Lecture 18. Chemical Reactions (Ch.

5)
TS PV U G + =
In chemical reactions, the products of reaction are intermixed with the reacting
substances (reactants). Thus, the process is governed by two factors: (a) the energy
change (V,T=const) or enthalpy change (T,P=const), and (b) the entropy change:
For a reaction to be energetically favorable, the Gibbs energy for products should be
lower than the Gibbs energy for reactants.
Chemical Reactions
- processes of molecular transformations that involve at least one of the following
changes: the number of atoms in a molecule, the type of atoms, their mutual
positioning in a molecule (isomers), or their charge.
O 2H CO 2O CH
2 2 2 4
+ +
O=O
O=O
H - C - H
H
H O=C=O
H-O-H
H-O-H
During this reaction, some bonds should be broken and other bonds (with a more
negative potential energy) should be formed. This process is characterized by a
potential barrier thus, the Boltzmann factor! For the direct reaction, the barrier is
, for the reverse one - .

H

A
H

A
H A
H
the enthalpy
released
in the reaction
at P,T=const
reac-
tants
products
reaction coordinate
H

A H

A
The reactions are characterized by directionality (which free energy is lower,
reactants or products), energy release, and rate.
( )
P T other
W dG
,
o =
The other work (electrical, chemical, etc.)
performed on a system at T = const and P =
const in a reversible process is equal to the
change in the Gibbs free energy of the system:
other
W PdV W o o + =
Directionality of Chemical Reactions
The directionality of a chemical reaction at fixed P,T is governed by the Gibbs free
energy minimum principle. Two factors are at play: the entropy and the enthalpy. Since
the change in G is equal to the maximum useful work which can be accomplished by
the reaction, then AG < 0 indicates that the reaction will proceed spontaneously.
2 2 2 2 9 3 5 3
0.5O 3N O 5H 6CO O N H 2C + + +
- clearly, S increases. Also, the energy of the products of the reaction is lower than the
reactant (the energy is released in the TNT explosion): the reaction is shifted strongly
toward the products.
H H H
2
+ - though S increases, the equilibrium is shifted to the left (AH >TAS) at 300K
S T H G A A = A
O 2H O 2H
2 2 2
+
- though S decreases, the equilibrium is shifted to the right
because the decrease of AH overpower the increase of -TAS
AH AS AG = AH-TAS
+ reaction will go spontaneously
+ + reaction needs input of energy to go


The sign of AG
depends on the
relative values of AH,
AS and T
If reaction is spontaneous, the
reaction is entropy-driven: the
increase in disorder is sufficient to
drive the reaction despite the fact that
it absorbs heat from its surroundings.
+ +
Examples:
reaction AH
kJ/mol
-T AS
kJ/mol
AG
kJ/mol
CO+H
2
C+H
2
O -130 +39 -91
CO+2H
2
CH
3
OH -85 +65 -20
2CO+2H
2
CH
3
COOH -257 +147 -110
Several channels of the reaction between CO and H
2
at 300K
reaction AH
kJ/mol
-T AS
kJ/mol
AG
kJ/mol
CO+H
2
C+H
2
O -130 +78 -52
CO+2H
2
CH
3
OH -85 +130 45
2CO+2H
2
CH
3
COOH -257 +394 137
Several channels of the reaction between CO and H
2
at 600K
at this T, CH
3
OH
and CH
3
COOH will
spontaneously dissociate
These estimates tell us nothing about the reaction rate ! (the process of
transformation of diamond into graphite also corresponds to negative AG = -2.9
kJ/mol, but our experience tells us that this process is extremely slow).
Exchange with the Environment
For reversible processes, 0 = A + A = A
env system Universe
S S S
AS in the system AS in the environment
0
" "
= A
Universe
S
If the entropy of a system is increased in the process of
chemical reaction, the entropy of the environment must
decrease. The associated with this process heat transfer from
the environment to the system in a reversible process:
0 < A =
env
S T q o
Universe = a nonisolated system + its environment
system
environment
Thus, an entropy increase pumps some energy out of the environment into the system.
The difference between the internal energies (V,T const) or enthalpies (P,T const)
of reactants and products represent the heat of reaction:
( ) H Q
P T
A =
,
o < 0 exothermic, > 0 - endothermic
If an exothermic reaction proceeds spontaneously, it means that (a) it is entropy-
driven, and (b) the system gets some energy necessary for the reaction from its
environment (heat bath). The latter process happens whenever the entropy of the
ptoducts is greater than that for the reactants.
Problem
Molar values of AH and AS for the reaction of dissolving of NH
4
Cl in water at
standard conditions (P=1 bar, T=298 K) are 34.7 kJ/mol and 0.167 kJ/(Kmol),
respectively.
(1) Does the reaction proceed spontaneously under these conditions?
(2) How does the entropy of the environment and the Universe change in this
reversible process?
0 J/mol < = = A A = A 1 . 15 167 . 0 298 7 . 34 S T H G
AG <0, thus the reaction proceeds spontaneously (despite its endothermic character).
High temperatures favor the spontaneity of endothermic processes.
) /( 167 . 0
298
/ 8 . 49
mol K kJ
K
mol kJ
T
q
T
q
S
sys
env
env
= = = = A
The reversible energy (heat) for this process:
mol kJ S T q
syst
revers
syst
/ 8 . 49 167 . 0 298 = = A =
0 ) /( 167 . 0 ) /( 167 . 0
.
= = A + A = A mol K J mol K J S S S
env syst Universe
k k
Oxidation of Methane
Consider the reaction of oxidation of methane: OH CH O CH
3 2 4
+ 5 . 0
For this reaction AH = -164 kJ/mol, AS = -162 J/molK.
( )
K 0
3
10
/ 162
/ 164
~

