MSE 231 Thermodynamics of Materials

06 Thermochemistry

Dr. Gil C. Claudio

First Semester 2015-2016
Table of Contents

Contents
1 Thermochemistry

2 Enthalpy of Formation

3 Calorimetry

References
References of these notes
Robert J. Silbey, Robert A. Alberty, and Mongi G. Bawendi, Physical
Chemistry, 4th ed.
Ira N. Levine, Physical Chemistry, 6th ed.
Bimalendu N. Roy,
Thermodynamics.

Fundamentals of Classical and Statistical

1 Thermochemistry
Standard States
Definition of standard states used in chemical thermodynamics
1. The standard state of a pure gas at a given temperature is the
(hypothetical) ideal gas at P = 1 bar.
2. The standard state of a pure liquid substance at a given temperature is
the pure liquid at P = 1 bar.
3. The standard state of a pure crystalline substance at a given temperature
is the pure crystalline substance at P = 1 bar.
4. The standard state of a substance in solution is the hypothetical ideal
solution of standard state molality (1 mol/kg) at P = 1 bar at each
temperature.
for electrolytes, the symbols used are: ai for completely dissociated
electrolytes in water, ao for undissociated molecules in water, and ao
ions in water where no further ionization occurs.

2 ENTHALPY OF FORMATION

Standard Enthalpy of Reaction

The standard enthalpy (change) of a reaction (or heat of reaction) HT
is the enthalpy change of a process of transforming stoichiometric number of
moles of the pure, separated reactants, each in its standard state at temperature
T, to stoichiometric numbers of moles of the pure, separated products, each in
its standard state at the same temperature T. For a reaction
aA+bBcC+dD
the standard enthalpy change HT is

HT cr H T (C) + dH T (D) aH T (A) bH T (B)

where H T (C) is the molar enthalpy of substance C in its standard

temperature T. This can be written as
r HT

i H T,i
i

Reaction Enthalpy of Graphite

For graphite at 25 C
C(graphite) + O2 (g)
CO2 (g)
C(graphite) + 12 O2 (g)

CO2 (g)
CO(g) +
CO(g)

1
2

O2 (g)

r H
-393.509 kJ/mol
282.984 kJ/mol
-110.525 kJ/mol

2 Enthalpy of Formation
Standard Enthalpy of Formation f HT
The standard enthalpy of formation (or standard heat of formation) f HT
of a pure substance in its standard state at T is formed from the corresponding
separated elements at T, each element being its reference form.
The reference form (or reference phase) of an element at temperature T
is usually taken as the form of the element that is most stable at T and
1-bar pressure.
f HT of Elements
The enthalpy of formation of an element in its standard state (reference
form) f HT is zero at every temperature.
of graphite is zero.
Example f H307

C(graphite, 307 K, P ) C(graphite, 307 K, P )

= 1.97 kJ/mol.
However, for diamond, f H307

C(graphite, 307 K, P ) C(diamond, 307 K, P )

r HT of Reactions
The standard enthalpy change r HT for a chemical reaction is given by
r HT =

i f HT,i
i

where
i is the stoichiometric number of substance i in the reaction,
is the standard enthalpy of formation of a substance i at T. No
f HT,i
overbar because the subscript f, for formation, indicates that the mol1
unit is involved.

2 ENTHALPY OF FORMATION

f HT from the Reaction of Graphite

From reactions given previously we can see how the following enthalpies
of formation at 25 C are obtained

CO2 (g)
CO(g)
C(g)
O(g)

f HT
kJ/mol
-393.509
-110.525
716.682
249.170

Experimental Determination of f HT
The values of enthalpies of formation given in tables come from
1. calorimetrically measured enthalpies of reaction, fusion, vaporization,
sublimation, transition, solution, and dilution;
2. temperature variation of equilibrium constants;
3. spectroscopically determined dissociation energies;
4. calculation from Gibbs energies and entropies
Calculation of H from f HT Data
INL 6e, Example 5.1, p 144
for the combustion of one mole of the simplest amino acid,
Find H298
glycine, NH2 CH2 COOH, according to
NH2 CH2 COOH (s) +

9
4

O2 (g) 2 CO2 (g) +

5
2

H2 O (l) +

1
2

N2 (g)

values
From a table of f H298


1
5
9
(0) + (285.830) (528.10) (0) kJ/mol = 973.49 kJ/mol
2
2
4

Hesss Law
Hesss Law states that if a reaction takes place in several steps then,
its standard reaction enthalpy is the sum of the standard enthalpies of the
intermediate reactions into which the overall reaction may be divided at the
same temperature.
r H (n rxn) = nr H (rxn)
r H (reverse) = r H (forward)
Formation of Ethane Gas C2 H6
for the reaction
To calculate f H298
2 C(graphite) + 3 H2 C2 H6 (g)
we can use the following values found in tables
7
2

C2 H6 (g) + O2 (g)
C(graphite) + O2 (g)
H2 (g) + 12 O2 (g)
= -85 kJ/mol.
We get f H298

