Experiment 1: Change of Standard Gibbs Free Energy for the Decomposition of

Sodium Hydrogen Carbonate.

ABSTRACT

This experiment is used to determine the change of standard Gibbs free energy (∆G ᶱ)
for the decomposition of sodium hydrogen carbonate (NaHCO 3) from the change of
standard enthalphy (∆Hᶱ) and the change of standard entrophy (∆Sᶱ). ∆Gtheory (1161.37
kJ/mol) presented a positive value while the ∆Gexp(-99357.43 kJ/mol) gives out a
negative value. In our experiment, the ∆H is less than 0 which is -34.03 kJ/mol while ∆S
which is 0.3333 kJ/mol K is greater than 0. Under these conditions, both the ∆H and
T∆S terms will be negative. So, ∆G will be negative regardless of the temperature. An
exothermic reaction whose entrophy increases will be spontaneous at all temperatures.

INTRODUCTION
Gibbs free energy is the energy associated with a chemical reaction that can be used to
do work. The free energy of a system is the sum of its enthalpy (H) plus the product of
the temperature (Kelvin) and the entropy (S) of the system [1].

Gibbs free energy combines enthalpy and entropy into a single value called free energy
[2]. In honour of its inventor, it is usually symbolized as G. The definition of free energy is

G = H – TS
free energy enthalpy (temperature) entropy

Where T is the temperature in Kelvin; entropies must be multiplied by temperature to

get units of energy.

The change of free energy is equal to the sum of its enthalpy plus the product of the
temperature and entropy of the system. ∆G can also predict the direction of the
chemical reaction. If ∆G is positive then the reaction is non-spontaneous. If it is
negative, then it is spontaneous [1].
Changes in the Gibbs free energy (∆G) correspond to changes in free energy for
processes at constant temperature and pressure. The change in Gibbs free energy
change is the maximum non-expansion work obtainable under these conditions. ΔG is
negative for spontaneous processes, positive for non-spontaneous processes and zero
for processes at equilibrium [3].

∆G = ∆H – T∆S
change in free energy change in enthalpy (temperature) change in
entropy

 If ∆H° < 0 and ∆S° > 0 then the reaction will be SPONTANEOUS (∆G° < 0) at
any temperature.
 If ∆H° > 0 and entropy ∆S° < 0 then the reaction will be NON SPONTANEOUS
(∆G° > 0) at any temperature [1].

Standard-state free energy of reaction (∆G°)

 The free energy of reaction at standard state conditions:
∆G° = ∆H° - T∆S°
By determining the quantity of ∆H° experimentally according to Hess’s Law and
extraction of ∆S° from the standard data, ∆G° of the reaction can be estimated easily.

In our experiment, a double vacuum stainless steel calorimeter is used to measure the
heat released or absorbed by decomposition of NaHCO3. The thermo chemical
equation for the decomposition of NaHCO3 (s) is
2NaHCO3 (s) Na2CO3 (s) + H2O (l) + CO2 (g)

However in the laboratory, the quantity of ∆H° of NaHCO3 (s) cannot be determined
directly. Instead, two separate experiments in determining the quantities for ∆H° for the
reaction of NaHCO3 (s) and Na2CO3 (s), respectively with H2SO4 (aq) are carried out [1].

Hess’s law is applied in estimation of ∆H° of NaHCO3 (s).

The reactions are as follow:
2NaHCO3 (s) + H2SO4 (aq) Na2CO4 (aq) + 2CO2 (g) + 2H2O (l) ∆H : y kJ mol-1
Na2CO3 (s) + H2SO4 (aq) Na2CO4 (aq) + CO2 (g) + H2O (l) ∆H : z kJ mol-1

A simple double-wall vacuum steel calorimeter is used for determining the quantity of
∆H°. It may serve as the constant-pressure calorimeter (at atmosphere pressure under
the experimental conditions). The enthalpy (H) is defined as
H = U + ρV

The amount of heat exothermic or endothermic is represented by the letter q. The

amount of heat ( qp) lost or gained depends on the formula:
qp = mC ∆T

PROCEDURE

1. 4.0 to 4.5 g of NaHCO3 was measured exactly.