< < A A = A
K mol J
mol kJ
T S T H G
(b) The energy transferred to the environment as heat:
( ) mol kJ mol K J K S T G H q
revers
syst
/ 28 . 48 / 162 298 = = A = A A =
For reversible processes: 0 = A + A = A
env system total
S S S
mol K J
K
mol kJ
T
q
S
env
env
= = = A / 162
298
/ 28 . 48
(a) Find the temperature range where this reaction proceeds spontaneously.
(b) Calculate the energy transferred to the environment as heat at standard
conditions (T = 298 K, P = 1 bar) assuming that this process is reversible.
(c) Calculate the change in the entropy of environment, AS
env
, at standard
conditions assuming that this process is reversible. What is the total entropy
change for the Universe (the system + environment) if the process is
reversible?
(a) For this reaction to proceed spontaneously, AG must be negative:
mol kJ q q
syst env
/ 28 . 48 = =
(c)
Glucose Oxidation
O H 6 6CO O 6 O H C
2 2 2 6 12 6
+ +
Mammals get the energy necessary for their
functioning as a result of slow oxidation of glucose :
At standard conditions, for this reaction AH = -2808 kJ/mol, AS = 182.4 J/molK.
Thus, at T=298K, this reaction will proceed spontaneously.
0 J/mol < = = A A = A
3 3
10 4 . 2862 4 . 182 298 10 2808 S T H G
If this process proceeds as reversible at P,T=const, the maximum other work
(chemical, electrical, etc.) done by the system is:
J/mol
3
max
10 2862 = A = G W
This work exceeds the energy released by the system (AH = -2808 kJ/mol). Clearly,
some energy should come from the environment. For reversible processes:
Thus, the environment transfers to the system 54.4 kJ/mol as the thermal energy (heat).
The system transforms into work both the energy released in the system (AH) and the
heat received from the environment (q
env
). For all reactions that are characterized by
enthalpy decrease and entropy increase, W
max
exceeds AH. Interestingly that the
Nature selected this process as a source of work: it not only releases a great deal of
energy, but also pumps the energy out of the environment!
( ) mol kJ mol J S T q
env env
/ 4 . 54 / 4 . 182 298 = = A =
The Rates of Chemical Reactions
H

A
H

A
H A
H
reac-
tants
products
reaction coordinate
The rates of both direct and reverse rections are
governed by their Boltzmann factors (the activation
over the potential barrier). Thus, each rate is an
exponential function of T. Catalysts reduce the
height of an activation barrier.
The rate is proportional to the probability of collisions between the molecules
(concentration of reactants).
Chemical equilibrium = dynamical equilibrium,
the state in which a reaction proceeds at the same
rate as its inverse reaction.
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A
=
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A

