Thermochemistry/Calorimetry LEC Heat capacity of gases. What you need: What you can learn about. Principle and tasks

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1 Thermochemistry/Calorimetry LEC 02 What you can learn about 1st law of thermodynamics Universal gas constant Isobars Isotherms Isochors and adiabatic changes of state Principle and tasks Heat is added to a gas in a glass vessel by an electric heater which is switched on briefly. The temperature increase results in a pressure increase which is measured with a manometer. Under isobaric conditions a temperature increase results in a volume dilatation that can be read from a gas syringe. The molar heat capacities C v and C p are calculated from pressure and volume change. What you need: Experiment P with Cobra3 Basic-Unit Experiment P with digital counter Precision manometer Barometer/Manometer, hand.held Cobra3 Basic-Unit, USB Power supply12 VDC/2 A Cobra3 current probe 6A Software Cobra3 Universal writer software Digital counter, 4 decades Digital multimeter Mariotte flask, 10 l Gas syringe, 100 ml Stopcock, 1.way, straight Stopcock, 3.way, T.shaped, capillary Rubber Stopper 26/32, 3 holes Rubber Stopper 50.5/59.5, 1 hole Rubber tubing, d = 6 mm Nickelel ectrode, d = 3 mm, with socket Nickelel ectrode, 76 mm x 40 mm Chrome-nickel wire, d = 0,1 mm Scissors, straight, blunt, l = 140 mm Two-way switch, single pole Push-button switch Connecting cord, 32 A, Connecting cord, 32 A, Connecting cord, 32 A, Connecting cord, 32 A, Connecting cord, 32 A, Tripod base -PASS Retord stand, 210 x 130 mm, h Pressure change p as a func tion of the heat-up time t. U = 4.59 V, I = 0.43 A. Universal clamp Right angle clamp PC, Windows XP or higher P /11 24 Laboratory Experiments Chemistry PHYWE Systeme GmbH & Co. KG D Göttingen

2 LEC Related topics Equation of state for ideal gases, 1st law of thermodynamics, universal gas constant, degree of freedom, mole volumes, isobars, isotherms, isochors and adiabatic changes of state. Principle Heat is added to a gas in a glass vessel by an electric heater which is switched on briefly. The temperature increase results in a pressure increase, which is measured with a manometer. Under isobaric conditions, a temperature increase results in a volume dilatation which can be read from a gas syringe. The molar heat capacities C V and C p are calculated from the pressure or volume change. Equipment Precision manometer Barometer/Manometer, hand-held Digital counter, 4 decades * 1 Digital multimeter * 2 Mariotte flask, 10 l Gas syringe, 100 ml Stopcock, 1-way, straight Stopcock, 3-way, T-shaped, capillary Rubber stopper, d = 26 / 32 mm, 3 holes Rubber stopper, d = 50.5 / 59.5 mm, 1 hole Rubber tubing, d i = 6 mm Nickel electrode, d = 3 mm, with socket Nickel electrode, 76 x 40 mm Chrome-nickel wire, d = 0.1 mm, l = 100 m Scissors, straight, blunt, l = 140 mm Two-way switch, single pole * 1 Connecting cord, l = 750 mm, blue * 1 Connecting cord, l = 500 mm, red Connecting cord, l = 500 mm, yellow * 2 Connecting cord, l = 750 mm, red Connecting cord, l = 500 mm, blue * 3 Tripod base -PASS Retort stand, h = 750 mm Universal clamp Right angle clamp Changes in the equipment required for use of the Basic- Unit: (instead of * above mentioned) Cobra3 Basic-Unit, USB Power supply 12 V/ 2 A Cobra3 current probe 6 A Push-button switch Connecting cord, l = 500 mm, blue Cobra3 Universal writer software PC, Windows 95 or higher Tasks Determine the molar heat capacities of air at constant volume C V and at constant pressure C p. Set-up and procedure Perform the experimental set-up according to Fig. 1. Fig. 1: Experimental set-up (C V ). PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D Göttingen P

3 LEC Insert the two nickel electrodes into two holes in the three-hole rubber stopper and fix the terminal screws to the lower ends of the electrodes. Screw two pieces of chrome nickel wire, which are each about 15 cm long, into the clamps between these two electrodes so that they are electrically connected in parallel. The wires must not touch each other. Insert the one-way stopcock into the third hole of the stopper and insert the thus-prepared stopper in the lower opening of the bottle. The 5 V output of the electrical 4-decade digital counter serves as the power source. The electrical circuit is illustrated in Fig. 3. To determine C V, connect the precision manometer to the bottle with a piece of tubing. To do this, insert the second stopper, which has been equipped with the three-way stopcock, into the upper opening of the bottle. The manometer must be positioned exactly horizontally. Read the pressure increase immediately after cessation of the heating process. The manometer must be filled with the oil which is supplied with the device. The scale is now calibrated in hpa. The riser tube of the manometer must be well wetted before each measurement. Start the measuring procedure by activating the push-button switch. The measuring period should be as short as possible (less than one second). Determine the current which flows during the measurement and the voltage separately at the end of the measuring series. To achieve this, connect one of the digital multimeters in series as an ammeter and the other in parallel as a voltmeter. Perform at least 10 measurements. After each measurement, perform a pressure equalisation with the ambient atmospheric pressure by opening the three-way cock. The electrical current which flows during the measurements must not be too strong, i.e. it must be sufficiently weak to limit the pressure increase due to the heating of the gas to a maximum of 1 hpa. Fig. 3: Connecting the counter-timer. Fig. 2: Experimental set-up (C p ) 2 P PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D Göttingen

