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Fundamental Thermodynamic Fundamental laws and rules in thermodynamics name closed systems open systems first law / / / ͘ʚ͡͏ ʛcv 1 ͦ ͘͏ ƍ ̿͘ ƍ ̿͘ Ɣ ͋ ƍ ͑ ƍ Δ Ƭƴ͂ ƍ ͩ ƍ ͮ͛ Ƹ ͡ʖ ư Ɣ ͋ʖ ƍ ͑ʖS ͨ͘ 2 fs second law ͘ʚ͍͡ ʛcv ͋sʖ / ͋rev ʖ universe ƍ Δʞ͍͡ʖ ʟfs Ǝ ȕ Ɣ ͍G ƚ 0 ͍͘ Ɣ ; Δ͍ ƚ 0 a,% ͎ ͨ͘ % ͎ third law for all perfect crystalline substances at absolute zero ͍ Ɣ 0 Gibbs phase rule ̀ Ɣ 2 Ǝ ƍ ͈ Fundamental definitions and relations in thermodynamics sat / ͘͏ 1 ͐͘ / ͊͘ ͑͘ Ɣ Ǝ͊͘ ͐ ̽ ȸ ƴ Ƹ ȸ Ǝ ƴ Ƹ Δ͍reservoir Ɣ ͋/͎ Δ͂latent Ɣ ͎Δ͐ ͎͘ ͐ ͊͘ ͎͘ ͊͐ ͂͘ 1 ͐͘ / Δ͂latent ͔ ȸ ̽ ȸ ƴ Ƹ ȸ ƴ Ƹ ͍ Ɣ ͟ ln Ω Δ͍latent Ɣ ͎͌ ͎͘ ͐ ͎͘ ͎ Fundamental thermodynamic functions for closed systems name definition differential form natural conditions at variables equilibrium internal minimized at energy ͘͏ Ɣ ͎͍͘ Ǝ ͊͐͘ ͏ʚ͍, ͐ʛ constant and ͍ ͐ enthalpy minimized at ͂͘ Ɣ ͘ʚ͏ ƍ ͊͐ ʛ ͂ ȸ ͏ ƍ ͊͐ Ɣ ͘͏ ƍ ͊͐͘ ƍ ͐͊͘ ͂ʚ͍, ͊ʛ constant and ͍ ͊ Ɣ ͎͍͘ ƍ ͐͊͘ Helmholtz minimized at free energy ̻͘ Ɣ ͘ʚ͏ Ǝ ͎͍ ʛ ̻ ȸ ͏ Ǝ ͎͍ Ɣ ͘͏ Ǝ ͎͍͘ Ǝ ͍͎͘ ̻ʚ͎, ͐ʛ constant and ͎ ͐ Ɣ Ǝ͍͎͘ Ǝ ͊͐͘ Gibbs minimized at free energy ́ ȸ ͏ ƍ ͊͐ Ǝ ͎͍ ́͘ Ɣ ͘ʚ͂ Ǝ ͎͍ ʛ Ɣ ̻ ƍ ͊͐ Ɣ ͂͘ Ǝ ͎͍͘ Ǝ ͍͎͘ ́ʚ͎, ͊ʛ constant and ͎ ͊ Ɣ ͂ Ǝ ͎͍ Ɣ Ǝ͍͎͘ ƍ ͐͊͘ Material property relations for specific substances ideal gas, ideal gas, nonideal substances, constant heat capacity variable heat capacity with cubic equation of state ͎͌ ͎͌ ͕ʚ͎ʛ ͊ Ɣ ͎͌ ͊ Ɣ Ǝ ͐ ͊ Ɣ ͐ Ǝ ͖ ʚ͐ ƍ #͖ ʛʚ͐ ƍ ͖ ʛ ͐ ͏ Ɣ ͏ʚ͎ʛ only ͏ Ɣ ͏ʚ͎, ͐ʛ ͏ Ɣ ͏ʚ͎ʛ only ̽ 3 ̽ 5 ̽ ͦ ͯͦ Ɣ , Ɣ ʚmonatomicʛ ̽ ͦ ͯͦ Ɣ ̻ ƍ ̼͎ ƍ ͎̽ ƍ ͎̾ ͌ 2 ͌ 2 Ɣ ̻ ƍ ̼͎ ƍ ͎̽ ƍ ͎̾ ͌ ͌ ̽ 5 ̽ 7 ͊͘ ͐͘ Ɣ , Ɣ ʚdiatomic ʛ ̽ Ɣ ̽ Ǝ ͌ ̽ Ɣ ̽ Ǝ ͎ ƴ Ƹ ƴ Ƹ ͌ 2 ͌ 2 ͎͘ ͎͘ Explanation of differential forms Let’s examine the internal energy, , whose differential form is . This notation tells us ͏ ͘͏ Ɣ ͎͍͘ Ǝ ͊͐͘ several things: • Consider to be a function of the two intensive state variables and . According to the Gibbs ͏ ͍ ͐ phase rule, these are two pieces of information we can use to completely specify for a single ͏ component system. For multicomponent systems, we need these two pieces of information plus the system composition (e.g., the mole fractions of all species). • We can think of as a function that will return for us the internal energy for any specified ͏ʚ͍, ͐ʛ state. Notice that is just a mathematical function with two independent variables. ͏ • The partial derivatives of are related to other thermodynamic properties: and ͏ ʚ͘͏⁄ ͍͘ ʛ Ɣ ͎ . Here, the subscripts indicate what is constant during the derivative. ʚ͘͏⁄ ͐͘ ʛ Ɣ Ǝ͊ • In general, we don’t have to pick and as the independent variables. For example, we could ͍ ͐ pick and , for . However, in this case, the partial derivatives of will not both be ͎ ͊ ͏ʚ͎, ͊ʛ ͏ related simply to other properties, like the temperature and pressure as before. Instead, they will be related to combinations of properties, or derivatives of properties, like the heat capacity. For this reason, we say that and are natural variables