Lecture 18. Chemical Reactions (Ch.

5)
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:

G U PV TS
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.

H
reactants

the enthalpy
released
in the reaction
at P,T=const

products

reaction coordinate

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:

W PdV Wother dG Wother T , P

CH 4 2O 2 CO 2 2H2O
H
H-C-H
H

O=O

O=C=O
H-O-H

O=O

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

H , for the reverse one - H .

The reactions are characterized by directionality (which free energy is lower,
reactants or products), energy release, and rate.

Directionality of Chemical Reactions

G H TS

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 G < 0 indicates that the reaction will proceed spontaneously.
H

G = H-TS

reaction will go spontaneously

reaction needs input of energy to go

The sign of G
depends on the
relative values of H,
S and T

Depends on the sign of G

2C 3H5N3O9 6CO 2 5H2O 3N2 0.5O 2

- 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.

H2 H H - though S increases, the equilibrium is shifted to the left (H >TS) at 300K

2H2 O2 2H2O

- though S decreases, the equilibrium is shifted to the right

because the decrease of H overpower the increase of -TS

Several channels of the reaction between CO and H2 at 300K

reaction

H
kJ/mol

-T S
kJ/mol

G
kJ/mol

CO+H2C+H2O

-130

+39

-91

CO+2H2CH3OH

-85

+65

-20

2CO+2H2CH3COOH

-257

+147

-110

Examples:

Several channels of the reaction between CO and H2 at 600K

reaction

H
kJ/mol

-T S
kJ/mol

G
kJ/mol

CO+H2C+H2O

-130

+78

-52

CO+2H2CH3OH

-85

+130

45

2CO+2H2CH3COOH

-257

+394

137

at this T, CH3OH
and CH3COOH will
spontaneously dissociate

These estimates tell us nothing about the reaction rate ! (the process of
transformation of diamond into graphite also corresponds to negative G = -2.9
kJ/mol, but our experience tells us that this process is extremely slow).

Problem
Molar values of H and S for the reaction of dissolving of NH4Cl 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?

G H TS 34.7 298 0.167 15.1 J/mol 0

G <0, thus the reaction proceeds spontaneously

The reversible energy (heat) for this process:

revers
qsyst
TSsyst 298 0.167 49.8kJ / mol

Senv

qsys
qenv
49.8 kJ / mol

0.167 kJ /( K mol)
T
T
298 K

SUniverse S syst S env. 0.167 kJ /( K mol ) 0.167 kJ /( K mol ) 0

Oxidation of Methane
Consider the reaction of oxidation of methane:

CH 4 0.5 O2 CH3OH

For this reaction H = -164 kJ/mol, S = -162 J/molK.

(a)
(b)
(c)

Find the temperature range where this reaction proceeds spontaneously.

Calculate the energy transferred to the environment as heat at standard
conditions (T = 298 K, P = 1 bar) assuming that this process is reversible.
Calculate the change in the entropy of environment, Senv, 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, G must be negative:

G H TS 0

164 kJ / mol
10 3 K
162 J / mol K

(b) The energy transferred to the environment as heat:

revers
qsyst
H G TS 298K 162J / K mol 48.28 kJ / mol

qenv qsyst 48 .28 kJ / mol

qenv 48.28 kJ / mol

162J / K mol
env
(c)
T
298K
S total S system S env 0
For reversible processes:

Glucose Oxidation
Mammals get the energy necessary for their
functioning as a result of slow oxidation of glucose :

C6 H12 O 6 6O 2 6CO 2 6H 2O

At standard conditions, for this reaction H = -2808 kJ/mol, S = 182.4 J/molK.

G H TS 2808103 298182.4 2862.4 103 J/mol 0

Thus, at T=298K, this reaction will proceed spontaneously.
If this process proceeds as reversible at P,T=const, the maximum other work
(chemical, electrical, etc.) done by the system is:
3

Wm ax G 2862 10 J/mol

This work exceeds the energy released by the system (H = -2808 kJ/mol). Clearly,
some energy should come from the environment. For reversible processes:

qenv TS env 298 182 .4 J / mol 54 .4 kJ / mol

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 (H) and the
heat received from the environment (qenv). For all reactions that are characterized by
enthalpy decrease and entropy increase, Wmax exceeds H. 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!

H
reactants

products

reaction coordinate

The Rates of Chemical Reactions

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).

k BT

conc.products exp

k BT

association
rate

Chemical equilibrium = dynamical equilibrium,

the state in which a reaction proceeds at the same
rate as its inverse reaction.

conc.reactants exp H

equilibrium

dissociation
t

Chemical Equilibrium
rate

association

equilibrium

dissociation

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.

G H TS
GA

ideal mixing

reactants

GB
products
of reaction

chemical equilibrium (strongly

shifted to the right, but still there is
a finite concentration of reactants)

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.

Lets consider a general chemical equation:

Chemical Equilibrium (cont.)

m

a B

a R1 R1 a R2 R2 a R3 R3 .... aP1 P1 aP2 P2 aP3 P3 ....

reactants

i 1

stoichiometric coefficients

products

The sign of coefficients ai is different for the reactants and for the products:

H2 Cl 2 2HCl

H2 Cl 2 2HCl 0

The numbers of different kinds of molecules, Ni, cannot change independently of each
other the equation of chemical reaction must be satisfied: dNi must be proportional to
the numbers of molecules appearing in the balanced chemical equation:

dNi ai

Here is a constant of proportionality, dNi>0 (dNi<0)

for molecules formed (disappeared) in the reaction.

dN HCl : dN H 2 : dN Cl 2 2 : 1 : 1

In equilibrium, at fixed T and P, The Gibbs free energy is at minimum: dG

dN
i 1

Combining with the expression for dNi :

2 HCl H 2 Cl 2 0

HCl

1
H 2 Cl 2
2

a
i 1

0 - the general condition

for chemical equilibrium

The chemical potentials i are functions of T, P, and all Ni. 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 Ni.

