Department of Chemical Engineering
University of San Carlos-Technological Center
Nasipit, Talamban, Cebu, City
CHE 323L
Physical Chemistry Laboratory 1
Determining Enthalpies of Formation Using the Bomb Calorimeter
Date Performed: February 3 and 5, 2015
Date Submitted: February 11, 2015
Submitted by:
Flores, Dynzl Dean B.
Laguna, Anna Lei M.
Navalta, Carl John Louie G.
A laboratory report submitted to
Engr. May V. Tampus
Instructor
Results
Table 1. System Temperature Before Ignition
T (0C) , Benzoic acid
t (min)
T (0C) , Naphthalene
Trial 1
Trial 2
Trial 1
Trial 2
24.7
24.8
27.8
27.8
24.7
24.9
27.8
27.8
24.7
25.0
27.8
27.8
24.7
25.0
27.8
28.0
24.7
25.0
27.8
28.0
24.7
25.0
27.8
28.0
Table 2. Purging and Charging Pressure (Benzoic Acid)
Purging 1 (atm)
Purging 2 (atm)
Purging 3 (atm)
Pressure Supplied (atm)
Trial 1
24
24
24
24
Trial 2
24.2
24
24.5
24.5
Table 3. Purging and Charging Pressure (Naphthalene)
Purging 1 (atm)
Purging 2 (atm)
Purging 3 (atm)
Pressure Supplied (atm)
Trial 1
24
25
25
25
Trial 2
24
24
24
24
Table 4. System Temperature After Ignition
T (0C) Benzoic acid
T (0C) Benzoic acid
T (0C) Naphthalene
T (0C) Naphthalene
Trial 1
Trial 2
Trial 1
Trial 2
24.7
25.0
27.8
28.0
0.5
25.9
26.0
28.5
28.4
1.0
26.5
26.7
29.8
29.7
1.5
26.8
27.0
30.4
30.3
2.0
27.0
27.1
30.6
30.5
2.5
27.0
27.2
30.8
30.7
t (min)
3.0
27.1
27.2
30.8
30.7
3.5
27.1
27.2
30.9
30.8
4.0
27.1
27.3
30.9
30.8
4.5
27.1
27.3
30.9
30.8
5.0
27.1
27.3
30.9
30.8
5.5
27.1
27.3
30.9
30.8
6.0
27.1
27.3
30.9
30.8
7.0
27.2
27.3
30.9
30.8
8.0
27.2
27.3
30.9
30.8
9.0
27.2
27.3
30.9
30.8
10.0
27.2
27.3
30.9
30.8
11.0
27.2
Benzoic Acid Thermogram
28.0
27.0
26.0
Temperature, 0C
Trial 1
Trial 2
25.0
24.0
23.0
0
10
Time, min
12
14
16
18
Figure 1. Temperature of water as a function of time for benzoic acid
Naphthalene Thermogram
32.0
31.0
30.0
Temperature, 0C
Trial 1
29.0
Trial 2
28.0
27.0
26.0
0
10
Time, min
12
14
16
18
Figure 2. Temperature of water as a function of time for naphthalene
Calculations
A. Calculating the Heat Capacity, C, of the Bomb Calorimeter
Trial 1
m = 0.9727 g Benzoic acid
J
Qm = 26 434
g
Lo = 10 cm
L = 3.5 cm
C1 =
Qtot
T
T1 = 24.7 oC = 297.85 K
T2 = 27.2 oC = 300.35 K
J
J
26 434 )( 0.9727 g )+(9.6
)(10 cm3.5 cm)
(
Q m+ q
g
cm
=
=
m
T 2T 1
300.35 K 297.85 K
C1 = 10 309.90
J
K
Trial 2
m = 0.9310 g Benzoic acid
J
Qm = 26 434
g
Lo = 10 cm
L = 3.5 cm
C2 =
Qtot Qm m+ q2
=
=
T
T 2T 1
