dissociation constant
Ka = [H3O+][A-]/[HA]
Base Hydrolysis
B (aq) + H2O () BH+ (aq) + OH- (aq)
Base hydrolysis or dissociation constant
Kb = [BH+][OH-]/[B]
53

Dissociation of Acetic Acid

Dissociation of Weak Acid/Base

Common Classes of Weak Acids and

Bases
Carboxylic acids RCO2H where R = an organic
substituent.
Most carboxylic acids are weak acids and
carboxylate anions are weak bases.
Amines are (RNH2, R2NH, R3N) weak bases.
Ammonium ions (RNH3+, R2NH2+, R3NH+) are weak
acids.
56

Polyprotic Acids and Bases

Polyprotic acids and bases are compounds that can
donate or accept more than one proton.
H3A(aq) + H2O() H2A-(aq) + H3O+(aq)
K1 = [H2A-][H3O+]/[H3A]
H2A-(aq) + H2O() HA2-(aq) + H3O+(aq)
K2 = [HA2-][H3O+]/[H2A-]
HA2-(aq) + H2O() A3-(aq) + H3O+(aq)
K3 = [A3-][H3O+]/[HA2-]

57

Relation Between Ka and Kb

Relationship between Ka and Kb of a conjugate acidbase pair
HA(aq) + H2O() H3O+(aq) + A-(aq) Ka = [H3O+][A-]/[HA]
A-(aq) + H2O() HA(aq) + OH-(aq)
2 H2O() H3O+(aq) + OH-(aq)

Kb = [HA][OH-]/[A-]

Kw = KaKb = [H3O+][OH-]

pKw = pKa + pKb

pKa + pKb = 14

Similar relationships hold for polyprotic acids/bases.

58