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Heat and Work First Law of Thermodynamics 9.1 Heat Heat and Work Thermodynamic Processes Work Thermodynamics is the science of heat and work Heat is a form of energy Calorimetry Mechanical equivalent of heat Mechanical work done on a system produces a rise in temperature like heat added to the system. Work Heat input into a system can produce work 1calorie =4.184 J First Law of Thermodynamics The change in the internal energy of a system U, is equal to the heat input Q minus the work done by the system. ∆U = Q − W ∆ W = F∆ x ∆W = PA∆x = P∆V For the case of thermal expansion work is done by the system. Heat input Q Heat Q Internal Energy U Work W System The internal energy is the energy stored in the system. For an ideal gas the internal energy is the kinetic energy of the gas 1 Thermodynamic processes in an ideal gas PV diagram T1 T2 U2 U1 State 1 (P1, V1, T1) State 2 (P2, V2, T2 ) • The state of the ideal gas is determined by the three parameters, PVT. • A thermodynamic process is the transition between states with input or output of heat and work with changes in internal energy. • The internal energy U is a property of the state. ∆U determined by the initial and final state and is independent of path • The heat absorbed and work done in the process depend on the path. P • State 2 • State 1 V Each point in the diagram represents a State of the system The temperature T is not plotted but is not an independent variable. T can be calculated from P and V using the ideal gas law. The points of constant temperature on the PV diagram are hyperbola P= Thermodynamic processes x Path A P For constant T Work can be calculated if the process is reversible. x State 2 (T2, P2, V2) Path B nRT V Path A State 2 (T2, P2, V2) P x State 1 (T1, P1, V1) x State 1 (T1, P1, V1) V The change in U going from 1 to 2 is the same for the two paths. ∆UA =∆UB The change in Q and W going from 1 to 2 is different between the two paths. QA ≠ QB , WA ≠ WB Reversible process V We can calculate the work done in going from 1 to 2 if the change is a reversible process. i.e. it goes slowly through well defined states that are in quasi-equilibrium. Work cannot be calculated for an irreversible process. x Path A T is increased slowly from 0 to 100o C P State 2 (T2, P2, V2) ? x State 1 (T1, P1, V1) The temperature is changed very slowly so that the gas sample is at a uniform temperature. V We cannot calculate the work done in going from 1 to 2 if the process is irreversible. i.e. goes rapidly through states that are not well characterized and not in quasi-equilibrium. However, we can determine ∆U, since this is a state property. 2 Irreversible process Work done in a process dW = PdV W= ∫ Pdv V1 The gas is not in a well defined thermodynamic state as it is heated. The work is the area under the PV curve. Some thermodynamic processes expansion of ideal gas Question Find the work done in going from A to B along the line. V2 T constant 1. Constant Temperature processConstant T Isothermal 2. Constant Pressure process – Isobaric. e.g heating a balloon heat bath P constant 2P1 B P1 3. A Constant Volume process. Heating a gas thermometer T changes at constant V Adiabatic process – no heat exchange. Rapid compression or T changes expansion of a gas with V 4. 2V1 V1 T2 T is constant ∆U = 0 Increasing T Constant T Constant P Constant V Adiabatic (Q=0) P V constant Q=0 No contact with heat bath Isothermal volume change Thermodynamic processes T1 T changes at constant P U is constant All the heat goes into work W=Q • Work W= P= V2 V2 V1 V1 ∫ PdV = ∫ nRT dV V Q =W • nRT V W = nRTln V2 − nRTln V1 V W = nRTln V2 V1 Expansion V2 >1 V1 Compression work is positive work is done by the gas V2 < 1 work is negative V1 work is done on the gas 3 Constant Volume At constant volume W=0 Constant Pressure P2 , T2 ∆U = Q P no work is done all the heat goes into internal energy P1 , T1 We can use this to find ∆U V Q = nc V ∆T ∆U = nc V ∆T Q Constant Pressure Work W= V2 ∫ PdV = P(V2 − V1) = P∆V V1 Heat input Q = ∆U + P∆V This is true for all processes since U is a State function and only dependent on T. specific heat at constant volume Q = nc V ∆T + P∆V = nc V ∆T + nR∆T Q = nc P ∆T Specific heat at constant pressure, cP ∆U the specific heat of the gas cV depends on the structure of the gas molecule. n∆T Units J / mole ⋅ K cV = cP = c V + R Adiabatic Process the specific heat at constant P is larger than the specific heat at constant V. because work is done by the gas Adiabatic compression Heat input Q=0 The air (γ=1.40) in an automobile engine is compressed quickly so that appreciable heat exchange does not occur. For a compression ratio V1/V2 =10. Find the temperature of the gas compressed from an initial temperature of 20o C. ∆U= -W Work is done at the expense of internal energy Q=0 Define “Adiabatic exponent” γ c c +R R = 1+ γ = P = V cV cV cV γdepends on the nature of the gas, γ =1.40 for air. PV relationship TV relationship γ γ PV 1 1 = P2V2 γ −1 TV 1 1 = T2V2 PV γ = cons tan t γ −1 TV γ −1 = cons tan t 1 1 − P2V2 W = PV γ −1 Adiabatic compression Santa Anna Conditions T= 20o C The air (γ=1.40) in an automobile engine is compressed quickly so that appreciable heat exchange does not occur. For a compression ratio V1/V2 =10. Find the work done in compressing a gas from 1atm if the capacity is 2.8 l. P= 85 kPa P = 100 kPa T=? High Desert. Coast Santa Ana winds originate in the high desert region of California and is heated by adiabatic compress during the rapid descent to the coast. For the above conditions what would the temperature at the coast be? 4 Thermodynamic processes Work done in expansion One mole of air (γ=1.40) at P1 = 0.25 atm, T1 = 300 K, V1=0.1m3 expands by a factor of 2. Find the work done if the expansion is a) isobaric,b) isothermal c) adiabatic. Which process does the most work? T1 Defining Characteristic T constant ∆U=0 V constant W=0 P constant No Heat input Q=0 First Law Q=W ∆U=Q ∆U=Q-W ∆U=-W W=0 P(V2-V1) PV 1 1 − P2V2 γ −1 PVγ =constant TVγ-1=constant Work done by nRTln(V2/V1) the gas Other relations PV=constant Q=mCV∆T Q=ncP∆T cP=cP +R Temperature change in expansion V1=0.1m3 One mole of air (γ=1.40) at P1 = 0.25 atm, T1 = 300 K, expands by a factor of 2. Find the temperature change if the expansion is a) isobaric, b) isothermal c) adiabatic. Which process produces the highest temperature rise? P T2 V1 V2 V Heat input on expansion One mole of air (γ=1.40) at P1 = 0.25 atm, T1 = 300 K, V1=0.1m3 expands by a factor of 2. Find the heat input if the expansion is a) isobaric, b) isothermal c) adiabatic. What process results in the largest heat input? cV (air) =5/2R T1 T1 P P T2 V1 V2 V T2 V1 V2 V 5