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Thermodynamics 1

Chemistry

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20 views12 pages

Thermodynamics 1

Chemistry

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mohammedzubiyaan
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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onver Mi pperentyriatnves implies flow of heat. It helps to lay down the criteria for predicting fe: awe a of a process, including a chemical reaction, under a given set of conditivns It alse helps to 6 tent to which a process, including a chemical reaction, can proceed before attainment of yume te O Thermodynamics is based on generalizations called Jaws of thermodynamics. Laws of ibrum state to another rent ‘nc apply only when a system is in equilibrium or moves from one equilil state yinewst fundamental terms in thermodynamics “jens The macroscopic part of universe under study is called the system. maining part of the universe that can interact with the system is called ings. The boundary or wall separates a system from its surroundings. The siuy shay be either fixed OF moving (real or imaginary), The surroundings sje everything other than the system, System and the surroundings together gosnute the UNIVERSE. Universe = System + Surroundings Surroundings wut eng ts exchanged between the system and surroundings through cither heat exchange or work beimg Untee types of systems depending on the kinds of exchanges taking place between a systesm re ane ied surroundings during 3 process Uipensystoms A system which cam exchange matter as well as energy with Assurroundings is called open system. The presence of reactants in an open beaker an example of an open system. The ocean is an example of an open system. Another good example for open system is photosynthesis hich both energy and matter are exchanged. Used system: A system which can exchange only energy but not matter *ithity surroundings is called a closed system, Pressure cooker is an example STS hang Aclosed system, holited stern: A system which can exchange neither energy por matter “Wi surrounding is called an isolated system. The presence of reactants Thermalty *thennoflask or any other closed insulated vessel is an example of an isolated insulated yen ON Jewth pubicatins Universe is the example for iwslated system = State of a system: The state of a thermodynamic system ix described by its meaxurable OF (hulk) properties The state of the system! is charcetensed by thermedy namic variables such ag Prue temperature. volume and compesition A system is said to be in a given state when the therm Yanables such as preswure, volume, temperature and compostion ofthe »ystern have Fixed value," = of the surroundings can never be completely specified: fortunately it ts not necessary t0 do ye State functions State funetons are thermodynamic variables whose magnitude depend only on the state of a system ang, (on the process or path taken to reach that state Thermodynamic variables such as pressure, temp. volume and composition are called state functions because the change in theie values depend oy mt smitial and final states of the system and not on the way in which the change lakes place, The fy. - internal energy 1 a wate function fs cxtemely useal because we ean measure the CHTEY change yg system by knowing the initial energy and the final energy Thermodynamic process Process isa path which changes the system from one slate to another, Whenever a system changes from ox state to another. it 1s accompanied by change in energy Ditterent types of processes Isothermal process A process which is carried out at constant temperature is called isothermal Process. The constancy o temperature 1s achieved by the system either by giving out the heat to the surrounsling or absorbing the bey from the surrounding. Therefore, during isothermal process heat exchange takes place. For isothermal pce AT =andg 2 0 Adiabatic process A process in which there is no exchange of heat between the system and surrounding is known x adiabatic process. In an adiabatic process there is a change in temperature of the system but there is ao hea exchange between the system and surroundings, Therefore AT ~ Oand q = 0. Isobaric process A process is said to be isobaric if the pressure of the system remains constant during each step of te process. Isochoric process A process is said to be isochoric if the volume of the system remains constant during each step of process. Cyclic process A process in which a system returns (o its initial state after passing through different states, the proce? is said to be a cyclic process. Reversible process A process which is carried out infinitesimally slowly so thatit can be reversed at any instast of a"? reversing the driving force by infinitesimal amount is called a reversible process. sito proc acess which cannot be reversed at any instant of time by reversing the driving force by # ore ig called Irreversible process. " odynamic properties spe wwo types of thermodynamic properties, nee? > Proper gvemive property nensive property exiensive property ty which depends of the quantity of matter present in the system is called extensive property. 