4 LEC For this reason it may be necessary to use only one heating wire. In order to be able to determine C p, replace the manometer with two gas syringes which are connected to the bottle via the three-way stopcock (see Fig. 2). One of the gas syringes is mounted horizontally and the other is positioned vertically with its plunger oriented downwards. While making measurements, the three-way cock must be positioned in such a manner that it only connects the vertical syringe with the bottle. To increase the plunger's mass, a nickel sheet metal electrode is attached to it with two-sided tape. Start the plunger rotating manually before the measurement so that it rotates throughout measurement. In this manner the static friction between the plunger and the body of the syringe is minimised and the measured values are sufficiently exact. If the plunger stops prematurely, the volume increase ( V) read on the vertically mounted syringe is too low. Determine the air pressure, which is required for the calculations, with the aid of a digital barometer. For the pressure in the gas container use a value which lies 14 hpa below the atmospheric pressure due to the weight of the syringe s plunger. For the determination of C p, also perform at least 10 measurements. After each measurement remove air from the system until the vertical syringe again exhibits the initial volume determined in the first measurement. To do this, turn the three-way cock in such a manner that both syringes and the bottle are connected with each other. Set-up and procedure with Cobra3 Perform the experimental set-up according to Fig. 4. Insert the two nickel electrodes into two holes in the threehole rubber stopper and fix the terminal screws to the lower ends of the electrodes. Screw two pieces of chrome nickel wire, which are each about 15 cm long, into the clamps between these two electrodes so that they are electrically connected in parallel. The wires must not touch each other. Insert the one-way stopcock into the third hole of the stopper and insert the thus-prepared stopper in the lower opening of the bottle. The 5 V output of the Cobra3 Basic-Unit serves as the power source. To determine C V, connect the precision manometer to the bottle with a piece of tubing. To do this, insert the second stopper, which has been equipped with the three-way stopcock, into the upper opening of the bottle (Fig. 4). The manometer must be positioned exactly horizontally. Read the pressure increase immediately after cessation of the heating process. The manometer must be filled with the oil which is supplied with the device. The scale is now calibrated in hpa. The riser tube of the manometer must be well wetted before each measurement. Connect the current sensor (A) to the first analog input of the Cobra3 Basic-Unit. To measure the voltage (V) connect the cords to the second analog input. Fig. 4: Experimental set-up (C V ). PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D Göttingen P

5 LEC Connect the Cobra3 Basic-Unit to the computer port COM1, COM2 or to USB port (use USB to RS232 Adapter). Start the Measure program and select Cobra3 Universal Writer Gauge. Begin recording the measured values using the parameters given in Fig. 6. Start the measuring procedure by activating the push-button switch. The measuring period should be as short as possible (ten seconds). Determine the current which flows during the measurement and the voltage separately at the end of the measuring series. Perform at least 10 measurements. After each measurement, perform a pressure equalisation with the ambient atmospheric pressure by opening the three-way cock. The electrical current which flows during the measurements must not be too strong, i.e. it must be sufficiently weak to limit the pressure increase due to the heating of the gas to a maximum of 1 hpa. For this reason it may be necessary to use only one heating wire. In order to be able to determine C p replace the manometer with two gas syringes, which are connected to the bottle via the three-way stopcock (see Fig. 5). Fig. 6: Measuring parameters Fig. 5: Experimental set-up (C p ) 4 P PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D Göttingen

