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CHM520

PHYSICAL CHEMISTRY II
EXPERIMENT 1
CHANGES OF STANDARD GIBBS FREE ENERGY FOR THE DECOMPOSITION OF
SODIUM HYDROGEN CARBONATE
DATE PERFORMED:___/___/_____
DATE OF SUBMIT:___/___/_____

PREPARED BY,
MOHD.KHAIRUL NIZAM BIN MOH RAFIE (2015588119)
GROUP MEMBERS,
_____________________________________ (___________)
_____________________________________ (___________)
CHECKED BY,
___________________________________________________

OBJECTIVES

To determine the change of standard Gibbs free energy

( G ) for the

decomposition of sodium hydrogen carbonate (NaHCO 3) from the change of


standard enthalpy

( H ) and the change of standard entropy

( S ) .

INTRODUCTION
Gibbs free energy (G) is defined as G = H TS. H, S and T are enthalphy, entropy
and temperature respectively. By determining the quantity
according to Hesss Law and extraction of

experimentally

from standard data,

G of the

reaction can be estimated easily.


In this experiment, a double-wall vacuum stainless steel calorimeter is used to
measure the heat released or absorbed by decomposition of NaHCO 3. The thermo
chemical equation for the decomposition of NaHCO 3 (s) is
2 NaHCO3 (s)

Na2CO3 (s) + H2O (l) + CO2 (g)

However in the laboratory, the quantity

of NaHCO3 (s) cannot be determined

directly. Instead, two separate experiments is carried out to determine the

quantities

for the reactions of NaHCO3 (s) and NaHCO2 (s) respectively with

H2SO4 (aq). Hesss Law is applied in estimation of

H of NaHCO3 (s). The reaction

are as follow :
2 NaHCO3 (s) + H2SO4 (aq)
Na2CO3 (s) + H2SO4 (aq)

Na2SO4 (aq) + 2 CO2 (g) + 2 H2O (l)


Na2SO4 (aq) + H2O (l) + CO2 (g)

A simple double-wall vacuum stainless steel calorimeter is used for determining the
quantity

H . The enthalpy (H) is defined as

H = U + PV
A known amount of NaHCO3 (s) or Na2CO3 (s) is added to an excess of H2SO4 (aq)
and the change in temperature

( T )

is measured. The heat released or absorbed

by each reaction (qp) is calculated by using the formula :


qp = mCp T

The quantity Cp for the double-wall vacuum stainless steel calorimeter is small and
any heat absorb is negligible. Quantity

is negative for exothermic reaction

while positive for endothermic reaction. The objective for this experiment is to
determine the change of standard Gibbs free energy

( G ) for the decomposition

of sodium hydrogen carbonate (NaHCO3) from the change of standard enthalpy

( H ) and the change of standard entropy

( S ) .

PROCEDURE
1.

NaHCO3 was weighed exactly 4.2611g .

2. 50 ml of 1M

H 2 SO 4 was transfered from a volumetric pipette into the

double wall vacuum stainless steel calorimeter.


3. The double wall and the thermometer were replaced.
4. The temperature of
5.

H 2 SO 4

was recorded every 1 minute for 4 minute.

NaHCO3 was quickly poured into

H 2 SO 4 at the fifth minute.

6. The cover was replaced and the contents was stirred using the thermometer
in the calorimeter.
7. The temperature was recorded every 10s for the next 4 minute.
8. All the steps were repeated with 3.0 to 3.5 g of

Na 2 CO 3 .

RESULTS
Temperature of sulphuric acid (H2SO4) every 1 min for 4 min for sodium
hydrogen
carbonate (NaHCO3).

NaHCO3
Time (s)
1
2
3
4

Temperature (C)
25.5
25.0
25.0
25.0

Temperature of sodium hydrogen carbonate (NaHCO3) with sulphuric acid


(H2SO4)
NaHCO3 with H2SO4
Time (s)

T (oC)

10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240

23.0
22.0
21.5
21.0
21.0
21.0
21.0
21.0
21.0
21.0
21.0
21.0
21.0
21.0
21.0
21.0
21.0
21.0
21.0
21.0
21.0
21.0
21.0
21.0

Temperature of sulphuric acid (H2SO4) every 1 min for 4 min for sodium
carbonate
(Na2CO3).