1 Mass, volume, internal energy, heat, free energy, entropy, etc. rape sntensive property x property which is independent on the quantity of matter present in the system is called intensive riy. Exumpley: Density, surface tension, viscosity. specific heat, thermal conductivity, refractive index, ee temperature, boiling point, freezing point, vapour pressure of a liquid. ete internal energy (U) ubstunce is associated with a definite amount of energy which depends upon its chemical nature as 2s upon ifs temperature, pressure and volume. The internal energy is the total amount of kinetic and potential energy possessed by the system. The change in the intemal energy (AU) of a system depends only seine anvunt of energy in the system at the beginning and end, Total of all forms of energy that a system posewes al a given state is called its internal energy. [tis denoted by the symbol U ‘niemal energy is a state function, i.¢., its value depends only upon the state of the substance but does not ‘pend upon how that state is achieved. The absolute value of internal energy of a substance cannot be ‘tcroined, But change in internal energy can be measured experimentally aU = Usa p Grant BU esction = Uiaun Urea U., where U, is initial intemal energy and U, final internal energy. The internal energy is made up tent kinds of energies like translational energy of molecules (U,), rotational energy of molecules ) Vibrational energy of molecules (U,), electronic energy (U_), nuclear energy (U,), and gravitational sey it) Wet edith i =U, +U, +U, +U+ Ut U, erma “Petey of any substance depends on temperature and amount of the sample. Vol the *ystem, will change, when * heat passes into or out of the system, Work is done on or by the system, Miter enters oF leaves the system. Jeevity pubtications ‘Types of energy changes & (a) Work:Exchange of energy between system and surroupdings can occur in the form, Of Work wh: bbe mechanical or electrical work, For example, let us take a system containing some quantity gp) aa thermos flask or in an insulated beaker, This would not allow exchange of heat between Wiley and surroundings through its boundary, Such systems are called adiabatic systems. Let ys change in the internal energy of the system by doing some work on it. Let us call the initia sty a system as state A and its temperature as T,. Let the internal energy of the system in state 4 tey te can change the state of the system in two different ways, 4 ‘One way: Let us do some mechanical work (say | kJ) by rotating a set of small paddles ang churning water, Let the new state be called B and its temperature, Ty, [tis found that T, 5-7 ¥ and change in temperature, AT = T,~ Ty. Let the internal energy of the system in state B be Ueie change in internal energy, AU =Uy—U,. Second way: If we do an equal amount of (ie. 10) electrical work with the help of an immerscn ny and note down the wemperature change, we find thatthe change in emperature is same as inthe exe case, AT=T,-T,. ‘The positive sign expresses that W gua positive when work is done on the system. Simla, e work is done by the system (w,) will be negative (b) Heat: Internal energy of a system can change by transfer of heat frorn the surroundings tothe system vice-versa without doing any of work. The exchange of energy as a result of temperature differesce called heat (q). 2 aad, In this case change in internal energy, AU = q, when no work is done at constant volume 4 is positive, when heat is transferred from the surroundings to the system and q is negative when bea s transferred from system to the surroundings (c) General case: Let us consider the general case in which a change of state is brought about bot by doing work and by transfer of heat. We write change in internal energy for this case as: AU=q+w ‘The first law of thermodynamics ‘The first law of thermodynamics states that “the energy of an isolated system is constant”, Itis commonly stated as the law of conservation of energy “energy can neither be created nor destroyed although, it can be transformed from one form to another”, Express the change in internal energy of u rystem when (i) No heat is absorbed by the system from the surroundings, but work (w) is done on the system, What TF of wall does the system have? . “ Gi) No work is done om the system, but ¢ amount of heat is taken out from the system and given surroundings. What type of wall does the sysiem have? a (iii) w amount of work is done by the system and q amount of beat is supplied to the system. What OF system would it be? (NCERT solved Problem). a, joy Wall is adiabatic q, thermally conducting walls ) AU =q-™, closed system, «i mathematical expr sion of first law of thermodynamics Letusconsider a system having initial internal energy U,. The internal energy of this system can be increased Jets sy ewo methods 4 Supplying heat to the system + by doing work on the system When ‘q’joules of heat is supplied to the system, its internal energy becomes = q + U, Lat'w’ be amount of work be done on it, so that internal energy increases to U, +4 + So. final state of internal energy U, is given by, U,=U, +44 U,-U,=q+w That is, change in internal energy = heat absorbed + work done on the system. Equation (1) is the mathematical form of the first law of thermodynamics, Letthe change in volume during an isothermal reversible contruction at constant pressure, p, be “AV" then the work is referred to as pressure-volume work and is given as ~ pAV. ‘Thus, w =~ p.AV (2) Now, if there is only pressure-volume work , the ‘expression (1) can be written as, AU =q+pAV oh) AU =q+w For an isothermal expansion at constant P, the expression for the first law will be AU =q-w: ». AU =q-p-AV Sign convention of ‘q' and ‘w' according to 1UPAC Heat absorbed by the system = Gis positive Heat evolved by the system = q is negative Work done on the system = w positive Work done by the system = w negative Join pttcationn ; Derivation of an expression for the ican ar done in isother, a Compression of an ideal gas (Additional informat Let us conander a cylinder of cross-sectional area ‘A’ fitted with a piston. The apparatus ig 4, the prston enckses a pascous sample at pressure (p,, )-and the piston is attached toa mechanuae ey maintain an external pressure (p,,,) 00 the gas. Let “V,” be the initial volume Of the gay 4p wh Pressure 1 apphed on the piston which ts greater than the internal pressure, piston move, ine Pressure inside 4s equal to external pressure The volume of the gas 1s decreased and fing) Vohome Dunng this compression, the piston moves through a distance */” then, iy ay Volume change = 1A © AV = v.