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PHYS1001 Physics 1 REGULAR Module 2 Thermal Physics. PRESSURE IDEAL GAS EQUATION OF STATE KINETIC THEORY MODEL THERMAL PROCESSES. PHYSICS: FUN EXCITING SIMPLE. ap06/p1/thermal/ptE_gases.ppt. Overview of Thermal Physics Module:
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PHYS1001 Physics 1 REGULAR Module 2 Thermal Physics PRESSURE IDEAL GAS EQUATION OF STATE KINETIC THEORY MODEL THERMAL PROCESSES PHYSICS: FUN EXCITING SIMPLE ap06/p1/thermal/ptE_gases.ppt
Overview of Thermal Physics Module: • Thermodynamic Systems:Work, Heat, Internal Energy0th, 1st and 2nd Law of Thermodynamics • Thermal Expansion • Heat Capacity, Latent Heat • Methods of Heat Transfer:Conduction, Convection, Radiation • Ideal Gases, Kinetic Theory Model • Second Law of ThermodynamicsEntropy and Disorder • Heat Engines, Refrigerators
Kinetic-Molecular Model of an Ideal Gas Thermal Processes * Ideal gas, Equation of state (§18.1 p611) * Kinetic-molecular model of an ideal (results only – not the mathematical derivations) (§18.3 p619) * Heating a gas: heat capacities, molar heat capacity (§17.5 p582 §18.4 p626 §19.6 p658 §19.7 p659) * First Law of Thermodynamics: Internal Energy, Work, Heat, Paths between thermodynamic states (§19.1 p 723-725, §19.2 p725-728, § 19.3 p728-729, §19.4 p729-735) * Thermal Processes and pV diagrams: Isothermal, Isobaric Isochoric (constant volume gas thermometer), Adiabatic Cyclic (§19.5 p735-737, §19.8 p741-744, §17.3 p644-645 References: University Physics 12th ed Young & Freedman
Phases of matter Gas - very weak intermolecular forces, rapid random motion high temp low pressure Liquid- intermolecular forces bind closest neighbours low temp high pressure Solid- strong intermolecular forces
Quantity of a gas number of particles N mass of particle m molar mass M (kg.mol-1) mass of 1 mole of a substance number of moles n ( mol) 1 mole contains NA particles Avogadro's constant NA = 6.023x1023 mol-1 1 mole is the number of atoms in a 12 g sample of carbon-12 1 mole of tennis balls would fill a volume equal to 7 Moons The mass of a carbon-12 atom is defined to be exactly 12 u u atomic mass units, 1 u = 1.66x10-27 kg (1 u)(NA) = (1.66x10-27)(6.023x1023) = 10-3 kg = 1 g mtot = N m If N = NA mtot = NA m = M M = NA m n = N / NA = mtot / M
1.00 kg of water vapour H2O M(H2O) = M(H2) + M(O) = (1 + 1 + 16) g = 18 g = 1810-3 kg n(H2O) = mtot / M(H2O) = 1 / 1810-3 = 55.6 mol N(H2O) = nNA = (55.6)(6.0231023) = 3.351025 m(H2O) = M / NA = (1810-3) / (6.0231023) kg = 2.9910-26 kg 1 amu = 1 u = 1.6610-27 kg m(H2O) = 18 u = (18)(1.6610-27) kg = 2.9910-26 kg
Pressure P Is this pressure? What pressure is applied to the ground if a person stood on one heel?
Patmosphere = 1.013105 Pa ~1032 molecules strike our skin every day with an avg speed ~ 1700 km.s-1
Rough estimate of atmospheric pressure air ~ 1 kg.m-3g ~ 10 m.s-2h ~ 10 km = 104 m p = F / A = mg / A = V g / A = A h / A = g h Patm ~ (1)(10)(104) Pa Patm ~ 105 Pa
Famous demonstration of air pressure (17thC) by Otto Van Guerickle of Magdeburg ? … and all the king's horses … What force is required to separate the hemispheres? Is this force significant?