2. 50 ml of 1 M H₂SO4 was transferred into the double-wall vacuum stainless steel
calorimeter using a volumetric pipette. The cover of the double wall and the
thermometer were replaced.
3. The temperature of H₂SO4 was recorded for every one minute for 4 minutes. At
the 5th, the NaHCO3 was quickly transferred into the H₂SO4.
4. The cover was replaced and the content in the calorimeter was being stirred
carefully using thermometer.
5. The temperature was recorded for the next 4 minutes every 10 seconds.
6. Step 1 to 5 was repeated with 3.0 to 3.5 g of Na₂CO3.
DATA AND RESULTS

1) a. Table of temperature of H2SO4 for NaHCO3

Time (min) Temperature (C)

1 34
2 34
3 34
4 34

b. Table of temperature of H2SO4 for Na2CO3

Time (min) Temperature (C)

1 33
2 33
3 34
4 34
2) Graphs of temperature as a function of time to obtain the corrected temperature
change (T).

a. T at 5th min, of NaHCO3 with H2SO4

T = Tf – Ti
= 32C - 34C
= -2C

b. T at 5th min, of Na2CO3 with H2SO4

T = Tf – Ti
= 38C - 34C
= 4C

3) The heat change (qp) for

a. NaHCO3 with H2SO4

qp = mCpT

qp = 50g x 4.18 J g-1 C-1 x (-2C)

qp = -418 J

qp = -0.418 kJ

b. Na2CO3 with H2SO4

qp = mCpT

qp = 50g x 4.18 J g-1 C-1 x (4C)

qp = 820 J

qp = 0.820 kJ

2NaHCO3 (s) + H2SO4 (aq)  Na2CO4 (aq) + 2CO2 (g) + 2H2O (l) H1 : y kJ mol-1

Na2CO3 (s) + H2SO4 (aq)  Na2CO4 (aq) + CO2 (g) + H2O (l) H2 : z kJ mol-1
Mol of NaHCO3 : 23 + 1 + 12 + (16x3)

: 84 g/mol
𝑚𝑎𝑠𝑠
No. of mol : 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠

4.44𝑔
: 84𝑔/𝑚𝑜𝑙

: 0.0528 mol

H1 : y kJ mol-1

H1 : - 0.418 kJ ÷ 0.0528 mol

H1 : -7.92 kJ mol-1

Mol of Na2CO3 : (23x2) + 12 + (16x3)

: 106 g/mol
𝑚𝑎𝑠𝑠
No. of mol : 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠

3.33𝑔
: 106𝑔/𝑚𝑜𝑙

: 0.0314 mol

H2 : z kJ mol-1

H2 : 0.820 kJ ÷ 0.0314 mol

H2 : 26.11 kJ mol-1

4) The thermo chemical equation for the decomposition of NaHCO 3 (s) is

2NaHCO3 (s)  Na2CO3 (s) + H2O (l) + CO2 (g) H = x kJ

Thus,

2NaHCO3 (s) + H2SO4 (aq)  Na2SO4 (aq) + 2CO2 (g) + 2H2O (l) H1 : -7.92 kJ mol-1

Na2SO4 (aq) + CO2 (g) + H2O (l)  Na2CO3 (s) + H2SO4 (aq) H2 : -26.11 kJ mol-1

 2NaHCO3 (s)  Na2CO3 (s) + H2O (l) + CO2 (g)

H = H1 + H2

H = (-7.92 kJ mol-1) + (-26.11 kJ mol-1)
H = -34.03 kJ mol-1

5) The S for the decomposition of NaHCO3 (s) from standard data is

2NaHCO3 (s)  Na2CO3 (s) + H2O (l) + CO2 (g)

Sreaction =  Sproduct -  Sreactant

Sreaction = (135.0 + 188.7 + 213.6) – (2 x 102)

Sreaction = 333.3 kJ/mol K

6) The G for the decomposition of NaHCO3 (s) is

Gexp = H - TS

Gexp = -34.03 kJ/mol – (25C + 273 K)(333.3 kJ/mol K)

Gexp = -99357.43 kJ/mol

7) Comparison between the experimental Gexp with that of the Gtheory extracted
from standard data is

Gexp = -99357.43 kJ/mol

Gtheory =  Gproduct -  Greactant

Gtheory = (-376.56 – 394.38 + 228.59) – (2 x -851.86)

Gtheory = 1161.37 kJ/mol

DISCUSSION

From this experiment, the decomposition of NaHCO3 (s) at standard conditions is a

spontaneous process. This is because the value of G below than zero (G<0).
Recalling the condition for spontaneous change, the temperature dependence of G
depends almost entirely on the entropy change associated with the process. In other
hands, the values of H and S are themselves slightly temperature dependent which
both increased gradually with temperature.

