Zeroth Law of Thermodynamics Statement: If a body 1 is in thermal equilibrium with body 2 and body 3, then the body 2 and body 3 are also in thermal equilibrium with each other sistem 1 ‘ane ay Figure 1 ‘Two systems 1 and 2 with independent variables ( Us, Vs, Nr) and (Uz, V2, Nz) are brought into contact with each other through a diathermal wall (figure 1). Let the system 1 be hot and system 2 be cold Because of interaction, the energies of both the systems, as well as their independent properties undergo 2 ‘a change. The hot body becomes cold and the cold body becomes hot. After sometime, the states of the two systems do not undergo any further change and they assume fixed values ofall thermodynamic properties. These two systems are then said to be in a state of thermal equilibrium with each other. The two bodies which are in thermal equilibrium with each other have a common characteristic called temperature. Therefore temperature is a property which has the same value forall the bodies in thermal equilibrium: ‘Suppose we have three systems 1, 2 and 3 placed in an adiabatic enclosure as shown in figure 2. ‘Adiabatic wall Daathermal wall System 1 [System 2 System 1 System 2 | UKM | eu UMM | Diathermal wail (8) (A) Figure 2 ‘and 2 do not interact with each other but they interact separately with systems 3 through a “Then system 1 is in thermal equilibrium with system 3 and system 2 is also in thermal n we can say that though system 1 and 2 are not interacting, they are The systems 1 diathermal wall equilibrium with system 3. By intuitior in thermal equilibrium with each other.‘Suppose system 1 and 2 are brought into contact with each other by replacing the adiabatic wall by a diathermal wall as shown in figure 2 (B). Further they are isolated from system 3 by an adiabatic wall Then one observes no change in the state of the systems 1 and 2. Temperature Scale Based on zeroth law of thermodynamics, the temperature of a group of bodies can be compared by bringing a particular body (a thermometer into contact with each of them in turn. To quantify the measurement, the instrument should have thermometric properties. These properties include: The length of a mercury column in a capillary tube, the resistance (electrical) of a wire, the pressure of a gas ina closed vessel, the emf generated at the junction of two dissimilar metal wires etc. are commonly used thermometric properties, To assign numerical values to the thermal state of a system, itis necessary to establish a temperature ‘scale on which temperature of a system can be read, Therefore, the temperature scale is read by assigning numerical values to certain easily reproducible states. For this purpose, itis customary to use ‘a. Ice Point: The equlibrium temperature of ice with air saturated water at standard atmospheric pressure which is assigned a value of 0°C. b. Steam Point: The equilibrium temperature of pure water with its own vapor at standard atmospheric pressure, which is assigned a value of 100°C. This scale is called the Celsius Scale named after Anders Celsius. Perfect Gas Scale {An ideal gas obeys the relation where Ris the Universal Gas Constant ( R = 8.314 Jimol K). This equation is only an approximation to the actual behavior of the gases. The behavior of al gases approaches the ideal gas limit at sufficiently low pressure (in the limit P ~ 0). The perfect gas temperature scale is based on the observation that the temperature of a gas at constant volume increases monotonically with pressure. If the gas pressure is made to approach zero, the gas behavior follows the relation pe =RT Ic Figure 3 shows a constant volume gas thermometer. The bulb Reference mak s is placed in the system whose temperature is to be measured. ‘The mercury column is so adjusted that the level of mercury stands atthe reference mark S . This ensures that the volume of the gas is held at a constant value. Let the pressure of the renvie gas be read as P, Let a similar measurement be made when oe the gas bulb is maintained at the triple point of water, Py. We = ccan obtain triple point by putting water and ice in an insulated chamber and evacuating air ( which is then replaced by water vapour) Figure 3 The temperature of the triple point of water has been assigned a value of 273.16 KPractice Questions-Set 1 Q.1 - An artificial satellite revolves round the earth with a relative velocity of 800 m/s. If