Indian Institute of Science Education & Research, Kolkata Semester IV – April 2009

Chemistry Project Report

Title: A comparison between the enthalpies

calculated using conventional methods and
computational methods

Indian Institute of Science Education & Research, Kolkata

Semester IV April 2009

By:
Harsh Purwar (07MS-76)
Satyam Singhal (07MS-66)
Jyothi V. Nair (07MS-72)

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Indian Institute of Science Education & Research, Kolkata Semester IV – April 2009

Introduction:
Experiments have always formed the basis of human quest in science. What keeps on
changing is the sophistication of the experimental techniques for a still greater precision.
One way of carrying out the experiment is the use of conventional methods which involve
manual experimentation have limited accuracy since the systematic and random errors can
never be fully removed. This is the age of computers wherein much advanced and complex
experiments are carried out using the computer programmes and soft-wares. These
techniques of experimentation are practically foolproof with negligible error involved. Here
in this experiment we wish to establish this fact convincingly by comparing the efficiencies
of both the methods for a particular experiment.

Aim of the Experiment:

To compare the enthalpy of hydration of an endothermic and an exothermic reaction using
the conventional experimental techniques (involving titrations) and computational methods
(using Gaussian).

Chemical Reactions:
• Exothermic Reaction:
‫ܽܥ‬ሺܱ‫ܪ‬ሻଶ ሺ‫ݏ‬ሻ ⟶ ‫ܽܥ‬ଶା ሺܽ‫ݍ‬ሻ + 2ܱ‫ ିܪ‬ሺܽ‫ݍ‬ሻ

• Endothermic Reaction:
ܰ‫ܪ‬ସ ܱܰଷ ሺ‫ݏ‬ሻ + ‫ܪ‬ଶ ܱሺܽ‫ݍ‬ሻ ⟶ ܰ‫ܪ‬ସ ܱ‫ܪ‬ሺܽ‫ݍ‬ሻ + ‫ܪ‬ା ሺܽ‫ݍ‬ሻ + ܱܰଷି ሺܽ‫ݍ‬ሻ
Theory:
The experiment involves determining the equilibrium concentration of OH- ions in a solution
containing excess of Ca(OH)2 by titrating it with about 0.01 M HCl.

‫ܽܥ‬ሺܱ‫ܪ‬ሻଶ ሺ‫ݏ‬ሻ ⟶ ‫ܽܥ‬ଶା ሺܽ‫ݍ‬ሻ + 2ܱ‫ ିܪ‬ሺܽ‫ݍ‬ሻ

Moles of hydroxide = moles of HCl = Volume of HCl in litres X [HCl]

Moles of Ca(OH)2 = 1/2 moles of hydroxide

Molar solubility of Ca(OH)2 = moles of Ca(OH)2 / Volume in litres

The solubility product, Ksp is then calculated as

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Indian Institute of Science Education & Research, Kolkata Semester IV – April 2009
ଶା ି ଶ ଷ
‫ܭ‬௦௣ = [‫ = ] ܪܱ[] ܽܥ‬4‫ݏ‬

∆‫்ܩ‬଴ = −ܴ݈ܶ݊‫ܭ‬௦௣

∆‫்ܩ‬଴ = ∆‫ܪ‬଴ − ܶ∆ܵ଴

Similar theory is applicable to the other reaction as well.

Experiment:
Part I
1. Standard oxalic acid solution was prepared by weighing.
2. Sodium hydroxide (NaOH) solution was prepared and was standardized using oxalic
acid solution.
3. HCl solution was prepared and was standardized with standardized NaOH solution.
4. Calcium hydroxide solution was then drawn off from a beaker containing excess of
solid Ca(OH)2 that was being stirred for 24 hours.
5. Temperature of the sample was recorded using a thermometer.
6. Sample was then filtered and diluted accordingly and was titrated with standardized
HCl using appropriate indicator.
7. Another Ca(OH)2 solution was prepared at a higher temperature (100° C) and steps 6
& 7 were repeated.
Part II
Similar procedure was followed for ammonium nitrate involving titration with HCl.
The only difference was that the second sample was made at a lower temperature (0° C
instead of 100° C) because this reaction being an endothermic reaction. That is the
solubility of NH4NO3 increases with the rise in temperature, and so if the sample would
have been prepared at a higher temperature then during the reaction due to cooling of the
sample NH4NO3 would have been precipitated.
Part III
Next the software Guassian is used to calculate the ∆‫ܪ‬ଶଽ଼ values for both the above
reactions using the standard protocol involving:
• ‫ܧ‬௘଴ is calculated by single point energy calculation using LSDA / B3LYP method and 6-
311+g(2df,2p) basis set for various entities in the reactions.
• Geometry optimization + frequency calculations were done using LSDA / B3LYP
method and 6-31+g(d) basis set.

