Property Comment First Law of thermodynamics Work of expansion ‘Work ofexpansion against a constant external pressure ‘Work of sothermal reversible expansion of a perfect gas Heat capacity at constant vo eat capacity constant presse Reaton between heat capacities Enthalpy ‘The standard reaction enthalpy Kirchhoff’slaw Internal pressure JouleThomson coefficient = UIT), G= (Han, AT) =A, y= (QURV)y (TIA) Acquistive convention Pas=0 corresponds to free expansion Isothermal, reversible, perfect gas Fora perfect gis, m= 0 Fora perfect gusOo. O2 ow Os. Oe. Ov. Os. Or. ‘Thermodynamics isthe study of the transformations of, energy. ‘The system is the part of the world in which we have a special interest. The surroundings isthe region outside the system. where we make our measurements. An open system hasa boundary through which matter can be transferred. A closed system has a boundary through which ‘matter cannot be transferred. An isolated system has a boundary through which neither matter nor energy can be transferred. Energy isthe capacity to do work. The internal energy isthe total energy of a system, 5, Workis the transfer of energy by motion against an opposing force, w= —Fa. Heat isthe transfer of energy asa result of a temperature difference between the system and the surroundings. >. Calorimetry isthe study of heat transfers during physical and chemical processes. The heat capacity at constant volume is defined as {AUIB)y. The heat capacity at constant pressure is AIH/AT),. For perfect ga, the heat capacities are related byG,—Cy=nr. The enthalpy is defined as H= Ut pV. The enthalpy change is the energy transferred as heat at constant pressure, dn During a reversible adiabatic change, the temperature of a perfect gas varies according to Ty= T(VjVM,e= Cyg/R. ‘The pressure and volume ate related by pV7= constant, with, 7= Cyl Cr ‘The standard enthalpy change isthe change in enthalpy fora process in which the initial and final substances are in their standard states. The standard state isthe pure substance at bar. Enthalpy changes are additive, as in AjggHl® = AjgdH® + Map Hl®- ‘The enthalpy change for a process and its reverse are related Dy AvsewardHt = —AreyereHt”. ‘The standard enthalpy of combustion isthe standard reaction enthalpy for the complete oxidation of an organic compound to CO, gas and liquid H,0 if the compound contains C, H, and O, and to N, gas if N is also present Hess's law states thatthe standard enthalpy of an overall reaction is the sum of the standard enthalpies ofthe individual reactions into which a action may be divided, Os oO» On. On. Oa Ox. O23. Ox. Ons. Ox. Ces. An exothermic process releases energy as heat to the surroundings. An endothermic process absorbs energy as heat from the surroundings. state function isa property that depends only on the current state ofthe system and is independent of how that state has been prepared. ‘The First Law of thermodynamics states that the internal ‘energy of an isolated system is constant, AU= q+ w. Expansion work is the work of expansion (or compression) of system, div=~p,,dV. The work of free expansion is w= ‘The work of expansion against a constant external pressure is PecAV. The work of isothermal reversible expansion of a perfect gasis w=—nRT in V/V). A reversible change isa change that can be reversed by an finitesimal modification ofa variable. Maximum work isachieved in a reversible change. ‘The standard embalpyofformaton (Aq) isthe standard reaction enthalpy fr the formation athe compound rom is ere are eee non stable state ofan element atthe specified temperature ers lr by combining embalpis of formation, AGH®= pyoductsYA¢H” — ZpesctannsVAYH”. ,—st n ACHT. 1 or integrated, gies a rst tat independent of the path select pay pelea apnea ss result hat depends on the path betwen the nial and fal The internal pressure is defined as = (UIOV)y. For a pevect gas y= ‘The onle“Thomson eet the coo eee ‘The foule-Thomson cet is dfined a= (27/y ‘The sothemal Joule“ Thomson coofient sdeind ob y= (@HIOp)y=—C,ut “The inversion temperatarein the emperaturet which the Joule-Thomwon cecficient changes sgn by Kirchhoff’s law, A.H°(T,) =A,H°(T,) + ofagas by