Chemical Equilibrium between Ideal Gases

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).
Example: transformation of the nitrogen in air into a form that can be used by plants

N 2 3H 2 2NH 3

ammonia

The chemical potential of an ideal gas:

G
V kT

B
P P N T , N N
P

T , P T , P 0 k BT ln

P
P
0

k
T
ln

0
B
0
P

P

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).
In equilibrium:

PN
k BT ln 02
P
x NA

0
N2

PN 2
k BT ln 0
P

P
3k BT ln H02

PH 2
0
3 H 2 3k BT ln 0

2k BT ln NH0 3

PNH 3

0
2 NH 3 2k BT ln 0

P P 3

2 0 3 0 0
k BT ln N 22 H 2
NH 3
H2
N2
P0 P 2

NH 3

P P 3
N2
H2
N 2 0 3 0 0 G 0 - the tabulated change in G
RT ln
A
NH 3
H2
N2
2
for this reaction at P0 = 1 bar
P0 2 P
NH 3

The Law of Mass Action

P P
P P

P P 3
N2
H2
G 0
RT ln
P0 2 P 2
NH 3

0 2

N2

NH 3
3
H2

P P
P P
0 2

G 0

exp
RT

N2

NH 3
3
H2

the equilibrium constant K

m

In general, for a reaction

a B
i 1

G 0
K P 0 , T
P P P ... exp
RT
a1 a2
1
2

G 0
ln P P P ...
RT

a3
3

a1
1

a2
2

a3
3

- all pressures are normalized by

the standard pressure P0

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:
0

G
K exp
RT

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):

S
U
exp
exp

R
RT

G 0
K
N N N ... exp
RT

a1
1

a2
2

a3
3

Ammonia Synthesis
N 2 3H 2 2NH 3

P P
P P
0 2

N2

NH 3
3
H2

G
exp

RT

At T = 298K and P = 1 bar, G = -32.9 kJ for

production of two moles of ammonia

32.9 103 J
G
5.9 105
K exp
exp
RT
8.3 J/K298K
Thus, the equilibrium is strongly shifted to the right, favoring the production of ammonia
from nitrogen and hydrogen.
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
7000C, 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.
Haber Process, developed into an industrial process by C. Bosch - a major chemical
breakthrough at the beginning of the 20th century (1909):
T = 5000C, 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 H0 =-46 kJ, see Pr. 5.86). To
shift the reaction to the right (higher concentration of the product), a very high
pressure is needed.

Example of Application of the Law of Mass Action

Lets look at a simple reaction

H 2 CO 2 H 2O CO

Notice that we have the same # of moles on both sides of the reaction equation. We
start with n0H2 and n0CO2 moles of the reacting gases and define as the yield y the
number of moles of H2O that the reaction will produce at equilibrium:

nH2O y

0
nCO y nH2 nH0 2 y nCO2 nCO
y
2

n n

0
nH0 2 nCO
2

equilibrium concentrations of H2 and CO2

The mass action law requires:

y2
K
0
0
nH 2 y nCO 2 y

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/dn0H2 = 0. The result:

nH0 2 n0 / 2

0
0
0
nCO

n
/
2

n
H
2
2

- 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.)

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.

G 0

K exp
RT

Lets find the partial derivative of lnK with respect to T at P=const

G 0
0
T

G
0

ln K G 1 T 2
T
T RT
R
T
G 0
For either the reactants or the products,
S
T

1 TS 0 H 0 TS 0
H 0
ln K

T
R
T2
RT 2

G 0
S 0
T

H 0 vant Hoffs
ln K 2 equation
T
RT

H 0 is the enthalpy change of the reaction. If H 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).
Tf

Tf

H 0
T d ln K T RT 2 dT
i
i

H 0 1 1
ln K T f ln K Ti

R Ti T f

Chemical Equilibrium in Dilute Solutions

Water dissociation:
GA

H2O H OH-

G 0 79 .9 kJ

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.
ideal mixing

0
H++OH-

GB

1
H2O

the shift is exaggerated:

xeq ~ 110-7

In equilibrium:

H OH H O

Assuming the solution is very dilute:

0
T , P k BT
solvent solvent

solute

N solute
0
T , P
solvent
N solvent
0 T , P k BT ln msolute

0
H0 O H0 kBT ln mH HO
kBT ln mHO

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.

0
0
0
RT ln mH mHO- N A H0 HO
- H O G
2

mH mHO-

G 0

exp
RT

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.

mH mHO- 1107

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.
Example: oxygen dissolved in water.

O 2 gas O 2 aqueous

G 0 16 .4 kJ

The Gibbs free energy change G0 for this reaction is for one mole of O2 dissolved
in 1 kG of water at P = 1bar and T = 298 K.

In equilibrium:

0
gas

2 ( gas )

T , P O ( aqueous) T , P
2

For O2 gas:

gas T , P 0 T , P 0 k BT ln

For O2 dissolved in water:

solute solute

P
0
k BT ln 0 solute
k BT ln msolute
P

G 0
msolute

exp
0
P/P
RT

P
0
P

0
T , P k BT ln msolute

P / P0
0
0
N A solute

RT ln
gas
G 0
msolute

Henrys law (the amount of dissolved gas is proportional to

the partial pressure of this gas)

G 0

16.4 103 J
exp
1.3 103
For O2 in water: exp
RT
8.3 J/K298 K
PO2 =0.2 bar, msolute = 1.310-3 x 0.2 = 2.6 10-4 equivalent of 6.6 cm3 of O2 gas at
normal conditions (1 mol at P=1 bar ~25 liters).