acceleration due to gravity is 9 m/s2 and gravitational force is 3600 N, calculate its kinetic energy. Q.2- The specific heat capacity of the system during a certain process is given by en = (0.4 + 0,004 T) ki/kg°C. If the mass of the gas is 6 kg and its temperature changes from 25°C to 125°C find: (i) Heat transferred; (ii) Mean specific heat of the gas. Q.3- A temperature scale of certain thermometer is given by the relation (t= a /» p + b) where a and b are constants and p is the thermometric property of the fluid in the thermometer. If at the ice point and steam point the thermometric properties are found to be 1.5 and 7.5 respectively what will be the temperature corresponding to the thermometric property of 3.5 on Celsius scale. Q.4- Gas from a cylinder of compressed helium is used to inflate an inelastic flexible balloon, originally folded completely flat, to a volume 0.6 m3. If the barometer reads 760 mm Hg, what the amount of work done upon the atmosphere by the balloon? Sketch the system before and after the process. It is assumed that the pressure in the balloon is atmospheric at all times. since the balloon fabric is light, inelastic and unstressed Lato tty) 9 Fearn ONE KPa Figure ~ Hint Q.S- The properties of a closed system change following the relation between pressure and volume as pV = 3.0 where p is in bar V is in m3. Calculate the work done when the pressure increases from 1.5 bar to 7.5 bar. Q.6- To a closed system 150 kJ of work is supplied. If the initial volume is 0.6 m3 and pressure of the system changes as p = 8 4V, where p is in bar and V is in m*, determine the final volume and pressure of the system,G Practice Set irst Law of thermodynam 1 Asa result of some process, the internal energy of a system is increased. According to the first law of thermodynamics. MEm = Q + W . How can one tell that the increase was due to orderly macroscopic work W or due to the flow of energy through disorderly microscopic means Q” (a) By measuring the temperature of the system before and after the process (b) By measuring the temperature of the surroundings before and after the process (c) It is not possible to distinguish between W and Q (d) Both (a) and (b) are correct 2. Man leamt the use of fire to raise the temperature of objects much earlier than the use of mechanical Work, © g in steam engines. Could you think of a reason why this could be true? 3- A fluid system undergoes a non-flow frictionless process following the pressure-volume relation as p= S/V + 15 where p isin bar and V is in m3. During the process the volume changes from 0.15 m' 100.05 m’ and the sy stem rejects 45 kJ of heat. Determine (1) Change in internal energy (1H) Change in enthalpy 4- S000 J of heat are added to two moles of an ideal monatomic gas, initially at a temperature of $00 K. while the gas performs 7500 J of work. What s the final temperature of the gas” 5- Compute the intemal energy change and temperature change for the two processes involving | mole of an ideal monatomic gas. (a) 1500 J of heat are added to the gas and the gas does no work and no work 1s done on the gas (b) 1500 J of work are done on the gas and the gas does no work and no heat is added or taken away from the gas 6- 2000 J of heat is added to a system and 2500 J of work is done on the system. What is the change in internal energy of the system?her nami ork, Heat Work Work is said to be done when a force moves through a distance. If a part of the boundary of a system undergoes a displacement under the action of a pressure, the work done W is the product of the force (pressure x area), and the distance it moves in the direction of the force. Fig (a) illustrates this with the conventional piston and cylinder arrangement, the heavy line defining the boundary of the system. Fig. 2.31 (b) illustrates another way in which work might be applied to a system. A force is exerted by the paddle as it changes the momentum of the fluid, and since this force moves during rotation of the paddle work is done. (a) Sign convention: If the work is done by the system on the surroundings, eg. when a fluid expands pushing a piston outwards, the work is said to be positive. ie, Work output of the system = + W _ If the work is done on the system by the surroundings, eg, when a force is applied to a rotating handle, or to a piston to compress a fluid, the work is said to be negative. i.e, Work input to system = - W