06 Thermochemistry
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.
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
i H T,i
i
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
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
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
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
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)
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
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
3 CALORIMETRY
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
O2 (g)
CO(g)
CO2 (g)
J/K-mol
25.67
28.74
21.64
Find and expression for r H T in the range of 298 K and 1500 K, and calculate
r H 1200
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)
= H ( T1 ) + HP = 0
= HR + H ( T2 ) = 0
3 CALORIMETRY
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)