The document discusses chemical equilibrium and spontaneous reactions. It defines chemical equilibrium as when the forward and reverse reaction rates are equal in a closed system. Spontaneous reactions either release heat (negative enthalpy change) or increase disorder (positive entropy change). The Gibbs free energy equation determines if enthalpy or entropy is the dominant driving force. Systems at the lowest Gibbs energy are the most thermodynamically stable. The Clausius-Clapeyron equation relates pressure and temperature changes during phase transitions. Compression processes increase pressure in fluids and require energy input.
The document discusses chemical equilibrium and spontaneous reactions. It defines chemical equilibrium as when the forward and reverse reaction rates are equal in a closed system. Spontaneous reactions either release heat (negative enthalpy change) or increase disorder (positive entropy change). The Gibbs free energy equation determines if enthalpy or entropy is the dominant driving force. Systems at the lowest Gibbs energy are the most thermodynamically stable. The Clausius-Clapeyron equation relates pressure and temperature changes during phase transitions. Compression processes increase pressure in fluids and require energy input.
The document discusses chemical equilibrium and spontaneous reactions. It defines chemical equilibrium as when the forward and reverse reaction rates are equal in a closed system. Spontaneous reactions either release heat (negative enthalpy change) or increase disorder (positive entropy change). The Gibbs free energy equation determines if enthalpy or entropy is the dominant driving force. Systems at the lowest Gibbs energy are the most thermodynamically stable. The Clausius-Clapeyron equation relates pressure and temperature changes during phase transitions. Compression processes increase pressure in fluids and require energy input.
The document discusses chemical equilibrium and spontaneous reactions. It defines chemical equilibrium as when the forward and reverse reaction rates are equal in a closed system. Spontaneous reactions either release heat (negative enthalpy change) or increase disorder (positive entropy change). The Gibbs free energy equation determines if enthalpy or entropy is the dominant driving force. Systems at the lowest Gibbs energy are the most thermodynamically stable. The Clausius-Clapeyron equation relates pressure and temperature changes during phase transitions. Compression processes increase pressure in fluids and require energy input.
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Chapter-4 & 5
Chemical Engineering Thermodynamics
Introduction • Chemical equilibrium: When the forward reaction rate equals the reverse reaction rate in a closed system (no energy inputs or outputs) • Static equilibrium: Amount of reactant and product are fixed and unchanging • Dynamic equilibrium: Reactant is turning into product and product is turning into reactant, but at the same rate such that the concentrations of each are unchanged on a macroscopic scale Spontaneous reaction – equilibrium
• Some reactions are spontaneous because they
give off energy in the form of heat (∆H < 0). Others are spontaneous because they lead to an increase in the disorder of the system (∆S > 0). • Calculations of ∆H and ∆S can be used to probe the driving force behind a particular reaction. • The beauty of the equation defining the free energy of a system is its ability to determine the relative importance of the enthalpy and entropy terms as driving forces behind a particular reaction. • The change in the free energy of the system that occurs during a reaction measures the balance between the two driving forces that determine whether a reaction is spontaneous. As we have seen, the enthalpy and entropy terms have different sign conventions. • Favorable ∆Ho < 0 , ∆So > 0 • Unfavorable ∆Ho > 0, ∆So < 0 • The entropy term is therefore subtracted from the enthalpy term when calculating Go for a reaction. The Clausius-Clapeyron Equation THERMODYNAMIC STABILITY • Thermodynamic stability occurs when a system is in its lowest energy state, or chemical equilibrium with its environment. • This may be a dynamic equilibrium, where individual atoms or molecules change form, but their overall number in a particular form is conserved. • This type of chemical thermodynamic equilibrium will persist indefinitely unless the system is changed. Chemical systems might include changes in the phase of matter or a set of chemical reactions.
• State A is said to be more thermodynamically stable than state B if
the Gibbs energy of the change from A to B is positive. EQUILIBRIUM AND STABILITY • Consider a closed system containing an arbitrary number of species and comprised of an arbitrary number of phases in which the temperature and pressure are uniform (though not necessarily constant). • The system is initially in a non-equilibrium state with respect to mass transfer between phases and chemical reaction. • Changes which occur in the system are necessarily irreversible, and they take the system ever closer to an equilibrium state. • We imagine that the system is placed in surroundings such that the system and surroundings are always in thermal and mechanical equilibrium. • Heat exchange and expansion work are then accomplished reversibly. Under these circumstances the entropy change of the surroundings is: The equilibrium state of a closed system is that state for which the total Gibbs energy is a minimum with respect to all possible changes at the given T and P. Thermodynamic aspects of compression process • Just as expansion processes result in pressure reductions in a flowing fluid, so compression processes bring about pressure increases. • Compressors, pumps, fans, blowers, and vacuum pumps are all devices designed for this purpose. • They are vital for the transport of fluids, for fluidization of particulate solids, for bringing fluids to the proper pressure for reaction or processing, etc. • We are here concerned not with the design of such devices, but with specification of energy requirements for steady-state compression of fluids from one pressure to a higher one.
