THERMODYNAMICS, ‘eli san engine: she equi fuel and oxygen to burnt andthe results work hat dives her forward tr exsees ase snore expelled inher evaporating scat. Thermodynamics i the study of heat and work epertuy, Work ie toner of et is a transfer of encray doe to a diference of by mechanical means, not due ta tnpetutute difference. The First law of themodynamics inks the to ina general satement of energy conservation: the heat O added toasystem munis thet Work I done bythe system equals the change is aera energy AU ofthe stem AU QW There ae many uses fora hes engine sch = toder calharning power plan, css locomotive, The photogrph shows a team Losomtive wich produces seam That does Work ona piston that moves linkage to tum lncomative wheel, The esinsyof any engine imi by teas dered inthe socond law of thermodynamic. This gst lw is beat saad a terms of quad called entropy which i not conserved. tut inscad i contained always to inereane in any fel poses. Entropy is Inetsre of disorder The second law of thermodyais lus tha sme moves forward the disorder in theumiverse increase, We alan dass ratcal ters sh as heat engines heat pump, rigsatrs. a8 sr conttones LEARNING GOALS + After studying this chapter students can describe the properties of a monatomic ideal gas + After studying this chapter students can analyze changes in the state of an ideal gas by applying the laws of thermodynamics We now direct our attention to the study of thermodynamies, which involves situations in which the temperature or state (solid, liquid, gas) of a system changes due to energy transfers. As we shall sce, thermodynamics is very changes successful in explaining the bulk properties of matter and the correlation between these properties and the ‘mechanics of atoms and molecules. System and Environment In thermodynamics, there are two important terms to know, they are sys > System is everything becoming our observation object > Environment is everything which is outside the system External Work ‘The gas does work with its magnitude can be expressed by the following equation W=p.av W=(+) if the system (gas) does work W=(-) if work is provided by the environment to the system Where W_ mechanical work of gases (J) p= gas pressure (Pa) AV change of volume (m*) Exei 1. A gas is compressed at constant pressure 2.10° Pa from a volume of 2 m’ to a volume of 0.5 m°. What is the work done to the gas? Ifthe temperature initially was 27° C. what is the final temperature of the gas? Ans. - 3e5, 75K CALCULATING THE WORK FROM A P-V GRAPH. Ifa graph is given that relates pressure P and volume V, then the amount of work can be calculated by calculating, the area of the graph under the curve. We area of the graph2. How much work is done in the process mira) a) Was b) Wie o) Wo 4) Woot (12 kd) ©) If the engine works 5 cycles per 20 seconds, what is the engine's output power? GW) Mot) ‘Thermodynamics Processes ‘The state of the ideal gas in a closed room can be altered by giving a certain treatment to the gas system. The process of changing the gas state can be classified into four process, they are isothermal process, isobaric process, isochoric process and adiabatic process. a, Isothermal Process Isothermal process is the change of gas state at constant temperature. From the ideal gas state equation pV =nkT, because nRT has a constant value, we get p.V = constant or P.Vi W=nkT Int? or W=P.V. In Note: n= the amount of the mole of gases (mole) R= universal gas constant= 8.31 J/mol. K T= the temperature (K) W= the work done by the gas (J) b. Isobaric Process Isobaric process is the change process of gas state at constant pressure. External work done by gas in isobaric process is formulated as follow W=pav Note: _p= the pressure (Pa) AV= the change of volume (m*) ¢. Adiabatic Process Adiabatic process is the process change of a gas state which does not ‘experience any transfer of heat or there is no heat entering or coming out of the system (gas). Pla pV” = cons cu PM = Phe Isothermal Tit atv 8 Po Adiabatic c Y CG c 777s the rato of heat capacities or adiabatic index ofthe gas. Extemal work done by gas in adiabatic process is formulated as follows (P2Ve— PVs) For monoatomic gas 1” For diatomic gas W4d. Isochoric Process Isochoric process is the change process of gas state at constant volume. ‘The work done by gas=W=0 Because V is constant and n R is always constant, then Aum Finding y (Laplace's constant) ‘ys the ratio of heat capacities or adiabatic index of the gas. © -G C)= heat capacity at constant