Thermodynamics: Study of Transformation of Energy MESc. 5025 The Four Laws of Thermodynamics: Zeroth Law: Concept of Temperature Instructor: Herve Marand First Law: Conservation of Energy in Isolated Systems Second Law: Evolution of the Entropy During a Process Third Law: Entropy is a State Function of well defined Chapter 1. magnitude. Thermodynamics Zeroth Law: If A is in thermal equilibrium with B and B is in thermal equilibrium with C, then A is in thermal equilibrium with C (TA = TB =TC). Thermometer and the Absolute Temperature (Kelvin) Scale (ideal gas law). Definitions: Energy: Energy of a system is its capacity to do work. System: Part of the Universe you wish to study and model. Heat: Experience has shown that the energy of a system can be Surroundings: Part of the Universe outside the System that interacts changed by means other than work. When the energy of a system with the System. changes as a result of a temperature difference between system and surroundings, energy has been transferred as heat. Note that Process: Evolution of a System from one State to another State (i.e. during isothermal expansion of an ideal gas heat is exchanged change in Physical State (Solid, Liquid, Vapor, Composition, with surroundings. Number of Phases) or change in Chemical State (reaction). Work: A Process that Does Work is one that could be used to bring Closed System: No matter is exchanged between system and surroundings. about a change in the height of a weight in the surroundings. Work = opposing force x distance Isolated System: No energy and no matter can be exchanged Volumetric Expansion/Compression: w = -Pext dV between system and surroundings. Surface Creation/Shrinkage: w = d Open System: Energy and matter can be exchanged with Uniaxial Tension/Compression: w = f dl surroundings Electrical: w = dq Adiabatic Process: No heat is exchanged between system and State Function: Function well defined for any equilibrium state of a surroundings. (Diathermic Process: Not adiabatic). system (homogeneous, time invariance, continuity, differentiability) Isothermal, Isochoric, Isobaric: resp. cst T, V, P Note that Work is a transfer of energy that makes use of an Concept of Mechanical and Thermal Equilibrium organized motion of its constituents (atoms, electrons, etc..) whereas Heat makes use of chaotic motion. A system is in equilibrium if infinitesimal changes in its state in opposite directions result in opposite changes in its state. The Energy of the System is called the Internal Energy (U, E). The work is denoted by w and the heat by q. Mechanical Equilibrium: Example Ideal Gas Comp./Exp. For elementary processes, we define dU, w, q. Note that whereas P P U is a state function (dU is an exact differential), w and q are not P1 P1 state functions (w and q are not exact differentials). First Law of Thermodynamics: P2 P2 U = Ufin - U init = w + q dU = w + q U is the CHANGE in internal energy of the system during the V1 V2 V V1 V2 V process for which q and w are the heat and the work exchanged between system and surroundings. Irreversible, Fast , Process: Note U = 0 for isolated system and U univ = cst Reversible, Slow , Quasistatic Process: System remains near System is out of equilibrium at sign Convention: w and q are positive when they flow into the all times except initial and final equilibrium at all times. P ext is system (work done on system is positive, by system is negative). states. Pext differs from P. equal to P throughout. Thermal Equilibrium: Temperature of the system is equal to that Isobaric Processes (Constant Pressure Processes): of the surroundings at all times during the process, the system is Many physical processes occur at constant P (dP = 0) in thermal equilibrium with the surroundings. Define an equivalent relationship at cst P using the Isochoric Processes (constant Volume Processes): enthalpy state function H = U + PV dH = d(U+PV) = dU + PdV + VdP dU = wexp + woth + q dH = wexp + woth + q + PdV dH = -Pext dV + woth + q + PdV If V is constant and no other work, then: dU = qV assume the system is under mechanical equilibrium C V = Heat Capacity at constant Volume (CVm , CV ) (Pext = P) and there is no other work. dH = qP C P = Heat Capacity at constant Pressure (CPm , CP ) q U CV = lim = q H dT0 T V T V C P = lim = dT0 T P T P U = C V T if CV can be assumed independent of T between T i and T f. H = C P T if CP can be assumed independent of Tf U = CV (T )dT general expression Tf T between T i and T f. Ti H = CP ( T )dT general expression Ti c C P,m = a + bT + 2 T General Expressions for U, H for Closed Systems of Constant Composition Enthalpy: H = H(P,T) or Hm = Hm(P, T): For a closed system with a single component, only two H H H dH = dT + dP = C P dT + dP intensive variables are sufficient to describe any other T P PT PT intensive property of the system (Gibbs Rule of Phase). H H P T H P Intensive Property: independent of the number of moles or = CP + = CP - T V P T T V P H T P T V mass of system. Extensive Property increases linearly with T 1 V : Joule-Thomson Coefficient the number of moles or mass of the system. = and T = PH V PT T: Isothermal Compressibility Internal Energy: U = U(V,T) or Um = Um(V m, T): H = 1 U dU = U dT + dV = CV dT + T dV T V CP T T V VT U V Universal Relationship Between C P and CV = CV + T = CV + TV TP T P Internal Pressure 2 VT 1 V C P CV = (demonstrate yourself !!!) = Isobaric Coefficient of Thermal V TP T Expansion Thermodynamic Definition of Entropy Entropy Change associated with a Phase Transition: If a phase transformation occurs under reversible conditions The entropy is an extensive state function defined by: (i.e. at equilibrium T, P states along the phase coexistence curve), dS Total = dSSurr + dS and dS Surr = - q / T dS = q / T = dH / T therefore: where q is the heat increment exchanged between system and S trans = Htrans / Ttrans (increase in order implies decrease in S) surroundings (note q > 0 if heat flows into the system). Therefore: dS = dSTotal + q / T Entropy Change resulting from a Reversible Expansion or Compression of an Ideal Gas under Isothermal Conditions: The Second Law of Thermodynamics states (without proof) that for a spontaneous (irreversible) process dSTotal > 0 (or dS > q / T) and for a reversible process (under mechanical, thermal and chemical equilibrium) dS Total = 0 (or dS = q /T). q Entropy is a state function: dS = =0 rev T
Entropy change for adiabatic reversible processes: S = 0
S = nR ln (Vf / Vi) Note: Equation of State f(P,V,T) is needed Measurement of Entropies: Entropy Change resulting from a Reversible Temperature Change at Constant Pressure (any material): Defining Tm and T b, respectively as the melting temperature and the boiling point of a pure substance at a pressure P, we can calculate the entropy change between zero Kelvin and some temperature T above the boiling point starting with: q dH dT dS = = = C P (T) for heating reversibly at constant P T T T S = CP ln (Tf / Ti) assuming Tf - Ti small q dH for a phase transformation occuring dS = = Entropy Change resulting from a Reversible Temperature T T reversibly at constant P, T Change at Constant Volume (any material): Tm dT H m Tb L dT H b T V dT S (T ) S(0 ) = C PS (T ) + + C P (T ) + + C P (T ) 0 T Tm T T Tb T T m b
All quantities on the R.H.S. of the above equation can be measured
readily by calorimetry. Data at very low T is obtained from the Debye eqn. (CP = a T 3 ) through fitting of data at slightly higher T. S = CV ln (Tf / Ti) assuming Tf - Ti small Only S(0) cannot be obtained experimentally. Helmoltz and Gibbs Free Energies The Third Law of Thermodynamics: Entropy and Disorder Entropy is the basic concept for discussing the direction of At T = 0 Kelvin, all thermal motion has been quenched and in a spontaneous change between two states. However it is awkward as perfect crystal all particles are in a regular uniform array. The it requires calculations both for the system and for the absence of both spatial disorder and thermal motion suggests that surroundings. such materials also have zero entropy as zero Kelvin. The goal here is to define new thermodynamic functions that Boltzmann Formula: S = k ln with = 1 and S = 0 provide us with a simple criterion for the direction of spontaneous Nernst Theorem: change under practical conditions (cst T, cst P, cst V, etc...) The entropy change accompanying any physical or chemical transformation approaches zero as the temperature approaches zero. Second Law: dSTotal = - q / T + dS > 0 (spontaneous) Therefore q - T dS < 0 (spontaneous) Third Law: If the entropy of every element in its most stable state at T = 0 K is Processes occuring at constant Temperature and Volume taken as zero, then every substance has a positive entropy which at qV = dU implies dU - T dS = d (U-TS) < 0 T = 0 K may become zero, and which does become zero for all We thus define the state function A (Helmoltz Free Energy): A = U - TS dA = dU - TdS at constant T perfect crystalline substance, including compounds. The Four Maxwell Relations Processes occuring at constant Temperature and Pressure: qP = dH implies dH - T dS = d (H - TS) < 0 First Maxwell Relation (based on dU) We thus define the state function G (Gibbs Free Energy). Let us consider a reversible process G = H - TS dG = dH - TdS at constant T w = - Pext dV = - P dV and q = T dS dU = -P dV + T dS The New Criteria for Spontaneity and Equilibrium are: U is a state function, therefore dU is an exact differential and dAT,V < 0 Spontaneous Process the value of dU is independent of the path chosen. dAT,V = 0 Reversible Process (Equilibrium State) U U U = f (V, S) dU = dV + dS and V S SV dGT,P < 0 Spontaneous Process U U dGT,P = 0 Reversible Process (Equilibrium State) = P and =T VS S V The maximum work that can be done by a system at cst T and V is wmax = A (work done under reversible conditions) U U dU is an exact differential = The maximum non-expansion work that can be done by a system S V SV V S V S at cst T and P is wnon-exp,max = G P T Therefore = S V V S Second Maxwell Relation (based on dH) Fourth Maxwell Relation (based on dG): dH = d(U + PV) = dU + P dV + V dP dG = d(H - TS) = dH - T dS - S dT dH = - P dV + T dS + P dV + V dP dG = dU + P dV + V dP - T dS - S dT dH = V dP + T dS dG = - P dV + T dS + P dV + V dP - T dS - S dT dG = V dP - S dT Therefore: G G T V = V and = S leads to: = PT T P PS S P Third Maxwell Relation (based on dA) V S = dA = d(U - TS) = dU - T dS - S dT TP P T dA = - P dV + T dS - T dS - S dT dA = - P dV - S dT Mnemotechnic and Common Sense: P T (P,V) and (S,T) are conjugate pairs P is differentiated only w/r to S & T P S S is differentiated only w/r to P & V = S V Use common sense for the signs... leads to: T V V T
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