Na2 CO 3
Time (s)
1
2
3
4

Temperature (C)
24.0
24.0
24.0
24.0

Temperature of sodium hydrogen carbonate (

Na2 CO 3 ) with sulphuric acid

(H2SO4)

Na 2 CO 3
Time (s)
10
20
30
40

with H2SO4
T (oC)
26.5
26.5
26.5
26.5

50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240

26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.0
26.0
26.0

CALCULATION
Calculation of the heat change (qP) for the reactions of:
a) NaHCO3 with H2SO4
b) Na2CO3 with H2SO4

Mass of H2SO4:
Density of H2SO4 = 1 g/ml
Mass of H2SO4= 1 g/ml x 50 ml
= 50 g
a. NaHCO3 with H2SO4
qp = mCp
qp = (4.2611 g + 50.00 g) x (4.18 Jg-1oC-1) x (21oC 23oC)
= (54.2611 g) x(4.18 Jg-1oC-1) x (-2oC)
= - 453.622796 J
b. Na2CO3 with H2SO4
qp = mCp
qp = (3.1191 g + 50.00 g) x (4.18 Jg-1oC-1) x (26oC 26.5oC)
= (53.1191 g) x(4.18 Jg-1oC-1) x (-0.5oC)
= - 111.018919 J

2 NaHCO3 (s) + H2SO4 (aq)

Na2SO4 (aq) + 2 CO2 (g) + 2 H2O (l) =


453.622796 J

Na 2CO3 (s) + H2SO4 (aq)

Na2SO4 (aq) + H2O (l) + CO2 (g) =

111.018919 J

Uses of Hesss Law to calculate the enthalpy for the decomposition of


NaHCO3 (s):
2 NaHCO3 (s) + Na2CO3 (s)

CO2 (g) + H2O (l)

H 1 = - 453.622796 J 1 kJ /1000 J
= - 0.45362 kJ / 0.05073 mol
= -8.94185 kJ/mol

H 2 = - 111.018919 J 1 kJ /1000 J
= - 0.11102 kJ / 0.02943 mol
= -3.77230 kJ/mol
2 NaHCO3 (s) + H2SO4 (aq)

Na2SO4 (aq) + 2 CO2 (g) + 2H2O (l)

H 1=8.9467 kJmol-1
Na2SO4 (aq) + CO2 (g) + H2O (l)

11

19.5707

2 NaHCO3 (s)

Na2CO3 (s) + H2SO4 (aq)

kJmol-1

Na2CO3 (s) + CO2 (g) + H2O (l)

8.94185 kJ /mol+ (3.77230 kJ /mol )


=

12.71415 kJ /mol

Table of standard thermodynamic data at 298K

Compound
H f (kJ mol-1)
S (J mol-1K-1)
NaHCO3

948 .0

102 .0

Na2CO3

1130.9

136 .0

(kJ mol-1)

852.0
1048 .0

CO2

393.5

213.6

394 .0

H 2O

285.8

69.9

237.2

Na2CO3 (s) + CO2 (g) + H2O (l)

2 NaHCO3 (s)

H reaction = H products H reactants


H reaction=

( 1130.9285.8393.5 (2948.0)
=

1810.2+1896

85.8 kJ mol-1

For 1 mole = 85.8 kJ mol-1


= 42.9 kJ mol

Calculation of

-1

for the decomposition of NaHCO3 (s) from standard

data:

Sreaction = S products Sreactants


Sreaction=( 136+ 69.9+ 213.6 )(2 102)
=
=

215.5
=

Calculation of

419.5204
J
1 kJ

mol K 1000 J
0.2155

kJ/mol K

G for the decomposition of NaHCO3 (s):

theory

= G products Greactants

Gtheory = (1048394237.2 )(2 852)


=

1679.2(1704 )

1679.2+1704

24.8

kJ/mol

Gexp= H T S
Gexp=12.71415 kJ /mol298 K( 0.2155

kJ/molK)

12.71415 kJ /mol64.219 (kJ /mol)

76.93315 kJ/mol

ANSWERS OF QUESTIONS
Answers of question number 2
NaOH (aq) + HCl (aq)
(75 mL)

NaCl + H2O

(50 mL)

density : 1.04 g mL-1


T1 : 22.6 oC
Tmax: 26.3 oC
Cp : 4.18 J g-1 oC-1

density=

mass
mass
density=
volume
volume
1

1.04 g mL =

mass
mass
1
1.04 g mL =
50 mL
75 mL

mass=1.04 g 50 mass=1.04 g 75
=

52 g ( mass of HCl )=78 g( mass of NaOH )

qp= mCp T
= (78g + 52g) (4.18 J g -1oC-1) (26.3 oC

22.6 oC)