pressure (J/K) ‘C= heat capacity at constant volume (J/K) Monatomic, ex He ca 5 a gmk gmk Cy 3 5 nk 2 mR Y a 7 3 5 3. Four moles of an ideal gas is expanded isothermally and reversibly as seen in figure below with initial temperature of 27°C. Find the work done by gas! Use In 2= 0.693 (ans 69125) P nam _ 6 atm x : v 4. ‘The compression ratio of an engine's cylinder is 15 to 1. This means that air in the eylinder is compressed to 1/15 of its ial volume. Ifthe initial pressure is | atm and the initial temperature is 27°C, assume y = 1.40 for air. nd the final temperature of the air in the cylinder and the final pressure of the air in the cylinder. (ans T-=886K, P2=44.3 atm) 5. The pressure of a monatomic ideal gas (y=5/3) doubles during an adiabatic compression. What is the ratio of the final volume to the initial volume? (2° or 1.52) 6, Imagine you do 2000 J of work on a system adiabatically. The work is used to compress one-half mole of a ‘monatomic ideal gas, causing its absolute temperature to double. What is the initial temperature of the gas, R=8.31 JimoLK? 321 K) The First Law of Thermodynamics ‘The First Law of Thermodynamics states that “Though heat energy has tuned into change of intemal energy and external work of gas, the amount of all energy is always constant’ aU=Q-W a, In isothermal process ‘The change of internal energy AU = 0, because the change of temperature 1Inisochorie process Work done by gas W 0 because the change of volume AV = 0 AU=Q in isobaric process AU=Q-W AU=Q-pAV in adiabatic process > Q-0 AU=Q-W AU=0-W AU=-W cal gas (monoatomic) expand from I to F along the three paths indicated in figure below, Two moles of i namely LAF, IF, and IBF Peawm For each path made by the gas, namely the IAF. IF and IBF paths. find a)work £800;500;200 b) AU 4-600 o) heat {200:-100:-400 A gas is compressed at a constant pressure of 0.8 atm from 9 L to 2 L. In the process, 400 J of energy leaves the gas by he (a) What is the work done on the gas? (b) What is the change in its internal energy’? A system consists of 1.5 kg of water at a temperature of 73 °C, About 30 kJ of work is done on the system by (567 (67 stirring, and 10 kcal of heat is removed. If | cal = 4.2 J, then (a) How much does the intemal energy of the system change (decrease/increase)? (b) What is the final temperature of the system’? (12K: 71)Heat Capacity Is the amount of energy required to raise the temperature of the gas by 1 K or 1°C. c= 2 A © =the heat capacity (VK) Q =heat absorbed (J) AT = the change in temperature (K) Co= the gas heat capacity at constant pressure (J/K) Cy =the gas heat capacity at constant volume (I/K) Cae n=the amount of gas (mole) R=8.31 Jmol. K GAS HEAT CAPACITY (Symbol: big C) a, inan isochoric process (V = constant) For monatomic gas ~» W = 0 —>AU= Qv = nRAT AT 2 C= Sn 6 For diatomic gases—> C,=2nR b. for isobaric process (p = constant) For monatomic gas > Cp Cy =n. 8 C= 2nR 2 2 For diatomic gases Cr=7nR ‘The relationship between the two can be formulated as —> Cp - Cy=n.R SPECIFIC HEAT OF GAS (Symbol: small c) a = specific heat of gas in units of J/kg. K) =Molar heat capacity (J/mol.K) ¢ Gy, = 0 maT "WAT For monatomic gases, the values of em and em are 3 a For isochoric processes ¢,,, = R b. for isobaric proces Cp =2R a ‘The relationship between the two can be formulated as — ¢)~ ey:Monatomicjex He Diatomic, ex O: G 5 7 er ank y 5 c 5nk 1 a 5 ce 7 aR Cm 2 sR 10, Ina container, there are 2 moles of He gas (Ar=4). Calculate: a. heat capacity of He gas at constant pressure b, molar heat capacity of He gas at constant pressure «. specific heat of He gas at constant pressure Ans: a. Because He is monoatomic gas, then heat capacity C, 2, 8.31= 41.55 JK 4355, b, molar heat capacity ey = 2 $0 Gm , i 0.78 = 20.78 <= 5195 Iihs.K 20.78 Wmol.K ©. specific heat o= A total of 56.10” kg of nitrogen is heated from 270 K to 310 K. If this nitrogen is heated in a vessel that is free to expand, 2.33 kJ of heat is required. If this nitrogen is heated in a rigid vessel (it cannot expand), 1.66 KJ of heat is required. (Mr N:=28), Count a. heat capacity of nitrogen at constant P b. The heat capacity of nitrogen at V is constant ¢. the universal gas constant Ans, a. The nitrogen in nature is diatomic gas —+ Nz ‘We know from problem that AT = 310 - 270 =40 K, Free to expand, this means isobaric + Q=2330J Ina rigid vessel, this means isochoric + Qu= 1660 3 56.107? ke 3510-5 kg/mote mole The mole of nitrogen is Q= Com AT 2330 = Cam 40 Com b. Q= Cyn. AT 1660 = Cy. 40+ Cy 