Famous demonstration of air pressure (17thC) by Otto Van Guerickle of Magdeburg p = 1x105 Pa R = 0.30 m A = 4R2 F = p A F = (105)(4)(0.3)2 N F = 105 N
Gauge and absolute pressures Pressure gauges measure the pressure above and below atmospheric (or barometric) pressure. P = P = 1 atm = 101.3 kPa = 1013 hPa = 1013 millibars = atm 0 760 torr = 760 mmHg Gauge pressure P 200 g Absolute pressure P 100 300 0 400 P = P + P g atm P = 200 kPa P = 100 kPa g atm P = 300 kPa
Ideal Gases – equation of state (experimental law) p V = n R T = N k T R, Universal gas constant (same value for all gases) R = 8.314 J.mol-1.K-1 Boltzmann constant k = 1.38x10-23 J.K-1 k = R / NAR = kNA must be in kelvin (K)
All gases contain the same number of molecules when they occupy the same volume under the same conditions of temperature and pressure (Avogadro 1776 - 1856) p V = n R Tn = N / NA= p V / R T Ideal gas, constant mass (fixed quantity of gas)
Boyle's Law (constant temperature) p = constant / V Charles Law (constant pressure) V = constant T Gay-Lussac’s Law (constant volume) p = constant T
Thermodynamic system (ideal gas) work internal energy U = Q – W = n CVDT p V = n R T p V = N k T k = R / NA mtot = n M N = n NA p V T U S heat Q = n C DT CV or Cp mtot N n Q = 0 pV = constant T V-1 = constant
Provided the temperature is not too high (< 3000 K), a diatomic molecule has 5 degrees of freedom
Kinetic–Molecular model for an ideal gas (p619) Large number of molecules N with mass m randomly bouncing around in a closed container with Volume V. z Experimental Law Kinetic-Molecular Model (Theory) y x For the two equations to agree, we must have:
Total kinetic energy for random translational motion of all molecules, Ktr is the average translational kinetic energy of a single molecule Average translational KE of a molecule For an ideal gas, temperature is a direct measure of the average kinetic energy of its molecules.
At a given temperature T, all ideal gas molecules have the same average translational kinetic energy, no matter what the mass of the molecule energy stored in each degree of freedom = ½ k T Theorem of equipartition of energy (James Clerk Maxwell): The thermal energy kT is an important factor in the natural sciences. By knowing the temperature we have a direct measure of the energy available for initiating chemical reactions, physical and biological processes.
Internal energy U of an ideal gas PE = 0 Degrees of freedom (T not too high) monatomic gas, f = 3 diatomic gas, f = 5, polyatomic gas, f = 6 Only translation possible at very low temp, T rotation begins, T oscillatory motion starts
Heating a gas Molar heat capacity
Heating a gas at constant volume 1st Law Thermodynamics U = n CVDT Q Constant volume process V = 0 W = 0 All the heat Q goes into changing the internal energy U hence temperature T Larger f larger CV smaller T for a given Q
Heating a gas at constant pressure W 1st Law Thermodynamics Q Constant pressure process W = p V It requires a greater heat input to raise the temp of a gas a given amount at constant pressure c.f. constant volume Q = U + WW > 0
Thermal processes T1 p1 V1 U1 S1 T2 p2 V2 U2 S2 W n N mtot Q Reversible processes
Isothermal change T = 0 Boyle’s Law (1627 -1691) T1= T2 p1V1 = p2 V2 U= 0pV = n R T
isotherm W is the area under an isothermal curve
Isobaric (p = 0) W = pV Q = n Cp T U = Q – W = n CV T T2 > T1U > 0 W > 0 Q > 0 W < Q V1/T1=V2/T2 isobar
Adiabatic (Q = 0) U = - W CV = (f / 2) RCp = CV + R = (f / 2 +1)R = Cp / CV = (f + 2) / f pV = constant diatomic gas f = 5 T V-1 = constant = 7 / 5 = 1.4
1 to 2: Q = 0 T1 > T2W > 0 U < 0 W adiabat An adiabat steeper on a pV diagram than the nearby isotherms since > 1
Adiabatic processes can occur when the system is well insulated or a very rapid process occurs so that there is not enough time for a significant heat to be transferred eg rapid expansion of a gas; a series of compressions and expansions as a sound wave propagates through air. Atmospheric processes which lead to changes in atmospheric pressure often adiabatic: HIGH pressure cell, falling air is compressed and warmed.LOW pressure cell, rising air expands and cooled condensation and rain.
