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  • CHAIR OF PHYSICAL CHEMISTRY

    TECHNISCHE UNIVERSITT MNCHEN

    Laboratory Course in Physical Chemistry

    for Fundamental Studies

    Experiments Manual

    The reproduction of this manual is funded by the tuition grant

    of the Chemistry Faculty

  • _

    2016 Chairs of Physical Chemistry of the Technische Universitt Mnchen

    3rd Edition (1st June 2017).

    Editing, typing and printing: Michele Piana, Karin Stecher, Alexander Ogrodnik, Sonja Uhl,

    Matthias Stecher and Peter Kmmerer.

    Chair of Technical Electrochemistry and Second Chair of Physical Chemistry

    Alle Rechte vorbehalten. Die Vervielfltigung auch einzelner Teile, Texte oder Bilder mit

    Ausnahme der in SS 53, 54 UrhG ausdrcklich genannten Sonderflle gestattet das

    Urheberrecht nur, wenn sie mit den Lehrsthlen oder dem Praktikumsleiter vorher vereinbart

    wurde.

  • 5

    Table of Contents 1 Vapour-Pressure Curve and Boiling-Point Elevation ................................................... 11

    1.1 Context and aim of the experiment ....................................................................... 11

    1.1.1 Important concepts to know .......................................................................... 11

    1.1.2 Most common questions to be answered ...................................................... 11

    1.1.3 Further preparations before the experiment ................................................... 12

    1.2 Theory ................................................................................................................... 12

    1.2.1 Phase diagrams ............................................................................................. 12

    1.2.2 Vapour pressure ............................................................................................. 13

    1.2.3 Colligative properties and boiling-point elevation .......................................... 14

    1.3 Experimental details and evaluation ...................................................................... 17

    1.3.1 Experimental execution .................................................................................. 17

    1.3.2 Data evaluation .............................................................................................. 19

    1.4 Applications of the experiment and its theory ....................................................... 20

    1.5 Appendixes ........................................................................................................... 20

    1.5.1 Derivation of the boiling-point elevation from the chemical potential ............. 20

    1.5.2 Basic instructions to use the software ............................................................ 22

    1.6 Literature ............................................................................................................... 24

    2 Freezing-Point Depression .......................................................................................... 26

    2.1 Context and aim of the experiment ....................................................................... 26

    2.1.1 Important concepts to know .......................................................................... 26

    2.1.2 Most common questions to be answered ...................................................... 26

    2.1.3 Further preparations before the experiment ................................................... 27

    2.2 Theory ................................................................................................................... 27

    2.2.1 Phase diagrams ............................................................................................. 27

    2.2.2 Colligative properties ..................................................................................... 27

    2.2.3 Derivation of freezing-point depression from chemical potential ................... 28

    2.2.4 Supercooling of a liquid ................................................................................. 30

    2.3 Experimental details and evaluation ...................................................................... 31

    2.3.1 Experimental execution .................................................................................. 31

    2.3.2 Data evaluation .............................................................................................. 33

    2.4 Applications of the experiment and its theory ....................................................... 33

  • 6

    2.5 Appendixes ........................................................................................................... 34

    2.5.1 Basic Instructions to use the software ........................................................... 34

    2.6 Literature ............................................................................................................... 36

    3 Joule-Thomson Effect ................................................................................................. 37

    3.1 Context and aim of the experiment ....................................................................... 37

    3.1.1 Important concepts to know .......................................................................... 37

    3.1.2 Most common questions to be answered ...................................................... 37

    3.1.3 Further preparations before the experiment ................................................... 38

    3.2 Theory ................................................................................................................... 38

    3.2.1 Internal energy and intermolecular interactions .............................................. 38

    3.2.2 The Joule-Thomson-Experiment .................................................................... 40

    3.2.3 Thermodynamic analysis of the Joule-Thomson effect .................................. 41

    3.2.4 Derivation of the expansion coefficient and the Joule-Thomson coefficient... 44

    3.2.5 Calculation of the inversion curve using the van-der-Waals equation of

    state ............................................................................................................... 45

    3.3 Experimental details and evaluation ...................................................................... 46

    3.3.1 Experimental execution .................................................................................. 47

    3.3.2 Data evaluation .............................................................................................. 49

    3.4 Applications of the experiment and its theory ....................................................... 50

    3.5 Appendixes ........................................................................................................... 51

    3.5.1 Basic instructions to use the software ........................................................... 51

    3.5.2 Instruction for data treatment ......................................................................... 52

    3.5.3 Van-der-Waals parameters ............................................................................ 55

    3.5.4 Further implementations in the derivation of the Joule-Thomson coefficient for

    real gases ....................................................................................................... 55

    3.5.5 Further implementations in the derivation of the inversion temperature for real

    gases ............................................................................................................. 56

    3.5.6 Virial coefficient .............................................................................................. 57

    3.6 Literature ............................................................................................................... 57

    4 Combustion Enthalpy via Bomb Calorimetry ............................................................... 58

    4.1 Context and aim of the experiment ....................................................................... 58

    4.1.1 Important concepts to know .......................................................................... 58

    4.1.2 Most common questions to be answered ...................................................... 58

    4.1.3 Further preparations before the experiment ................................................... 58

    4.2 Theory ................................................................................................................... 59

  • 7

    4.2.1 Heat transactions, internal energy and reaction enthalpy............................... 59

    4.2.2 Combustion reactions .................................................................................... 60

    4.2.3 Bomb calorimetry ........................................................................................... 61

    4.3 Experimental details and evaluation ...................................................................... 63

    4.3.1 Experimental execution .................................................................................. 63

    4.3.2 Data evaluation .............................................................................................. 68

    4.4 Applications of the experiment and its theory ....................................................... 68

    4.5 Appendixes ........................................................................................................... 69

    4.5.1 Basic Instructions to use the software ........................................................... 69

    4.6 Literature .....................................