Lecture 10

Standard Thermodynamic
Functions of Reaction
Dr. A.K.M. Shafiqul Islam
Dept. of Chemical Engineering Technology
Industrial Biotechnology
27/03/2015

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 Calorimetry
The most common type of reaction studied
calorimetrically is combustion
 Heat capacities also determined in a
calorimeter
 Reaction where some of the species are gases
(combustion reaction)are studied in constant-
volume calorimeter
 Reaction not involving gases are studied in a
constant-pressure calorimeter.
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The standard enthalpy of combustion
of a substance is for the reaction in which
1 mole of the substance is burned in 02 .

Some values are plotted in Figure 2

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 Figure 2:Standard enthalpies of combustion at 25°C. The products are CO2(g) and
H20(l)

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 Adiabatic change
• Relation between ∆H° and ∆U°
• A decrease in temperature will change in
internal energy. The volume will change
HU+PV
At constant Pressure
H= U+PV
since the standard Pressure is P0
H  U  P V
o 0 0 0

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 Products minus
reactants

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• The molar volumes of gases at 1 bar are much
greater than those of liquids or solids, so it is an
excellent approximation to consider only the gaseous
reactants and products.
• For example, consider the reaction

• Neglecting the volumes of the solid and liquid

substances A and E, we have

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• The standard state of a gas is an ideal gas
Vm0  RT / P0
• Hence,
Vm0  c  d - b RT / P 0
• Where (c+d-b) is total number of moles of product
gas minus the total number of moles of reactant
gases.
c  d - b  n g / mole

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• Thus we can write,
V0  c  d - bRT / P0

H  U  ng RT / mol
0
T
0
T

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 Example:
• For CO(NH2)2 (s), = -333.51 kJ/mol .
Find of CO(NH2)2 (s).

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 Solution:
• The formation reaction is:
C (graphite) + ½ O2 (g) + N2 (g) +2H2(g) = CO(NH2)2

= 0-2-1-1/2 = -7/2

= -333.51 kJ/mol – (-7/2) (8.314 X 10-3

kJ/molK)(298.15K)
= -324.83 kJ/mol

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• An adiabatic bomb calorimeter is used to
measure heats of combustion.
This system is thermally insulated, and
does no work on its surrounding
∆U =0
R+K at 25°C P+K at 25°C + ∆T
(a)

(c) (b)
Uel
∆rU298 Ub=Uel=Vlt
∆rU298 = - Uel R+K at 25°C

q=0, w=0, ∆U=0 R= Mixtures of reactants

P= Product mixture
K= bomb wall+surrounding waterbath
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• Alternative procedure:
Imagine carrying out step (b) by supplying heat qb to the system
K+P (instead of using electrical energy),then we would have

Heat capacity of the system K+P over

Thus, temperature range

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 Example:
• Combustion of 2.016g of solid glucose at 25°C
in an adiabatic bomb calorimeter with heat
capacity 9550 J/K gives a temperature rise of
3.282°C. Find of solid glucose.

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 Solution:

• ∆U= -(9550J/K)(3.282K)
= - 31.34kJ for combustion of 2.016g of glucose
The experimenter burned (2.016g)/(180.16g/mol)
=0.001119 mol
Hence ∆U per mole of glucose burned is:
(-31.34kJ)(0.001119mol)= -2801 kJ/mol

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 Hess’s Law
• The standard enthalpy of an overall reaction is
the sum of the standard enthalpies of the
individual reactions into which a reaction may
be divided.

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 Hess’s Law
• Suppose we want the standard enthalpy of
formation H0f,298 of ethane gas at 25°C, This is
H0298 for 2C(graphite) + 3H2(g)  C2H6(g).
• Unfortunately, we cannot react graphite with
hydrogen and expect to get ethane, so the heat
of formation of ethane cannot be measured
directly. This is true for most compounds. Instead,
we determine the heats of combustion of ethane,
hydrogen, and graphite, these heats being readily
measured.

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 The following values are found at 25°C:

Multiplying reaction (1), (2), and (3) by -1, 2 and 3 respectivewly

Addition of this equation gives

= Enthalpy of formation for C2H6

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Example

• The standard enthalpy of combustion CH0298

of C2H6(g) to CO2(g) and H20(l) is — 1559.8
kj/mol. Use this CH0298 and Appendix data on
CO2(g) and H20(l) to find fH0298 and fU0298 Of
C2H6(g).

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• Combustion means burning in oxygen. The
combustion reaction for one mole of ethane is

• The H0C value gives for this reaction

• Substitution of the values of H0f of CO2(g) and H20(l)

and H0C gives at 298 K
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• To find from we must write the formation
reaction for C2H6 which is:
• 2(C) (graphite) +3H2 C2H6
• This reaction has = 1-3 =-2
HT0  UT0  ng RT / mol
• = - 84.7 kj/mol – (-2)90.008314 kj/molK)(298.1K)
• = -79.7 kj/mol

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 The temperature-dependence of
reaction enthalpies
• When a substance is heated from T1 to T2 its enthalpy changes
from H( T1)) to H( T2))

• Equation is known as Kirchhoff's law.

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 Assignment

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 Assignment

3/24/2015