2 CO2 (g) + 3 H2 O(l)

CO2 (g)
H2 O(l)

kJ/mol
r H298
-1560
-393.5
-286

2 ENTHALPY OF FORMATION

Formation of PCl5
To calculate the r H for the reaction
PCl3 (l) + Cl2 (g) PCl5 (s)
we can use the following values found in tables
2 P(s) + 3 Cl2 (g)
2 P(s) + 5 Cl2 (g)

kJ/mol
r H298
-640
-887

2 PCl3 (l)
2 PCl5 (s)

Temperature Dependence of Reaction Heats

After determining H at T1 , we can solve H at T2 by differentiating
H with respect to T gives the standard heat-capacity change, CP .
dH
=
dT

CP
i CP,m,i
i

Another derivation is
dH
dT

d(Hprod
Hreact
)

dT

= CP,prod
CP,react

dHprod

dT

H
T

since

= CP

dHreact
dT

= CP

Kirchoffs Law
Integration of the previous equation gives

H T2 H T1 =

Z T2
T1

C P dT

This is called Kirchoffs law.

standard-state reactants at T2 a standard-state products at T2 b

d standard-state reactants at T1 c standard-state products at T1

Calculating the r H at Constant T

SAB 4e, Example 2.8, p 61
What are the standard enthalpy changes at 298.15 K and 2000 K for the
following reaction?
CO2 (g) + C(graphite) 2 CO(g)
Use the following data

CO(g)
CO2 (g)
C(graphite)

f H
kJ/mol
298 K
-110.572
-393.522
0.000

Cp
J/mol-K
298 K
29.142
37.129
8.571

f H
kJ/mol
2000 K
-118.896
-396.784
0.000

Cp
J/mol-K
2000 K
36.250
60.350
24.094

ANSWER: 172.468 kJ/mol at 298.15 K and 158.992 kJ/mol at 2000 K.

3 CALORIMETRY

Change in H with Temperature

INL 6e, Example 5.5, p 152
Use the data below and the approximation that CP is independent of T to

estimate H1200
for the reaction
2 CO (g) + O2 (g) 2 CO2 (g)
kJ/mol
f H298

O2 (g)
CO(g)
CO2 (g)

-110.525
-393.509

CP,298
J/mol-K
29.355
29.116
37.11

ANSWER: H1200
= 578.03 kJ/mol

Change in H with Temperature

INL 6e, Example 5.6, pp 152-153
For the reaction
2 CO(g) + O2 (g) 2 CO2 (g)
C P coefficients in the range of 298 to 1500 K are

O2 (g)
CO(g)
CO2 (g)

J/K-mol
25.67
28.74
21.64

102 J/K2 -mol

1.330
-0.179
6.358

105 J/K3 -mol

-0.3764
1.046
-4.057

109 J/K4 -mol

-0.0731
-4.288
9.700

Find and expression for r H T in the range of 298 K and 1500 K, and calculate

r H 1200

ANSWER: r H 1200 = -563.85 kJ/mol.

3 Calorimetry
Calorimeters
Heats of reaction are determined using adiabatic calorimeters
the reaction or solution process occurs in a container
the calorimeter includes a a weighed quantity of water and is surrounded
by insulation or an adiabatic shield that is kept at the same temperature
as the calorimeter so that no heat is gained or lost.
At constant pressure, then HA = 0
Calorimetric Measurements (1)
For reactants (R) to products (P) in a calorimeter (C)

H(T2)

P(T2) + Cal(T2)

HR

R(T2) + Cal(T2)

R(T1) + Cal(T1)

H(T1)

HP
P(T1) + Cal(T1)

The enthalpy for the process can be written in two ways

HA
HA

= H ( T1 ) + HP = 0
= HR + H ( T2 ) = 0

3 CALORIMETRY

Calorimetric Measurements (2)

Assuming a constant CP , then
H ( T1 )
H ( T2 )

= HP = [CP (P) + CP (Cal)] ( T2 T1 )

= HR = [CP (R) + CP (Cal)] ( T2 T1 )

The results of the calorimetric experiments can be interpreted to obtain H for

the conversion of a certain amount of R to P either at T1 or T2 .
Also, r HT r H T
Bomb Calorimetry
In a bomb calorimeter at constant V, then w PV = 0 and U = qV .
At constant pressure, H = q P .
To relate U to H when using a bomb calorimeter,
r H = r U + RT g
where g is the sum of the stoichiometric numbers of gaseous products
minus gaseous reactants.
Heat of Combustion
SAB 4e, Example 2.10, p 65
The combustion of ethanol in a constant-volume calorimeter produces
1364.34 kJ/mol at 25 C. What is the r H value of for the following
combustion reaction
C2 H5 OH(l) + 3 O2 (g) 2 CO2 (g) + 3 H2 O(l)
ANSWER: -1366.82 kJ/mol
Heat of Solution
When a solute is dissolved in a solvent, heat may be absorbed or evolved; in
general, the heat of solution depends on the concentration of the final solution.
The integral heat of solution is the enthalpy change for the solution of 1
mol of solute of n mol of solvent.
Some examples
HCl(g) + 5 H2 O HCl5H2 O
CH3 COOH(l) CH3 COOH(ao)

sol H (298 K) = -63.467 kJ/mol

sol H (298 K) = -1.3 kJ/mol

Neutralization Reactions
For dilute solutions, the heat of reaction of strong bases with strong acids is
independent on the nature of acid or base. The only chemical reaction is
OH (aq) + H+ (aq) H2 O(l)

r H (298 K) = -55.835 kJ/mol