T k
H
T k
H
B
B

exp
exp
cts conc.produ
ants conc.react
t
dissociation
association
r
a
t
e

equilibrium
Chemical Equilibrium
G
A

G
B

ideal mixing
x
reactants products
of reaction
chemical equilibrium (strongly
shifted to the right, but still there is
a finite concentration of reactants)
S T H G A A = A
This can be understood using the concept of the
minimization of the Gibbs free energy in equilibrium.
The reason for the incompleteness of reactions is
intermixing of reactants and products.
Without mixing, the scenario would be
straightforward: the final equilibrium state would be
reached after transforming 100% of reactants into
products. However, because the products are
intermixed with the reactants, breaking just a few
products apart into the reactant molecules would
increase significantly the entropy (remember, there
are infinite slopes of G(x) at x = 0,1), and that shifts
the equilibrium towards x < 1.
t
dissociation
association
r
a
t
e

equilibrium
This plot shows that despite the fact that a particular
reaction could be energetically favorable, it hardly
ever go to comletion. At any non-zero T, there is a
finite concentration of reactants.
Chemical Equilibrium (cont.)
The chemical potentials
i
are functions of T, P, and all N
i
. Hence this condition implies that
in equilibrium, there is a definite connection between the mean numbers of molecules of
each kind. In principle, the statistical physics allows one to calculate the chemical potentials

i
and thus to deduce explicitly the connection between the numbers N
i
.

Combining with the expression for dN
i
: 0
1
=

=
m
i
i i
a
0
1
= =

=
m
i
i i
dN dG In equilibrium, at fixed T and P, The Gibbs free energy is at minimum:
- the general condition
for chemical equilibrium
.... ....
3 2 1 3 2 1
3 2 1 3 2 1
P a P a P a R a R a R a
P P P R R R
+ + + +
reactants products
0
1
=

=
m
i
i i
B a
The sign of coefficients a
i
is different for the reactants and for the products:
The numbers of different kinds of molecules, N
i
, cannot change independently of each
other the equation of chemical reaction must be satisfied: dN
i
must be proportional to
the numbers of molecules appearing in the balanced chemical equation:

i i
a dN =
Here is a constant of proportionality, dN
i
>0 (dN
i
<0)
for molecules formed (disappeared) in the reaction.
Lets consider a general chemical equation:
0 2HCl Cl H 2HCl Cl H
2 2 2 2
= + = +
stoichiometric coefficients
1 : 1 : 2 : :
2 2
=
Cl H HCl
dN dN dN
0 2
2 2
=
Cl H HCl

( )
2 2
2
1
Cl H HCl
+ =
Chemical Equilibrium between Ideal Gases
Example: transformation of the nitrogen in air into a form that can be used by plants
3 2 2
2NH H 3 N + ammonia
Lets consider the reaction that occurs in the gas phase, and assume that each
reactant/product can be treated as an ideal gas. For this case, we know = (T,P).
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+ =
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+ +
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|

\
|
+
0
0
0
0
0
0
N
3
3
2
2
2
2
ln 2 2 ln 3 3 ln
P
P
T k
P
P
T k
P
P
T k
NH
B NH
H
B H
N
B

In equilibrium:
( ) ( ) ( )
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+ =
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\
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+ = = =
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|

\
|
c
c
=
c
c
0
0
0
0
,
ln ln , ,
P
P
T k T
P
P
T k P T P T
P
T k
N
V
N
G
P P
B B
B
N T

0
represents the chemical potential of a gas in its standard state, when its partial
pressure is P = P
0
(usually

P
0
= 1 bar).
( )
( ) ( )
0
N
0 0
2
2
0
3
0 0 0 2 2 3
3
2 2 3 2 2
3 2 ln ln 2 ln 3 ln =
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=
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|

\
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+
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.
|

\
|
H NH
NH
H N
B
NH
B
H
B
N
B
P P
P P
T k
P
P
T k
P
P
T k
P
P
T k
( )
( ) ( )
( )
0 0
N
0 0
2
2
0
3
2 2 3
3
2 2
3 2 ln G N
P P
P P
RT
H NH A
NH
H N
A = =
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|

\
|

x N
A

- the tabulated change in G
for this reaction at P
0
= 1 bar
The chemical potential of an ideal gas:
The Law of Mass Action
( )
( ) ( )
( ) ( )
( )
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|