41.5 YK =58.25 VK mR = 41.55 J/K, ce Cp Cy=aR 58.25 — 41,5 =2.R + 16,75 = 2R > R= 8.38 J/mol.KThermodynamics Cycle A thermodynamic cycle consists of linked sequences of thermodynamic processes that involve transfer of heat and work into and out of the system, while varying pressure, temperature, and other state variables within the system, and that eventually returns the system to its initial state. In the process of passing through a cycle, the working fluid (system) may convert heat from a warm source into useful work, and dispose of the remaining heat to a cold sink, thereby acting as a heat engine. Conversely, the cycle may be reversed and use work to move heat from a cold source and transfer it to a warm sink thereby acting as a heat pump. If at every point in the cycle the system is in thermodynamic equilibrium, the cycle is reversible, Whether carried out reversible or irreversibly, the net entropy change of the system is zero, as entropy is a state function. Some example thermodynamic cycles and their constituent processes are as follows. Cycle | Process 1-2 | Process2-3 | Process 34 | Process 4-1 Notes (Compression) | (Heat Addition) (Expansion) (Heat Rejection) Power cycles normally with external combustion - or heat pump cycles: Bell Coleman | adiabatic isobaric ‘adiabatic | isobaric A reversed Brayton cycle Brayton | adiabatic isobaric adiabatic [isobaric Fetengines ‘aka first Eriesson eycle from 1833 Carnot isentropic | isoxhermal isentropic | isothermal Erlesson isothermal | isobaric isothermal | isobaric the second Eriessom eyele from 1853 Seuderi | adiabatic variable ‘adiabatic | isochorie pressure and volume Stirling | isothermal | isochorie isothermal | isochorie Stoddard | adiabatic isobaric ‘adiabatic | isobarie Power eyeles normally with internal combustion: Diesel [adiabaic —_|isohare ‘adiabatic | isochore Lenoir [isobaric isochoric | adiabatic | nohare Pale jes (Note: 3 ofthe 4 processes are different Otto | adiabatic | sochorie [adiabatic | sochore Gasoline / perl engines Rankine [adiabatic | sohare adiabatic | bobare ‘Steam engine Carnot Cycle ‘The Camaot cycle is important because it represents the maximum efficiency that any heat engine can achieve. It is a theoretical cycle that consists of four reversible processes: isothermal expansion, adiabatic expansion, isothermal compression, and adiabatic compression In the Camot engine, W = Qi ~ Q, so the efficiency of Camot engine can be formulated as follows n=O # 100% orn=[i- rao ot a a 2 Because W = Q\ - Qo, then W == 100% n=GF According to Kelvin,Note: efficiency (%) 1 absorbed heat (J) ) = the released heat (J) the work done by gas (J) the higher temperature (K) the lower temperature (K) a 1 Te rf anh Isothermal expansion @ @ dora bre ‘Adiabatic Adiabatic ‘compression expansion (2) Next the gas expands adiabatically from "b" to "<"— no heat i exchanged, but the temperature drops to 7, , (G3) The gas is then compressed at constant temperature T. path ed, and heat Q, flows out. (4) Finally, the gas is compressed adiabatically, path da, back to its original state 8 FIGURE The Camot cycle. Heat engines work in Few cycle, and the eyle for the theoretical Carnot engine Isothermal bezins at point “a” on this PV diagram for an ideal gas ‘compression (1) The gas is first expanded isothermally, with the addition ‘of heat Qy, along the path “ab” at temperature Ty 12. A Camot engine operates with an efficiency of 40% when the temperature of its hot reservoir is 800 K. Assuming that the temperature of the cold reservoir remains the same, what must be the temperature of the (960 K) 13, A steam engine operating between a boiler temperature of 220°C and a condenser temperature of 35°C delivers hot reservoir in order to increase the efficiency to 50%! 8 hp (I hp=746 W). If its efficiency is 30 percent of that for a Carnot engine operating between these temperature limits, how many calories are absorbed each second by the boiler? How many joules are exhausted to the condenser cach second? ——_(#=0.113, 52 KJ, 46,8 KI) ‘The Seconds Law of Thermodynamics ‘To explain the lack of reversibility on The first law of thermodynamics, scientists in the later half of the nineteenth century formulated a new principle known as the second law of thermodynamics, Experimental evidence suggests strongly that itis impossible to build a heat engine that converts heat completely to work—that is, an engine with 100% thermal efficiency. This impossibility is the basis of one statement of the second law of thermodynamies, as