6 LEC For the determination of C p, also perform at least 10 measurements. After each measurement remove air from the system until the vertical syringe again exhibits the initial volume determined in the first measurement. it follows that C V f 2 R (9) Theory and evaluation The first law of thermodynamics can be illustrated particularly well with an ideal gas. This law describes the relationship between the change in internal intrinsic energy U i, the heat exchanged with the surroundings Q and the constant-pressure change pdv. dq = du i + pdv (1) The molar heat capacity C of a substance results from the amount of absorbed heat and the temperature change per mole: n Number of moles One differentiates between the molar heat capacity at constant volume C V and the molar heat capacity at constant pressure C p. According to equations (1) and (2) and under isochoric conditions (V const., dv = 0), the following is true: and under isobaric conditions (p = const., dp = 0): Taking the equation of state for ideal gases into consideration: (2) (3) (4) pv = n R T (5) it follows that the difference between C p and C V for ideal gases is equal to the universal gas constant R. C p C V = R (6) It is obvious from equation (3) that the molar heat capacity C V is a function of the internal intrinsic energy of the gas. The internal energy can be calculated with the aid of the kinetic gas theory from the number of degrees of freedom f: where C 1 n dq dt C V 1 n du i dt C p 1 n k B = J/K (Boltzmann Constant) N A = mol -1 (Avogadro's number) Through substitution of a du i dv p dt dt b U i 1 2 fk B N A T n R = k B N A (8) (7) and taking equation (6) into consideration: (10) The number of degrees of freedom of a molecule is a function of its structure. All particles have 3 degrees of translational freedom. Diatomic molecules have an additional two degrees of rotational freedom around the principal axes of inertia. Triatomic molecules have three degrees of rotational freedom. Air consists primarily of oxygen (approximately 20%) and nitrogen (circa 80%). As a first approximation, the following can be assumed to be true for air: and f = 5 C V = 2.5 R C V = 20.8 J K -1 mol -1 C p = 3.5 R C p = 29.1 J K -1 mol -1. Determination of C p The energy Q is supplied to the gas by the electrical heater: where U C p a f 2 2 Q = U I t (11) I t Voltage which is applied to the heater wires (measured separately) Current which flows through the heater wires (measured separately) Period of time in which current flowed through the wires At constant pressure the temperature increase T induces a volume increase V. From the equation of state for ideal gases, it follows that: V nr p T V T T (12) and taking equation (2) into consideration, the following results from equations (11) and (12): C p 1 n U I t V V T (13) The molar volume of a gas at standard pressure p 0 = 1013 hpa and T 0 = 273.2K is: V 0 = l/mol. The molar volume is: V mol p 0 V 0 T 0 T p b R (14) PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D Göttingen P

7 LEC In accordance with the following, the number of moles in volume V is: (15) C p can be calculated using equation (13) under consideration of (14) and (15): (16) The pressure p used in equation (16) is calculated from the atmospheric pressure minus the pressure reduction due to the weight of the syringe's plunger. The pressure reduction is calculated from: where p n p V V mol C p p 0 V 0 T 0 p K m K g F K kg 9.81 ms 2 = m 2 = 1480 kg m -1 s -1 = 14.8 hpa = p a p K = 975 hpa 14.8 hpa = 960 hpa UI p t V Atmospheric pressure minus the pressure reduction due to the weight of the syringe's plunger p K Pressure reduction due to the weight of the plunger p a Measured atmospheric pressure (= kg) m K Mass of the plunger g Acceleration of gravity (= 9.81 m s -2 ) F K Area of the plunger (= m 2 ) The slope of the straight line in Fig. 7 is equal to with V t = U = 4.59 V and I = 0.43 A C p is obtained with equation (16) C p = J K -1 mol -1 ±7% Determination of C V Under isochoric conditions, the temperature increase T produces a pressure increase p. The pressure measurement results in an alteration of the volume which must be taken into consideration in the calculation: It follows from equations (3) and (1) that: C V 1 n ml s T p nr V V T p 1p V V p2 nr pv Q p V T and with equations (11) and (17) one obtains: C p V U I t p V n T p V V p (17) (18) (19) The indicator tube in the manometer has a radius of r = 2 mm. A pressure change of p = hpa causes an alteration of 1 cm in length; the corresponding change in volume is therefore: V = a p (20) Fig. 7: Volume change V as a function of the heat-up time t. U = 4.59 V, I = 0.43 A. where thus a = pr 2 1 cm 3 = cm hpa hpa (21) pvu I t ap p C V = nt (ap V) p (22) Taking equations (14) and (15) into consideration, it follows that: p 0 V 0 U I t C V = a (23) (ap V) p ap ap V b T 0 The slope of the straight line in Fig. 8 is equal to p t = hpa s 6 P PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D Göttingen

8 LEC Fig. 8: Pressure change p as a function of the heat-up time t. U = 4.59 V, I = 0.43 A As a consequence of heat losses to the surroundings, the experimentally determined values for C p and C V are somewhat larger than the theoretical ones. The difference between the molar heat capacities provides the value for R. The experimental result is R = C p C v = 9.27 J K -1 mol -1 ±9% Value taken from literature: R = 8.3 J K -1 mol -1 Note Using this apparatus, other gases (e.g. carbon dioxide or argon) can also be measured. These gases are then introduced through the stopcock on the bottom of the vessel. C v can be calculated using equation (23) if equation (21) is taken into consideration. With the atmospheric pressure p = 1011 hpa (this part of the experiment was done the next day), a volume of V = 10 l U = 4.59 and = 0.43 A the following value for C V is obtained: C V = J K -1 mol -1 ±5% Data and Results Literature values: C p(oxygen) = 29.4 J K -1 mol -1 C V(oxygen) = 21.1 J K -1 mol -1 C p(nitrogen) = 29.1 J K -1 mol -1 C V(nitrogen) = 20.8 J K -1 mol -1 R = J K -1 mol -1 = hpa l K -1 mol -1 Experimental results: C p (air) = 33 J K -1 mol -1 C v (air) = 26 J K -1 mol -1 PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D Göttingen P

9 LEC 8 P PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D Göttingen