convergence divergence divergence convergence HIGH LOW - more uniform - less uniform conditions - inhibits cloud conditions - encourages cloud formation formation sunshine Atmospheric adiabatic processes Q = 0 U = - W T V-1 = constant Burma Cyclone 5 May 2008 +50 000 killed ?
Cyclic Processes: U = 0 reversible cyclic process
Problem E.1 Oxygen enclosed in a cylinder with a movable piston (assume the gas is ideal) is taken from an initial state A to another state B then to state C and back to state A. How many moles of oxygen are in the cylinder? Find the values of Q, W and U for the paths A to B; B to C; C to A and the complete cycle A to B to C to A and clearly indicate the sign + or – for each process. Does this cycle represent a heat engine?
Thermodynamic system (ideal gas) work internal energy U = Q – W = n CVDT p V = n R T p V = N k T k = R / NA mtot = n M N = n NA p V T U S heat Q = n C DT CV or Cp mtot N n Q = 0 pV = constant T V-1 = constant
Solution Identify / Setup oxygen diatomic f = 5 CV = (f / 2) RCp = CV + R = (f / 2 +1) R CV = 5/2 RCp = 7/2 R R = 8.315 J.mol-1.K-1 CV = 20.8 J.mol-1.K-1 Cp = 29.1 J.mol-1.K-1 p V = n R T = N k T
Execute At A
1 A to B is isobaric T1= TB – TA = (400 – 100) K = 300 K pA = pB = p1 = 40 kPa = 4.00104 Pa V1 = (0.080 – 0.020) m3 = 0.060 m3 W1 > 0 since gas expands W1 = p1 V1 = (4.0104)(0.06) = 2.4103 J U1 > 0 since the temperature increases U1 = n CV T1 = (1)(20.8)(300) J = 6.2103 J Q1 > 0 since U1 > 0 and U1 = Q1 – W1 > 0 Q1 > W1 > 0 Q1 = n Cp T1= (1)(29.1)(300) J = 8.7103 J Check: First law U1 = Q1 - W1 = (8.73103 – 2.4103) J = 6.3103 J Q1
2 B to C is isochoric T2= TC – TB = (800 – 400) K = 400 K V2 = 0 m3 W2 = 0 since no change in volume U2 > 0 since the temperature increases U2 = n CV T2 = (1)(20.8)(400) J = 8.3103 J Q2 = U2 since W2 = 0 Q2 = 8.3103 J Q2
3C to A T3= TA – TC = (100 – 800) K = -700 K pA = 40 kPa = 4.0104 PapC = 80 kPa = 8.0104 PapCA = 4.0104 Pa VA = 0.02 m3VC = 0.08 m3 V3= 0.06 m3 W3 < 0 since gas is compressed W3 = area under curve = area of rectangle + area of triangle W3 = - { (0.06)(4.0104) + (½)(0.06)(8.0104- 4.0104)} J = - 3.6103 J U3 < 0 since the temperature decreases U3 = n CV T3 = (1)(20.8)(-700) J = - 14.6103 J Q3 = U3 + W3 Q3 = (- 14.5103 - 3.6103) J = - 18.2103 J Q3
Complete cycle U = 0 J Refrigerator cycle: |QH| = |QC| +|W| |W| TC TH |QC| |QH|