Heat Heat (denoted by the symbol Q), may be, defined in an analogous way to work as follows : “Heat is ‘something’ which appears at the boundary when a system changes its state due to a difference in temperature between the system and its surroundings”. Heat, like work, is a transient quantity which only appears at the boundary while a change is taking place within the system. It is apparent that neither JW or f Qare exact differentials and therefore any integration of the elemental quantities of work or heat which appear during a change from state 1 to state 2 must be written as- J 807 = Wor 1W, tor Wi, and |, 2 or We f 3Q = Q,. or ,Q, (or Q) Sign convention: | Ifthe heat flows into a system from the surroundings, the quantity is said to be positive conversely, if heat flows from the system to the surroundings itis said to be negative In other words Heat received by the system = + Q and,Heat rejected or given up by the system = Pressure- Positive Qauge pressure Atmospheric pressure Negative gauge prassure or vacuum _ Absolute 7 pressure Pressure ——» Zero absolute pressure Pressure is defined as a force per unit area. Pressures are exerted by gases, vapours and liquids. The instruments that we generally use, however, record pressure as the difference between two pressures. Thus, it is the difference between the pressure exerted by a fluid of interest and the ambient atmospheric pressure. Such devices indicate the pressure either above or below that of the atmosphere. When it is above the atmospheric pressure, it is termed gauge pressure and is positive. When it is below atmospheric, it is negative and is known as vacuum. Vacuum readings are given in millimetres of mercury or millimetres of water below the atmosphere. It is necessary to establish an absolute pressure scale which is independent of the changes in atmospheric pressure. A pressure of absolute zero can exist only in complete vacuum. Any pressure measured above the absolute zero of pressure is termed an ‘absolute pressure’. Mathematically: (i) Absolute pressure = Atmospheric pressure + Gauge pressure pabs. = patm. + pgauge. (ii) Vacuum pressure = Atmospheric pressure - Absolute pressure. Vacuum is defined as the absence of pressure. A perfect vacuum is obtained when absolute pressure is zero, at this instant molecular momentum is zero. REVERSIBLE WORK ~ When (a) the process is frictionless and (b) the difference in pressure between the fluid and its surroundings during the process is infinitely small. Hence when a reversible process takes place between state 1 and state 2,wehave- Work done by the unit mass of fluid [ pav Vhwen a Nud undergoes a reversible process a series of state pomts canbe jomed up to form a bine on a diagram of properties. The work done by the fluid during any reversible Js therefore given by the area under the Line of process proce plotted ona p-v diagramPractice Questions- Q.1 - An artificial satellite revolves round the earth with a relative velocity of 800 m/s. If acceleration due to gravity is 9 m/s2 and gravitational force is 3600 N, calculate its kinetic energy. Q.2- The specific heat capacity of the system during a certain process is given by ca= (0.4 + 0.004 T) kJ/kg°C. If the mass of the gas is 6 kg and its temperature changes from 25°C to 125°C find: (i) Heat transferred; (ii) Mean specific heat of the gas. Q.3- A temperature scale of certain thermometer is given by the relation (t= a ln p + b) where a and b are constants and p is the thermometric property of the fluid in the thermometer. If at the ice point and steam point the thermometric properties are found to be 1.5 and 7.5 respectively what will be the temperature corresponding to the thermometric property of 3.5 on Celsius scale. Q.4- Gas from a cylinder of compressed helium is used to inflate an inelastic flexible balloon, originally folded completely flat, to a volume 0.6 m3. If the barometer reads 760 mm Hg, what is the amount of work done upon the atmosphere by the balloon? Sketch the system before and after the process. It is assumed that the pressure in the balloon is atmospheric at all times, since the balloon fabric is light, inelastic and unstressed Ze faeen yt = Figure Hunt Q.5- The properties of a closed system change following the relation between pressure and volume as pV = 3.0 where p isin bar Vis in m3, Calculate the work done when the pressure increases from 1.5 bar to 7.5 bar.