Thermodynamic Study on the Polymorphism of Cyclohexanol-Water Binary System by Differential Scanning Calorimetry

Leah Foscaldi, Jackie Guo, Michael Stanowski, Serena Xu

Motivation

Observed interesting phenomena when cyclohexanol was used as a solvent Similar phenomena in a published paper at different temperature Could this be due to different amounts of water in the cyclohexanol?

Cyclohexanol-Water mixtures

FT-NIR Small amounts of water have a minor effect on the structure of room temperature cyclohexanol

Polymorphism of Cyclohexanol

Exists in 2 stable and 2 metastable states below the freezing point Second-order phase transitions Supercooling/cold crystallization

Differential Scanning Calorimetry (DSC)

Compares heat flow to/from a sample and reference as temperature changes Heat flow changes with chemical or phase changes in materials

Can be used to find enthalpies, specific heats, activation energy

Figure 1: TA Instruments Differential Scanning Calorimeter

Experimental

DSC of distilled cyclohexanol, 5 C/min DSC of distilled cyclohexanol with 5% wt water

10, 5, 2.5, 1.25, 0.63 C/min

DSC of distilled cyclohexanol, 5 C/min

DSC of 5% cyclohexanol, 5 C/min

DSC Cyclohexanol-5% Water at 5 Celsius/min
5

0 -90 -70 -50 -30 -10 10 30

-5 Heat Flow (mW)

-10

-15

-20

Temp (Celsius)

-25

DSC of 5% cyclohexanol, various rates

DSC Cyclohexanol-5% Water
5

0 -90 -70 -50 -30 -10 10 30

-5 Heat Flow (mW) 0.63 C/min -10 1.25 C/min 2.5 C/min 5 C/min 10 C/min -15

-20

Temp (Celsius)

-25

Thermogram of Cyclohexanol With 5% Added Water at 5C/min with Enthalpy Peaks Integrated

Energy of Activation

Kissinger analysis on the crystallization E = 23.76 J/mol

Kissinger Plot
-16.5 0.0042 -17 0.0043 0.0044 0.0045 0.0046 0.0047 0.0048 0.0049 0.005

-17.5 ln( /Tm^2) y = -2857.4x - 4.3622 R = 0.6614 -18

-18.5

-19

-19.5

1/Tm

Conclusions

DSC of distilled cyclohexanol appeared to agree with observations in literature Water appears to affect the phase changes Negative energy of activation

Significance

Cyclohexanol is a common laboratory solvent Information about the effects of impurities (water) is vital Little previous research on this binary system

Further Study

Uncertainty about quantity of water in distilled cyclohexanol Larger range of water concentrations Larger temperature range, esp. in the higher range

Acknowledgements

The group members would like to acknowledge Dr. Bratoljub H. Milosavljevic, Brian Conway and Jennifer Tan for their assistance with new principles and their guidance in analyzing and obtaining the experimental data.

References

Mayer, J.; Rachwalska, M.; Sciesinska, E.; Sciensinski, J. J. Phys. France. 51 (1990) 857-867. Czarnecki, M.; Muszynski, A.; Troczynskia, H. J. Mol. Struc. 974 (2010) 60-67. Adachi, K.; Suga, H.; Seki, S. Bull. Chem. Soc. Jpn. 41 (1968) 10731087.