\
| A
= A =
|
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.
|

\
|
RT
G
P P
P P
G
P P
P P
RT
H N
NH
NH
H N
0
3
2
2
0
0
2
2
0
3
exp ln
2 2
3
3
2 2
the equilibrium constant K
( ) ( )
( )
K
P P
P P
H N
NH
=
3
2
2
0
2 2
3
In general, for a reaction 0
1
=

=
m
i
i i
B a ( )
RT
G
P P P
a a a
0
3 2 1
... ln
3 2 1
A
=
( ) T P K
RT
G
P P P
a a a
, exp ...
0
0
3 2 1
3 2 1
=
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.
|

\
| A
=
- all pressures are normalized by
the standard pressure P
0

The product of the concentration of the reaction partners with all concentrations
always taken to the power of their stoichiometric factors, equals a constant K
which has a numerical value that depends on the temperature and pressure. In
particular, - the exponential temperature dependence of the equilibrium constant K is
due to the Boltzmann factor:

|
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\
|
A

|
.
|

\
|
A
=
|
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.
|

\
| A
=
RT
U
R
S
RT
G
K exp exp exp
0
Generalization of this law for the concentrations
of the reaction partners in equilibrium (not
necessarily in the gas phase) is known as the
law of mass action (Guldberg-Waage, 1864):
K
RT
G
N N N
a a a
=
|
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|

\
| A
=
0
3 2 1
exp ...
3 2 1
Ammonia Synthesis
( ) ( )
( )
|
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|

\
|
A
=
RT
G
P P
P P
H N
NH
exp
3
2
2
0
2 2
3
At T = 298K and P = 1 bar, AG = -32.9 kJ for
production of two moles of ammonia
3 2 2
2NH H 3 N +
( )( )
5
3
10 9 . 5
298 J/K 8.3
J 10 9 . 32
exp exp =
|
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.
|

\
|
=
|
.
|

\
|
A
=
K RT
G
K
Thus, the equilibrium is strongly shifted to the right, favoring the production of ammonia
from nitrogen and hydrogen.

Haber Process, developed into an industrial process by C. Bosch - a major chemical
breakthrough at the beginning of the 20
th
century (1909):
T = 500
0
C, P = 250 bar, plus a catalist (!!!). At this temperature, K = 6.910
-5
(the drop
of K can be calculated using vant Hoffs equation and AH
0
=-46 kJ, see Pr. 5.86). To
shift the reaction to the right (higher concentration of the product), a very high
pressure is needed.
The calculation of the equilibrium constant K is only the first step in evaluating the
reaction (e.g., its usefulness for applications). However, the value of K tells us nothing
about the rate of the reaction. For this particular reaction, at the temperatures below
700
0
C, the rate is negligible (remember, the rapture of N-N and H-H bonds is an
activation process). To increase the rate, either a high temperature or a good catalist is
required.
Example of Application of the Law of Mass Action
Lets look at a simple reaction
CO O H CO H
2 2 2
+ +
Notice that we have the same # of moles on both sides of the reaction equation. We
start with n
0
H2
and n
0
CO2
moles of the reacting gases and define as the yield y the
number of moles of H
2
O that the reaction will produce at equilibrium:
( )( )
K
y n y n
y
=

0
CO
0
H
2
2 2
0
CO
0
H
0 0
CO CO
0
H H CO O H
2 2 2 2 2 2 2
n n n n y n n y n n y n y n + = = = = = =

equilibrium concentrations of H
2
and CO
2

The mass action law requires:
This is a quadratic equation with respect to y, the solution is straightforward but messy.
What kind of starting concentrations will give us maximum yield? To find out, we have
to solve the equation dy/dn
0
H2
= 0. The result:
0
H
0 0
CO
0 0
H
2 2 2
2 / 2 / n n n n n = = =
- maximum yield is achieved if you mix just the right amounts of the starting stuff.
This result is always true, even for more complicated reactions.
The Temperature Dependence of K (vant Hoff Eq.)
|
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\
| A
=
RT
G
K
0
exp
Its important to know how the equilibrium concentrations are affected by temperature
(Pr. 5.85). We also need this result for solving Problems 5.86 and 5.89.
( )
2
0
0
0
1
ln
T
G
T
G
T
R RT
G
T
K
T
A
c
A c
=
|
|
.
|