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Indian Institute of Science Education & Research, Kolkata Semester IV – April 2009

Results:
Part I
The temperatures of the two samples of Ca(OH)2 are 33° C (R.T.) and 100° C.

Table # 1: Preparation of Oxalic acid solution.

Amount of Oxalic acid Volume of the solution Strength of the solution

taken (g) (mL) (M)
0.4027 100 0.045

Table # 2: Standardization of NaOH solution.

S. No. Volume of Burette Reading Volume of Strength of

Oxalic acid Initial Final NaOH NaOH
solution (mL) solution (mL) solution (M)
1 10 0 16.8 16.75 0.054
2 10 0 16.7

Table # 3: Standardization of HCl solution.

S. No. Volume of Burette Reading Volume of Strength of

HCl solution Initial Final NaOH HCl solution
(mL) solution (mL) (M)
1 10 0 6.8 6.9 0.037
2 10 7.0 14.0

Table # 4: Titration of Ca(OH)2 solution prepared at room temperature.

S. No. Volume of Burette Reading Volume of HCl

Ca(OH)2 Initial Final solution (mL)
solution (mL)
1 10 0 10.8 10.85
2 10 11 21.9

Molar solubility of Ca(OH)2 (s) in the solution prepared at 33° C is given by,
[‫݈݋ܸ × ]ܮܥܪ‬. ‫ ݈ܥܪ ݂݋‬0.037 × 10.85
‫=ݏ‬ = = 0.020 ‫ܯ‬
2 × ܸ‫݈݋‬. ‫݊݋݅ݐݑ݈݋ݏ ݂݋‬ 2 × 10
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Indian Institute of Science Education & Research, Kolkata Semester IV – April 2009
Table # 5: Titration of Ca(OH)2 solution prepared at 100° C.

S. No. Volume of Burette Reading Volume of HCl Solubility of

Ca(OH)2 Initial Final solution (mL) Ca(OH)2 in
solution (mL) solution (M)
1 10 0 6.0 6.05 0.011
2 10 6.0 12.1

Molar solubility of Ca(OH)2 (s) in the solution prepared at 100° C is given by,
[‫݈݋ܸ × ]ܮܥܪ‬. ‫ ݈ܥܪ ݂݋‬0.037 × 6.05
‫=ݏ‬ = = 0.011 ‫ܯ‬
2 × ܸ‫݈݋‬. ‫݊݋݅ݐݑ݈݋ݏ ݂݋‬ 2 × 10

Part II
The temperatures of the two samples of NH4NO3 are 33° C (R.T.) and 4° C.

Table # 6: Titration of NH4NO3 solution prepared at room temperature.

S. No. Volume of Burette Reading Volume of HCl Strength of

NH4NO3 Initial Final solution (mL) NH4NO3
solution (mL) solution (M)
1 10 0 1.9 1.9 0.00703
2 10 2.5 4.4

Table # 7: Titration of NH4NO3 solution prepared at 4° C.

S. No. Volume of Burette Reading Volume of HCl Strength of

NH4NO3 Initial Final solution (mL) NH4NO3
solution (mL) solution (M)
1 10 0 1.8 1.8 0.00666
2 10 0 1.8

Part III
Table # 8: Computational Data.

S. Entity Electronic energies at 0° K Thermal energy Energies

No. ሺ‫ܧ‬௘଴ ሻ (Kcal/mole) corrections including the
(Kcal/mole) corrections
1 Ca(OH)2 -829.3791467 0.031191 -829.3479557

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Indian Institute of Science Education & Research, Kolkata Semester IV – April 2009
2+
2 Ca -676.9057451 0.002360 -676.9033851
3 OH- -75.82967035 0.011636 -75.81803435
4 NH4NO3 *** *** ***
5 NH4+ -56.92138592 0.053741 -25.57884592
6 NO3- -280.4598192 0.018000 -271.7486892

Calculations:
Part I
Molar solubility for Ca(OH)2 at 306° K is:

sଷ଴଺ = 0.020 M

So, we have
ଷ଴଺
‫ܭ‬௦௣ = 4‫ ݏ‬ଷ = 3.2 × 10ିହ
ଷ଻ଷ
‫ܭ‬௦௣ = 5.324 × 10ି଺

Since, we know that

∆‫ ܩ‬଴ = −ܴ݈ܶ݊‫ܭ‬௦௣
଴
∆‫ܩ‬ଷ଴଺ = −8.314 × 306.15 × ݈݊ሺ3.2 × 10ିହ ሻ

= −2545.3311 × ሺ−10.35ሻ

= 2.634 × 10ସ ‫ܬ‬/݉‫݈݋‬

Similarly,
଴
∆‫ܩ‬ଷ଻ଷ = 3.767 × 10ସ ‫ܬ‬/݉‫݈݋‬

So now we have two simultaneous equations in ∆‫ܪ‬଴ and ∆ܵ ଴ as,

଴ ଴ ଴
∆‫ܩ‬ଷ଴଺ = ∆‫ܪ‬ଷ଴଺ − ܶ∆ܵଷ଴଺ ⋯ ⋯ ⋯ ሺ1ሻ
଴ ଴ ଴
∆‫ܩ‬ଷ଻ଷ = ∆‫ܪ‬ଷ଻ଷ − ܶ∆ܵଷ଻ଷ ⋯ ⋯ ⋯ ሺ2ሻ

Here we neglect the difference between the enthalpy at two different temperatures i.e.
଴ ଴
∆‫ܪ‬ଷ଻ଷ and ∆‫ܪ‬ଷ଴଺ and also between the entropies at the two temperatures as the
differences are small and insignificant.