follows It is impossible for any system to undergo a process in which it absorbs heat from a reservoir at a single temperature and converts the heat completely into mechanical work, with the system ending in the same state in which it began. It was not until the later half of the nineteenth century that the second law of thermodynamics was finally stated in a general way—namely, in terms of a quantity called entropy. introduced by Clausius in the 1860s. Entropy. unlike heat, is a function of the state of a system. That is, a system in a given state has a temperature, a volume, a pressure, a mass, and also has a particular value of entropy. In the next Section, we will see that entropy can be interpreted as a measure of the order or disorder of a system, When we deal with entropy—as with potentialenergy—it is the change in entropy during a process that is important, not the absolute amount. According to ‘Clausius, the change in entropy S of a system, when an amount of heat Q is added to it by a reversiblet process at constant temperature, is given by Where AS= the change of entropy (W/K) Q =heat entrering / evening system (J) T absolute temperature (K) Sample problem ‘An ice cube of mass 56 g is taken from a storage compartment at 0°C and placed in a paper cup. After a few ‘minutes, exactly half of the mass of the ice cube has melted, becoming water at 0°C. Find the change in entropy of the ice/water, Ans. Q= mL = (0.028 kg)(333 kl/kg) = 3k Sample problem ‘The figure below shows that 1,200 J of heat flows spontaneously from a hot reservoir at 600 K to a cold reservoir at 300 K, Determine the entropy of the system, Assume no other changes occur. Answer: It is known that Q= 1,200.7 aang as. 600 K, and T2 200). 2k 00K. Changes in the entropy of the hot reservoir: ROK 12003 = 12001 nay Cold reservoir entropy change: **? ~ 7, "300K ~ 1/1 - So the total change in entropy JK reenirdingn Refrigerators, Air Conditioners, and Heat Pumps (a) Typical refrigerator system. The electric compressor motor forces a gas at high pressure through a heat exchanger (condenser) on the rear outside wall of the refrigerator, where is given off and the gas cools to become “ % liquid. The liquid passes from a high-pressure region, via a valve, to low-pressure tubes on the inside walls of the reffigerator, the liquid evaporates at this lower pressure and 2 thus absorbs heat (Q1) from the inside of the re a ‘The fluid returns to the compressor, where the cycle begins AC, sual.) Schematic diagram, ike Fig, below ‘The operating principle of refrigerators, air conditioners, and heat pumps is just the reverse of a heat engine. Each operates to transfer heat out of a cool environment into a warm environment. As diagrammed in Fig, belowBy doing work WV, heat is taken from a low-temperature region, (such as inside a refrigerator), and a greater amount of heat is exhausted at a high temperature, (the room). Heat is removed from cooling coils inside the refrigerator and heat is given off by coils outside the rear of the refrigerator, Figure above. You can often fee! this heated air coming out beneath the refrigerator. The work His usually done by an electric motor which compresses a fluid, as illustrated in Fig, above, (We assume, and Qi, Qu, Ware all positive). A perfect refrigerator—one in which no work is required to take heat from the low-temperature region to the high+ temperature region: is not possible. This is the Clausius statement of the second law of thermodynamics, already ‘mentioned in Section before: it can be stated formally as “no device is possible whose sole effect is to transfer heat from one system at a temperature into a second system at a higher temperature To make heat flow from a low-temperature object (or system) to one at a higher temperature, work must be done, ‘Thus, there can be no perfect refrigerator. ‘The coefficient of performance (COP) of a reftigerator is defined as the heat removed from the low-temperature area (inside a refrigerator) divided by the work IV done to remove the heat (Figure above): & te cop=% cop =~ Sample problem A freezer has a COP of 2.8 and uses 200 watts of power. How long would it take to freeze an ice-cube tray that contains 600 g of water at 0°C. Ans. a (0,600 kg) (3.33. 108 Hkg) = 2. 10°J is the total energy that needs to be removed from the water. The freezer does work at the rate of which is the work. Wit ean do int soconds, We solve for: For W, we ean also use Eq, Cop = 228-22, wa71428 3 ‘Thus W= P.t—> 71428 = 200.1 t= 357s