= 130 g (4.18 J g-1oC-1) (3.7 oC)


= 2010.58 J

The reaction is endothermic because heat is absorbed by the reaction process


of hydrochloric acid and
sodium hydroxide. So, q is positive.
Answers for question number 2.
H2 (g) +

1
2

H2O (l)

O2 (g)

Mg (s) + 2 HCl (aq)

Mg (s) + 2 HCl (aq) +

MgCl2 (aq) + H2O (l)

Mg (s) +

1
2

O2 (g)

(b)

MgCl2 (aq) + H2 (g)

1
2

O2 (g)

(c)

MgCl2 (aq) + H2O (l)

MgO (s) + 2 HCl (aq)


MgO (s)

(d)

(a)

DISCUSSION
In this experiment, we are going to determine the change of standard Gibbs
free energy ( G

) for the decomposition of sodium hydrogen carbonate (NaHCO 3)

from the change of standard enthalpy ( H

( S

) and the change of standard entropy

). Firstly , 4.2611 g of NaHCO 3 was weighed. Then, 50 mL of H 2SO4 from a

volumetric pipette was transferred into the double-wall vacuum stainless steel
calorimeter. The temperature of H2SO4 was recorded every 1 min for 4 min. The
temperature obtained was 25oC for every 1 min. At the 5th minutes, the NaHCO 3
was poured quickly into the H 2SO4. The contents in the calorimeter was stirred by
using the thermometer. The temperature for every 10 s for the next 4 minute then
was recorded. For 20 s, the temperature obtained was 22 oC. The temperature was
decreased to 21oC at 40 s to 240 s. Secondly , 3.1191 g of Na 2CO3 was weighed.

Then, the steps of experiment in the first part were repeated. The temperature of
H2SO4 was also recorded for every 1 minute for 4 minutes. The temperature
obtained was 24oC at 1 minute. At the 5th minute, the Na 2CO3 was poured quickly
into the H2SO4 and the contents was stirred by using the thermometer. The
temperature for every 10 s for the next 4 minutes was recorded. The temperature
obtained at the time of 10 s to 210 s was 26.5 oC. Then, the temperature decreased
to 26oC at 220 s to 240 s. It showed that the endothermic reaction occurred as the
temperature decreased during the experiment.
The standard free energy change ( G ) was calculated to compare the free
energy

changes

G = H T S

of

different

reactions.

The

Gibbs

equation

is

was used to calculate the experimental value of ( G ). It

shows was a spontaneous process since the value of

76.93315 kJ/mol. The theoretical value of the


Go = Go products Goreactants

formula

which

G < 0 which is

was calculated using the

. We can take the value from the Table of

standard thermodynamic data at 298K. The value obtained was 24.8 kJ/mol. Since
the value of

G > 0 , so it was nonspontaneous process and endothermic

reactions. From our observations, the decomposition of NaHCO 3 (s) at standard


conditions is a spontaneous process since the value H < 0 that is -28.5174 kJ
mol-1,

S > 0 that is 0.2155 kJ mol -1 K-1. Both contributions favour the

spontaneity of the reaction.


is negative, thus the value of

is

H is negative and
G

is positive, so

T S

is always negative.The value that we got for

76.93315 kJ/mol.

Besides, some errors maybe has occurred. The major sources of errors in
this experiment are when the heat lost during the addition of the sodium hydrogen
carbonate into the sulphuric acid in the double-wall vacuum stainless steel
calorimeter and maybe it also occurred when we were struggled to stir the contents
in the calorimeter.
CONCLUSION
The objective of the experiment was achived.The change of standard Gibbs free
energy ( G

)for the decomposition of sodium hydrogen carbonate from the

change of standard enthalpy and the change of standard entropy has been

determined. The theoretical value for


experimental value for

Gexp

is

t h eory

is 24.8 kJ mol-1 while the

76.93315 kJ/mol.

REFERENCES
1. Laboratory Manual Physical Chemistry ll.
2. Reiss, Howard (1965). Methods of thermodynamics. Dover publications. ISBN
0-486-69445-3
3. Peter Atkins;loretta jones (1 August 2007). Chemical Principles : The Quest
for Insight. W. H. Freeman