T1 = 25.0 oC = 298.15 K
T2 = 27.3 oC = 300.45 K
(26 434 Jg )( 0.9310 g) +(9.6 cmJ )(10 cm3.5 cm)
300.45 K 298.15 K
J
K
C2 = 10 727.15
Average C
C 1 +C2
C=
2
10 309.90
C=
J
J
+10 727.15
K
K
2
C=10
518.53
K
B. Calculating for the Heat of Formation
Temperature (298.15 K)
H of
Trial 1
m
= 0.9857 g of Naphthalene
MW
= 128.19
T1
T2
g
mol
= 27.8 oC = 300.95 K
= 30.9 oC = 304.05 K
of Naphthalene at Standard
C10 H 8
)
H 300.95 =C T
J
H 300.95 =10518.53 ( 304.05 K300.95 K )
K
H 300.95 = 32 607.44 J
Per mole of C10 H 8 ,
H 300.95 =
32 607.44 J
1 mol C 10 H 8
0.9857 g C 10 H 8 (
)
128.19 g C 10 H 8
H 300.95 =4 240.59
Solving for
H 298.15 :
kJ
mol
T2
H 298.15 = H 300.95 C p dT
T1
where:
Cp, C
10
H8
=150.5+0.6 T
in
H 298.15 =4 240.59
J
mol K
)|
J
0.6 T 2 304.05
150.5+
mol
2
300.95
H 298.15 =5 238.18
C10H8 + 12O2 10CO2 + 4H2O
From the equation:
H f , C
10
H8
=10 [ H f , C O ] +4 [ H f , H
2
kJ
mol
] H
298.15
where:
H f , H O=285.83
2
kJ
mol
H f , CO =393.509
2
kJ
mol
therefore,
H f , C
10
H8
=10 393.509
kJ
kJ
kJ
+ 4 285.83
5 238.18
mol
mol
mol
) (
)(
H f , C
10
Trial 2
H8
=159.77
kJ
mol
= 0.9810 g of Naphthalene
MW
= 128.19
g
mol
o
= 27.8 C = 300.95 K
= 30.8 oC = 303.95 K
T1
T2
C10 H 8
)
H 300.95 =C T
J
H 300.95 =10518.53 ( 303.95 K300.95 K )
K
H 300.95 = 31 555.59 J
H 300.95 =
Per mole of C10 H 8 ,
31555.59 J
1 mol C10 H 8
0.9810 g C 10 H 8 (
)
128.19 g C 10 H 8
H 300.95 =4 123.46
Solving for
kJ
mol
H 298.15 :
T2
H 298.15 = H 300.95 C p dT
T1
where:
Cp, C
10
H8
=150.5+0.6 T
in
H 298.15 =4 123.46
J
mol K
J
0.6 T
150.5+
mol
2
H 298.15 =5119.37
From the equation:
H f , C
10
H8
=10 [ H f , C O ] +4 [ H f , H
2
303.95
)|300.95
kJ
mol
C10H8 + 12O2 10CO2 + 4H2O
] H
298.15
where:
H f , H O=285.83
2
kJ
mol
kJ
mol
H f , CO =393.509
2
therefore,
H f , C
10
H8
=10 393.509
kJ
kJ
kJ
+ 4 285.83
5 119.37
mol
mol
mol
) (
)(
H f , C
10
Average
H f , C
10
H8
=40.96
kJ
mol
H8
H f , C
159.77
10
H8
H f , C
10
H8
kJ
kJ
+ 40.96
mol
mol
2
=100.37
kJ
mol
Percent error:
theoretical value of
H f , C
10
H8
= 78.0+1.5 kJ/mol
error =
Actual valueTheoretical Value
x 100
Theoretical value
error =
100.3778.0
x 100
78.0
error =28.68
Discussion
The standard enthalpy of formation of a compound is defined as the change
of enthalpy from the formation of 1 mole of the compound from its constituent elements, with all
substances in their standard states at a given temperature and constant pressure.