G = H - TS < 0

From the equation of Gibbs energy above, the sign of the entropy change determine
whether the reaction becomes more or less spontaneous as the temperature is raised.
For any given reaction, the sign of H can also be positive or negative. From our
experiment, Gtheory presented a positive value which is 1161.37 kJ/mol while the Gexp
gives out negative value that is -99357.43 kJ/mol. Furthermore, in our experiment, the
H is less than zero that is -34.03 kJ/mol while the S is greater than zero which is
333.3 kJ/mol K. Under this condition, both the H and TS terms will be negative, so it
will gives G negatives regardless of the temperature.

In order to make use Gibbs energies to predict the chemical changes, we need to know
the free energy of the individual components of the reaction. For this purpose, we had to
combine the standard enthalpy of formation and the standard entropy of a substance to
get its standard free energy of formation.

G = H - TS

We then can determine the standard Gibbs energy of the reaction according to this
formula.

Gtheory =  Gproduct -  Greactant

The one of the major sources of error in this experiment is the heat loss as we added
NaHCO3 into the H2SO4 in the double-wall vacuum stainless steel calorimeter. This heat
loss influence the value of q. Plus, it is hard to stir literally the content of the
calorimeter while having to take the reading of the temperature of the thermometer for
every 10 seconds which might cause small faults in the temperature reading.
QUESTIONS

1. A student mixed 50.0 mL of HCl (aq) and 75.0mL of NaOH (aq) in a calorimeter.
Each of the reactant solutions had a density of 1.04g/mL and an initial
temperature of 22.6C. after HCl (aq) and NaOH (aq) reacted, the mixed solution
reached a maximum temperature of 26.3C. calculate the heat released or
absorbed by the reaction process in unit J. assume the product solution has Cp =
4.18 J g-1 C-1. Is the reaction exothermic or endothermic? Explain your answer.

HCl + NaOH  NaCl + H2O

𝑚𝑎𝑠𝑠
For NaOH : density, p = 𝑣𝑜𝑙𝑢𝑚𝑒
𝑚𝑎𝑠𝑠
1.04 g/mL = 75𝑚𝑙

Mass = 78 g

𝑚𝑎𝑠𝑠
For HCl : density, p = 𝑣𝑜𝑙𝑢𝑚𝑒
𝑚𝑎𝑠𝑠
1.04 g/mL = 50𝑚𝑙

Mass = 52 g

Thus, qp = mCpT
= m x Cp x (Tf - Ti)
= (78g + 52g) x (4.18 J g-1 C-1) x (26.3C – 22.6C)
= 2.01 x 103 J

 The reaction is endothermic process because the value is positive as heat is

absorbed by the system from surrounding.
 2. By applying Hess’s Law, show the steps for the derivation of reaction (a) from
reaction (b) to (d).

Mg (s) + 1⁄2 O2 (g)  MgO (s) (a)

H2 (g) + 1⁄2 O2 (g)  H2O (l) (b)
Mg (s) + 2HCl (aq)  MgCl2 (aq) + H2 (g) (c)
MgO (s) + 2HCl (aq)  MgCl2 (aq) + H2O (l) (d)

 Derivation of reaction (a) by Hess’s Law :

H2 (g) + 1⁄2 O2 (g)  H2O (l) (b)

Mg (s) + 2HCl (aq)  MgCl2 (aq) + H2 (g) (c)
MgCl2 (aq) + H2O (l)  MgO (s) + 2HCl (aq) (d)

Where reaction (d) is in reverse direction.

Thus, this derivation forming reaction (a) that is

Mg (s) + 1⁄2 O2 (g)  MgO (s)

CONCLUSION

The change of standard Gibbs free energy for the decomposition of sodium hydrogen
carbonate (NaHCO3) from the change of standard enthalphy and the change of
standard entrophy is obtained. The value is -99357.43 kJ/mol meanwhile the theoretical
value is found to be 1161.37 kJ/mol.

The experiment would be lot more accurate and successful if the major error occurring
is avoided.
REFERENCES

1. Change of standard Gibbs free energy for the decomposition of sodium hydrogen
carbonate. (2013). Retrieved from
http://www.scribd.com/doc/172662989/chnage-of-standard-gibbs-free-energy-for-
the-decomposition-of-sodium-hydrogen-carbonate

2. Gibbs Free Energy. (2013). Retrieved from

http://www.cliffsnotes.com/sciences/chemistry/chemistry/thermodynamics/gibbs-
free-energy

3. Gibbs Free Energy Definition. (2013). Retrieved from

http://chemistry.about.com/od/chemistryglossary/g/gibbs-free-energy-
definition.htm