of . ͍ ͐ ͏ • The second law of thermodynamics can be reformulated to show that always tends towards a ͏ minimum at equilibrium for systems held at constant and . This is mathematically equivalent ͍ ͐ to saying that tends toward a maximum at constant and , i.e., for an isolated system. ͍ ͏ ͐ Similar arguments extend towards the other thermodynamics functions: • The natural variables of the enthalpy are and , with and . ͂ ͍ ͊ ʚ͂͘⁄ ͍͘ ʛ Ɣ ͎ ʚ͂͘⁄ ͊͘ ʛ Ɣ ͐ tends toward a minimum for systems that are held at constant and . ͂ ͍ ͊ • The natural variables of the Helmholtz free energy are and , with and ̻ ͎ ͐ ʚ̻͘⁄ ͎͘ ʛ Ɣ Ǝ͍ . tends towards a minimum for systems held at constant and . ʚ̻͘⁄ ͐͘ ʛ Ɣ Ǝ͊ ̻ ͎ ͐ • The natural variables of the Gibbs free energy are and , with and ́ ͎ ͊ ʚ́͘⁄ ͎͘ ʛ Ɣ Ǝ͍ . tends towards a minimum for systems held at constant and . Because so ʚ́͘⁄ ͊͘ ʛ Ɣ ͐ ́ ͎ ͊ many processes are performed at constant temperature and pressure (e.g., chemical reactions), the Gibbs free energy is an extremely important quantity that indicates to what state a system will evolve (e.g., in which direction and to what extent a reaction will proceed). Maxwell relations For any well-behaved mathematical function of two variables, the cross second derivative doesn’t depend on the order of the independent variables. In other words, for a function ͚ʚͬ, ͭʛ: ͘ ͚͘ ͚ͦ͘ ͚ͦ͘ ͘ ͚͘ ʨƴ Ƹ ʩ Ɣ Ɣ Ɣ ʨƴ Ƹ ʩ ͭ͘ ͬ͘ 4 3 ͭͬ͘͘ ͬͭ͘͘ ͬ͘ ͭ͘ 3 4 We can apply this logic to each of the four fundamental thermodynamic functions. Consider ͏ʚ͍, ͐ʛ: ͘ ͘͏ ͘ ͘͏ Ƭƴ Ƹ ư Ɣ Ƭƴ Ƹ ư ͐͘ ͍͘ ͍͘ ͐͘ Substituting for the inner partial derivatives, based on the differential form of : ͏ ͘ ͘ ʞ͎ʟ Ɣ ʞƎ͊ʟ Simplifying: ͐͘ ͍͘ ͎͘ ͊͘ ƴ Ƹ Ɣ Ǝ ƴ Ƹ This equation establishes a relationship between͐͘ derivatives͍͘ of thermodynamic variables. This is called a Maxwell relation, named after James Maxwell, an early founder of thermodynamics. This is a fundamental relationship, and it is never violated for systems at equilibrium. Therefore, one cannot set independently the derivatives on the left and right hand side. Since there are four thermodynamic potentials, there are four Maxwell relations. The remaining three are derived in an analogous manner to the approach before. These relations are extremely useful in thermodynamics because they enable us to relate derivatives involving quantities that are not directly measurable, like the entropy, to ones that are, like the pressure, molar volume, and temperature. The table below summarizes the four relations. Maxwell relations for closed systems thermodynamic derivation Maxwell relation function internal energy ͘ ͘͏ ͘ ͘͏ ͎͘ ͊͘ Ƭƴ Ƹ ư Ɣ Ƭƴ Ƹ ư ƴ Ƹ Ɣ Ǝ ƴ Ƹ ͐͘ ͍͘ ͍͘ ͐͘ ͐͘ ͍͘ enthalpy ͘ ͂͘ ͘ ͂͘ ͎͘ ͐͘ Ƭƴ Ƹ ư Ɣ Ƭƴ Ƹ ư ƴ Ƹ Ɣ ƴ Ƹ ͊͘ ͍͘ ͍͘ ͊͘ ͊͘ ͍͘ Helmholtz ͘ ̻͘ ͘ ̻͘ ͍͘ ͊͘ free energy Ƭƴ Ƹ ư Ɣ Ƭƴ Ƹ ư ƴ Ƹ Ɣ ƴ Ƹ ͐͘ ͎͘ ͎͘ ͐͘ ͐͘ ͎͘ Gibbs ͘ ́͘ ͘ ́͘ ͍͘ ͐͘ free energy Ƭƴ Ƹ ư Ɣ Ƭƴ Ƹ ư ƴ Ƹ Ɣ Ǝ ƴ Ƹ ͊͘ ͎͘ ͎͘ ͊͘ ͊͘ ͎͘ .
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