\
| A

c
c
=
c
c
For either the reactants or the products, S
T
G
=
c
c
0
0
0
S
T
G
A =
c
A c
( )
( )
2
0
2
0 0 0
1
ln
RT
H
T
S T H S T
R
K
T
A
=
A A A
=
c
c
( )
2
0
ln
RT
H
K
T
A
=
c
c vant Hoffs
equation
Lets find the partial derivative of lnK with respect to T at P=const
( )
} }
A
=
f
i
f
i
T
T
T
T
dT
RT
H
K d
2
0
ln ( ) ( )
|
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.
|

\
|

A
=
f i
i f
T T R
H
T K T K
1 1
ln ln
0
AH
0
is the enthalpy change of the reaction. If AH
0
is positive (if the reaction
requires the absorption of heat), then higher T shifts the reaction to the right
(favor higher concentrations of the products). For the exothermic reactions, the shift
will be to the left (higher concentration of the reactants).
Chemical Equilibrium in Dilute Solutions
Assuming the solution is very dilute:
( )
solute
0
solute
ln , m T k P T
B
+ =
- -
2 HO
0
HO H
0
H
0
O H
ln ln m T k m T k
B B
+ + + =
+ +

where
0
are the chemical potentials for the substance in its standard state: pure liquid
for the solvent, 1 molal for the solutes. This differs from the reactions in the gas phase,
where the standard state corresponds to the partial pressure 1 bar.
( ) ( ) P T
N
N
T k P T
B
, ,
0
solvent
solvent
solute
0
solvent solvent
~ =
kJ OH H O H
-
9 . 79
0
2
= A +
+
G
Under ordinary conditions, the equilbrium is strongly
shifted to the left, but still there is a finite
concentration of ions H
+
and OH
-
dissolved in water.

In equilibrium:
0 1
H
+
+OH
-
H
2
O
G
A

G
B

ideal mixing
x
the shift is exaggerated:
Ax
eq
~ 110
-7
O H
OH H 2
= +
+
( ) ( )
0 0
O H
0
HO
0
H HO H 2
- -
ln G N m m RT
A
A = + =
+ +

|
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|

\
| A
=
+
RT
G
m m
0
HO H
exp
-
In the final equation, partial pressures are replaced with the molalities. Most importantly,
the water concentration vanishes from the left side its standard concentration
remains =1 because the number of dissociated molecules is tiny.
Water dissociation:
7
HO H
10 1
-

= =
+
m m The 7 is called the pH of pure water.
Chemical Equilibrium between Gas and Its Dilute Solution
The same technique can be applied to the equilibrium between molecules in the gas
phase and the same molecules dissolved in a solvent.
( ) ( ) kJ 4 . 16 aqueous O gas O
0
2 2
= A G
The Gibbs free energy change AG
0
for this reaction is for one mole of O
2
dissolved
in 1 kG of water at P = 1bar and T = 298 K.
In equilibrium: ( ) ( ) P T P T
aqueous gas
, ,
) ( O ) ( O
2 2
=
( ) ( )
|
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|

\
|
+ =
0
0 0
ln , ,
P
P
T k P T P T
B gas
For O
2
gas:
For O
2
dissolved in water: ( )
solute
0 0
solute solute
ln , m T k P T
B
+ =
( )
0 0
gas
0
solute
solute
0
solute
0
solute
0
0
gas
/
ln ln ln G N
m
P P
RT m T k
P
P
T k
A B B
A = =
|
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|

\
|
+ =
|
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|

\
|
+
|
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|

\
| A
=
RT
G
P P
m
0
0
solute
exp
/
Henrys law (the amount of dissolved gas is proportional to
the partial pressure of this gas)
For O
2
in water:
( )( )
3
3 0
10 3 . 1
K 98 2 J/K 3 . 8
J 10 4 . 16
exp exp

~
|
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.
|

\
|
=
|
|
.
|

\
| A

RT
G
P
O2
=0.2 bar, m
solute
= 1.310
-3
x 0.2 = 2.6 10
-4
equivalent of 6.6 cm
3
of O
2
gas at
normal conditions (1 mol at P=1 bar ~25 liters).
Example: oxygen dissolved in water.