-¥, But, pressure = Force/area Therefore, force on the piston = pressure x area = Pea A : Peat . VS Volos y If 'w isthe work done on the system by the » movement of the piston, then we force x distance (coxa = Pew | = Py (AV) ee Fig. 6.1 Work done om an ideal pu wf AV) ina cylinder when itis competed ty constant pressure Note: "*" becomes posinive when work 1s done on the system during compression. Hee V, ~ V, becomes negative because V, < V, during compression 1f the pressure is not constant at every stage of compression, the work is equal to sum of all the sepe Therefore, w=-Ep,,, AV Work done in an isothermal reversible expansion of an ideal gas During reversible isothermal expansion of an ideal gas, the gas expands in a large number of steps team samll volumes against the external pressure (p,,) Suppose the gas expands through a smal volume “dV” against external pressure, p.,, the small work a0 the gas 1s given by bw =-p,, dV For reversible expansion, —_p,, = p,, ~ dp see bw =—(p.,-dp) dV =-p-dV+ dp-dV o eglgibly small # bw = -P, dV an Total work done by the gas from an initial volume of V,¢0 final volume of V, is gglioy nears equation. 7 * ORT te's aw, v= Pt Applying Boyle's law, vy, Py =, W=-2-303 aRT log 2 The above equation can be used for work of compression also, wae Expressions for mechanical work done in an isothermal reversible a1 ind irreversible process //forareversible isothermal expansion, work done w is given by y, =-2:303RT log —£ va-2-308RT log 2 Foran reversible isothermal compression, work done w is given by wa-p.tV, -V,) of Foran ieversible isothermal compression, work done w is given by ¥=+2 0BRT log o * Foran imeversible isothermal compression, work done w is given by “=4p(V.~V,) Work done in a free expansion, ie + against 00 external preasure, w=0 (. p,, =0) Thatis why ‘work done by an ideal gas during its expansion into vacuum is zero * nate > W ere Tisbecause that. (p,,,), es > (Pose ee Weasy Te wok done uring an adiabatic expansion of an ideal ga is w =-uC, (T, ~T,) Jeevith pubficatons: Expression for rev For an adiabatic process, q = 0 ersible adiabatic expansion aust For reversible adiabatic contraction, AUetw =C,(7,-1) =C,AT e-wa-C,(1,-T) = CAT For reversible adiabatic expansion, AU Thank tank - 1 1 Why is that air at higher altitude is coller than at sea level? 2. How are hails formed in the clowd. 3. Airis blown through the mouth to feel cooler. Whi this process, Liquid air used as coolant, But how do we liqufy the aif, iat is the thermodynamic principle j ‘mvolvedia Problems 1A pas absorbs 120 Jo to 2.0 L. What is the change in internal energy 1 heut and expands against the eternal pressure of 1.10 atm from a volume ct HAL atm = 1013) at Solution: AU =q+w q= +120) w Pel¥:~V) =-1-10x1-5=-1-65 Latm = -1-65x101-3 = -167-145 3 ve AU = (+120) + (167-145) = 47-1355 2. Caleulate the work done when ages expands atu constant temperature from volume 216° = 67% 3 em? agunst u constant pressure of 1.2 x 108 Nev, Solution: w =-pav p=1-2x10°Nm"; AV=V, ~V, =(4x10°)-(2x10")=2x107m’; w=? W= 1.210" Nav? 210m! = -2:4x10? Nm ‘ = -2-4x10°J (since Nm = J). } ‘Thermodynamics the total wark done when | mole of gas expands isothermally and reversity from an initial div! to a final value of 40 den" at 29 K (R = 8.314 JK“! mot !), at slate cate V, 2-303 aRT log gel, R=8:314 JK" mol"', T= 298 K,V, = 20dm’, V, = 40dm’,w =? 2-2: 303x8- 314x208 lop ==2-303x8-314 x298 log? =-2- 3038-314 2980-3010 = 1717-46 J mol” Twonles of an ideal gas initially at 27°C and one atmospheric pressure are compressed isothermally and reversibility tll the final pressure of the gas is 10 atm, Calculate q, w and AU) for the process. Here, n= 2 moles, T= 27°C = 300 K. p, =1 atm, p we2 303 aRT tog Ps , =2-3032x8. 314300%log 2 = 2.303 28-314 x 300x1 =11488.3 J For isothermal compression of ideal gas, AU =0 = —w =-11488.3 Twortilres of un ideal gas at a pressure of 10 atm expands isothermally into vacuum until its total volume 45 ites uch heat is absorbed und how much work is done in the expansion? What would be the vebed and work dene, Funher, AU=g+w 2. beat a Ifthe sume expansion ti ii Fe tion: es place against a constant external pressure of 1 atm? expansion takes place toa final volume of 10 litres conducted reversibly? [NCERT exainple] “*k of expansion against vaccum is zero, -. w =0 f ‘fan isothermal change, AU=0 t AU =qew “q=0 ‘ “2NO(g) AH = +180.7Kd nthalpy (H) ‘Ke know thatthe heat absorbed at constant volume is equal to change in the internal energy i¢.. AU = dy. lo vdeo study the heat changes of chemical reactions at constant temperature and pressure, a new function, +s is introduced. Enthalpy is the total energy associated with any system which includes its internal andextemal energy such as pressure-volume energy. The enthalpy of a system may be defined as the sam of the internal energy and the product of its pressure and volume. The product of pressure amd sume js called external energy. Enthalpy is denoted by the symbol “H’ and is given by, H=U+pvV AD shee. U = intemal energy. p = pressure and V = the volume of the system. Bathalpy is also called beat

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