CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2020

SOLID SOLUTION EQUILIBRIUM

Marks:
Experiment done on: 05/02/2020

100
Report submitted on: 12/02/2020

For Instructors use only:

No Section Max. Marks Marks

1 Introduction / Background Theory -

2 Experimental Details: Materials and Methods -

3 Experimental Observations & Raw Data 20

4 Sample Calculations 20

5 Results, Discussion and Conclusions

7 Suggestions for Improvement 10

8 Overall Formatting & References 10

Total 100

Batch: Wednesday
Group: W5

Name Roll Number

P SAI DHARANI CH18B017
P SRAVANI CH18B018
RAHUL JAIN CH18B019
S VISHAL CH18B020

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 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2020

1. INTRODUCTION / BACKGROUND THEORY

In the saturated solution of KNO3 in water the equilibrium established is, KNO3 (s)
⇄ K+(aq) + NO3- (aq)
The equilibrium constant which is also called as the solubility product is given by,
K sp = [K+][NO3ー]
To understand the solubility process of KNO3 in water we use the thermodynamic properties
Δg, Δh and Δs
The relationship between these quantities is given by,
Δg = Δh – T*Δs.
We also relate the solubility product and the molar change in Gibbs free energy by,
Δg = − RTlnKsp.
Finally we get a linear relationship between ln(Ksp ) and 1/T.
ln(Ksp) = − (ΔH/RT) + (ΔS/R)

1.1 Aim
● Study the nature of solubility of solid in liquid and interpret the equilibrium data.
● Calculate 𝐾𝑠𝑝(𝑇) and Δgdissolve using measured equilibrium concentration in the law
of mass action.
● Plot Δg dissolve vs. T ( ln(Ksp) vs 1/T ) and find Δh dissolve and Δs dissolve.
● Compare measured solubility data with literature data. Also compare the obtained
thermochemical data with literature.

2. EXPERIMENTAL DETAILS
2.1 Materials Chemicals:
● Potassium Nitrate (KNO3 )
● Distilled Water
Apparatus:
● Weighing Balance
● Beakers and measuring flask
● Test tube
● Thermometer
● Stirrer
● Water-bath
● Hot-plate heater
● Marker
● Burette

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 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2020

2.2 Experimental Setup & Procedure :

● Assemble a hot water bath for KNO3 dissolving .
● Measure about 20 g of KNO3 on a balance. Record the exact mass of KNO3 and transfer
the compound to a dry clean 200 mL test tube.
● Measure 15 mL of distilled water and add it to the test tube with KNO3 . Heat the tube in
water bath with the hot plate and stir the mixture with a metal wire rod until all of the KNO3
dissolves.
● Remove the test tube from the hot water bath .
● Mark the solution level on the test tube with a sharpie and label it as 1 . Let the test tube
with KNO3 solution cool naturally while slowly stirring the solution.
● Observe the KNO3 solution when it cools and record the temperature when the first white
crystal appears. This will be the temperature for the equilibrium .
● Add 1 mL of distilled water to the test tube after you record the temperature. Put the test
tube back to hot water bath and heat it until all KNO3 dissolves. Repeat the process 6 times
by adding 1ml, 2ml alternatively and mark the solution levels as 2,3,4,5,6,7 and record the
equilibrium temperatures. (But we added in the following fashion: 2mL, 3mL, 1mL and 2mL)
● When the experiment is finished, disposal the KNO3 solution into the waste container
● Finally fill the burette with water and measure volume for all the marks made on test tube.

2.3 Precautions :
●Constantly keep stirring the solution while heating and cooling to maintain uniform
temperature throughout the solution.
● Avoid direct contact with the chemical as they are hazardous for health.
●KNO3 is flammable and strong oxidizing agent. Therefore, dispose of all wastes by flushing
them down the sink with plenty of water.
 Also, avoid direct heating (use a water bath) to avoid explosions.