Solving the two equations,

2.634 × 10ସ = ∆‫ܪ‬଴ − 306.15 × ∆ܵ ଴
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Indian Institute of Science Education & Research, Kolkata Semester IV – April 2009
3.767 × 10 = ∆‫ ܪ‬− 373.15 × ∆ܵ ଴
ସ ଴

we get, standard change in enthalpy for the hydration of Ca(OH)2,

∆‫ܪ‬଴ = −14.272 ‫ܬܭ‬/݉‫݈݋‬

Part II
Molar solubility of NH4NO3 at 306° K,

‫ = ݏ‬0.00703 ‫ܯ‬

So, we have
ଷ଴଺
‫ܭ‬௦௣ = 4‫ ݏ‬ଷ = 1.389 × 10ି଺
ଶ଻ଷ
‫ܭ‬௦௣ = 1.182 × 10ି଺

Since, we know that

∆‫ ܩ‬଴ = −ܴ݈ܶ݊‫ܭ‬௦௣
଴
∆‫ܩ‬ଷ଴଺ = −8.314 × 306.15 × ݈݊ሺ1.389 × 10ି଺ ሻ

= −2545.3311 × ሺ−13.487ሻ

= 3.433 × 10ସ ‫ܬ‬/݉‫݈݋‬

Similarly,
଴
∆‫ܩ‬ଶ଻ଷ = 3.099 × 10ସ ‫ܬ‬/݉‫݈݋‬

The two equations involving enthalpy and entropy,

3.433 × 10ସ = ∆‫ܪ‬଴ − 306.15 × ∆ܵ ଴

3.099 × 10ସ = ∆‫ܪ‬଴ − 273.15 × ∆ܵ ଴

we get, standard change in enthalpy for the hydration of NH4NO3,

∆‫ܪ‬଴ = 65.3 ‫ܬܭ‬/݉‫݈݋‬

Part III
Standard change in enthalpy for the hydration of Ca(OH)2 can be calculated using the data
obtained from Gaussian by frequency and single point energy calculations listed in table # 8
as,
଴
∆‫ܪ‬ଶଽ଼ = ∆‫ܧ‬௘଴ + ∆ሺcorrection termsሻ

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Indian Institute of Science Education & Research, Kolkata Semester IV – April 2009
Here ∆ on the right side signifies difference between the products and reactants.

The governing chemical equation here written as,

‫ܽܥ‬ሺܱ‫ܪ‬ሻଶ ሺ‫ݏ‬ሻ ⟶ ‫ܽܥ‬ଶା ሺܽ‫ݍ‬ሻ + 2ܱ‫ ିܪ‬ሺܽ‫ݍ‬ሻ

So the enthalpy can be written as,

଴
∆‫ܪ‬ଶଽ଼ = 0.808501888 ‫݁݁ݎݐݎܽܪ‬/ܲܽ‫݈݁ܿ݅ݐݎ‬

= 2.123 × 10ଷ ‫ܬܭ‬/݉‫݈݋‬

Conclusion:
The enthalpy of hydration of Ca(OH)2 calculated via experimentation is found to be
-14.272KJ/mol.

The enthalpy of hydration of NH4NO3 calculated via experimentation is found to be

65.3 KJ/mol.

The enthalpy of hydration of Ca(OH)2 calculated via computational method is found to be

2.123 × 10ଷ KJ/mol.

Discussion:
Seeing the results obtained we can firmly conclude that computational methods are much
superior compared to conventional methods when it comes to experimentation.

But still the conventional methods continue to hold their importance because they give
better visualization and establish theoretical principles more convincingly. Moreover they
may not be accurate in absolute terms but on a relative scale they are still pretty helpful
and of great use. So the need of the hour is to take the middle path and have a balanced
approach.

References:
• Our very own acquired knowledge along with the big creativity bank we have with us.
• World Wide Web (Google search)
• Wikipedia: http://en.wikipedia.org/wiki

Acknowledgement:
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Indian Institute of Science Education & Research, Kolkata Semester IV – April 2009
• Prof. Sanjib Bagchi, HOD Chemistry
• Dr. Srikanth
• Mr. Saroj Naik, Lab Assistant