The standard enthalpy of combustion for a substance is defined as the enthalpy change,
H , which accompanies a process wherein in the substance will undergo a reaction with
oxygen to form specified combustion products such as CO 2(g), H2O(l), SO2(g), and N2(g) with all the
reactants and products being in their respective standard states at a given temperature. Thus, the
standard enthalpy of combustion of benzoic acid at a temperature of 298.15K is H 298.15 for
the process
o
T
C6H5COOH(s) +
15
O2
2
7CO2(g) + 3H2O(l)
with all the reactants and products in their standard states for this specific temperature.
The enthalpy of combustion can be calculated from the temperature rise due to the
combustion reaction that occurs under adiabatic conditions in the bomb calorimeter. It is essential
that the reaction in the calorimeter will take place rapidly and completely, and the material must
be burned in a steel bomb with oxygen under a pressure of about 25 atm.
For an adiabatic-jacket bomb calorimeter, the bomb is immersed in a can of water that is
also fitted with a precise thermometer. This assembly is then placed within an outer water-filled
jacket. Before and after the combustion occurs, the temperature of the jacket is maintained at the
same value as that of the water in the can, and if the temperatures are matched with the sufficient
accuracy, it means that the can and its contents do not gain or lose any energy by radiation or
conduction or that all the heat liberated during the reaction remains in the calorimeter, therefore
we can say that the process is adiabatic.
In an actual calorimeter process, the initial and the final temperatures are not equal and
the reactants and products are also not in their standard states. The figure below shows the
relationship of the calorimeter process to the isothermal standard-state process.
Products at pressure P3
temperature T3
Uc
T2
CdT
T1
Reactants at pressure P1
temperature T1
UT
Products at pressure P2
temperature T1
The initial temperature is given by the symbol T1 and the final temperature in the
calorimeter Reactants
is given inbystandard
the symbol T2. The U c isProducts
the energy
change for the actual
in standard
states at temperature T1
states at temperature T1
o
UT
calorimeter process and the U T is the energy change for the imagined process in which the
final state is at T1 rather than at T2. The heat capacity given by the symbol C is for the can and its
contents under the conditions of the experiment. The expansion work of water in the can is
entirely negligible.
1
From the first law of thermodynamics,
U =qw
where U is the internal change for the system, q is the energy transfer into the system by
heat flow and w is for the work done by the system, and this can be applied to the actual
calorimeter process, which is assumed to be adiabatic. In the experiment the w, which consists
mainly of the work due to stirring, can be neglected so the equation becomes
U c =0
Since the change in energy is independent of the path, the equation becomes
T2
U c = U T + CdT
1
T1
Since the change in temperature is small, the C can be considered constant, and the
integral becomes equal to C(T2-T1) . The equation becomes U T =C(T 2T 1) .
1
The temperature rise corresponds to a negative
energy for the imagined isothermal process. Then the
UT
o
T1
because of the decrease in
can then be calculated from
U T . The Washburn correction, which is the correction for standard states, may be applied
1
to obtain a work of high accuracy. The principal Washburn correction allow for the changes in U
that is associated with changes in pressure, mixing of reactant gases and separating product gases,
and dissolving reactant gases in and extracting product gases from the water in the bomb.
The standard enthalpy change
H oT may then be calculated and the equation for this
1
is
o
H T = U T + ( PV ) . Since the standard enthalpy and energy for a real gas are the same,
1
as the enthalpy and energy of the gas in the zero-pressure limit, the ideal-gas equation can be used
to evaluate the gases contributions to
that will result to an equation
(PV )
( PV )=(n2n 1) RT , where the n1 is the number of moles of the gaseous reactants and the
n2 is the gaseous moles of the gaseous products. The contribution to ( PV ) from the net
change in PV of the solids and liquids going from reactants to products is generally negligible.
Reference:
Daniels, F., Williams, J.W., Bender, P., Alberty, R. A., Cornwell, C. D., (1962).
Experimental Physical Chemistry (6th ed.). New York:McGraw-Hill, pp. 15-21.
J. Phys. Chem. Ref. Data, Vol. 37, No. 4, 2008