3. EXPERIMENTAL OBSERVATIONS AND DATA

Mass of KNO3 = 20.0 g

Temperature Volume of Volume of Moles of Concentration Ksp ( mol2/L2 )
(°C) water (ml) solution (ml) KNO3 ( mole/L )
68.7°C 15ml 23.6ml 0.19782 8.3820 70.258
63.0°C 17ml 26.6ml 0.19782 7.4368 55.306
55.4°C 20ml 30.2ml 0.19782 6.5503 42.906
52.5°C 21ml 31.3ml 0.19782 6.3201 39.944
49.0°C 23ml 33.5ml 0.19782 5.9050 34.870

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 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2020

4. SAMPLE CALCULATIONS

Calculating concentration of the solution for the first Reading:

Molecular weight of KNO3 = 101.1 g/mole
Mass of KNO3 = 20.0 gm
Number of moles of KNO3 (n) = 20.0/101.1 =0.19782 mol
Concentration (C) =0.19782mol/0.0236L = 8.38202 mol/L

Calculating Ksp :ー Potassium Nitrate dissociates in the water as

follows: ー KNO3 (s) ⇄ K + (aq) + NO 3 (aq)

Ksp = [K +][NO3 ]= (8.38202 mol/l)2 = 70.258mol /L

Calculating Δg:
Δg = − RTlnKsp =- ( 8.314)*(68.7+273)*ln(70.258)= -12079.9753 J/ mol

Calculating Δh and Δs:

Δg = Δh-T*Δs Δg was fitted as a linear function of T and Δh and Δs were found
from the intercept and slope respectively.
Δh = 31859 J/mol
Δs = 128.41 J/mol-K

lnK vs 1/T

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 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2020

∆g vs T (K)

5. RESULTS, DISCUSSION & CONCLUSION

Tc (K) Ksp ( mol2/l2 ) ∆g(J/mol)

341.7K 70.258 -12079.9753
336.0K 55.306 -11210.00
328.4K 42.906 -10263.296
325.5K 39.944 -9979.080
322.0K 34.870 -9508.089
 The reaction is endothermic as ∆h is positive. So, the increase in temperature favours the
forward reaction which is mixing.
 We can see that as the temperature increases, Ksp of KNO3 increases which

implies that its solubility increases with temperature.

 The high value of Ksp for KNO3 shows that KNO3 is soluble in water as it is
also a salt formed by combining a strong alkali base KOH and HNO3 .
 The change in molar Gibbs free energy is positive for all the temperatures
indicating that the mixing of KNO3 in water is favourable.

5.1 Conclusions

● KNO3 mixing in water is entropically favoured, spontaneous and endothermic.

● The entropy of mixing, Ksp and solubility increase with increase in temperature.
● The plot of ∆g vs T is a straight line with an intercept equal to the Enthalpy of mixing and
slope equal to the negative of Entropy of mixing, both of which were graphically calculated.
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 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2020

● The solid liquid equilibrium was identified as the point where the KNO3 crystals first
appear.
● Dissolving potassium nitrate in water is an endothermic process because the hydration of the
ions when the crystal dissolves does not provide as much energy as is needed to break up the
lattice.

6. SUGGESTIONS

● Avoid rapid cooling or heating as this might cause the equilibrium to be attained but
won’t provide sufficient time for the thermometer to adjust to temperature changes.
● Mark the volume of water correctly using the marker, so that concentration can he measured
within reasonable error.
● Do not use the initial volume for any calculations. The 20g KNO3 contributes to the total
volume and must be measured.
● Since V depends on T, the final volume measured depends on the time of heating. Do not overheat
the solution after the last of the solid is dissolved as this might increase the total volume.
● Ensure constant stirring to ensure Uniform Temperature in the mixture.
All the crystals must be dissolved at the same time at the T crystal to avoid overheating.
● Do not remove the thermometer while adding more water as this will cause fluctuations in
temperature and not let the thermometer settle at the correct temperature immediately.

7. REFERENCES

1. M. D. Koretsky, Engineering and Chemical Thermodynamics; 2nd Edition, Wiley: New

York, 2012; pp 523-529.
2. MSDS sheet of KNO3

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 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2020

Data sheet :