Thermodynamics 1st law

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1. What is the 1st law?
• Energy is conserved: if one form of energy disappears, another for must reappear simultaneously.
• Change in E(sys)+E(surr)=0
2. What is a reversible process?
• Can be reversed with an infinitesimal change in external conditions
• No path hysteresis
• Never more than differentially removed from equilibrium so transverses a series of equilibrium states
• Driving force must be differential and have no resistance
• Frictionless

NO REAL PROCESS IS REVERSIBLE
3. Closed system
only energy can be transferred, not mass
4. Work
• Force acting through a distance
• May increase the temperature - no heat required necessarily
5. Heat
• Energy transferred due to temperature difference
• Never stored
• Cannot be determined without analysing effect on system
6. State functions
• defined by a system's current set of conditions (P,T,V), independent of the pathway used to achieve them
• eg. U, H, S, P, V, T
7. Pathway functions
• dependent on how system changes from one state to another
• eg. W, Q
8. Ideal gases definition
• molecules have zero volume
• no intermolecular forces
9. When can real gases be modelled as ideal gases?
• at low pressure (eg. atmospheric)
• when compression is slow PV=nRT
• when process is reversible
10. Which pressure do you use to calculate the work in an ideal gas expansion?
The resistive pressure, ie. the surroundings pressure
11. Joule's experiment
• showed the U=f(T) for an ideal gas
• gas expansion in insulated water bath, temperature change measured and found to be negligible
• this is because IGs have no intermolecular forces so no energy can be stored
12. Equilibrium
• system unchanging on macroscopic scale due to no net driving force
• systems where resistance=driving force~=0 are not at true equilibrium but can be modelled with thermodynamics if process is slow
• thermodynamics: systems at equilibrium or transitioning between equilibrium states
13. Irreversible process
• finite driving force
• energy dissipated: W to U, so not all work is transferred to surroundings
14. Enthalpy
• State function: made up of state functions
• H=U+PV
• kJ/kg
15. Heat capacity
• NOT ability to store heat - heat is not stored
• state function
• Cp (IG)= 29.099 J/mol K
• Cp=Cv+R for ideal gases
16. Work produced in an irreversible process is
• smaller than the work produced in a reversible process
• W(irrev)=W(rev)*n
17. Work consumed in an irreversible process is
• greater than the work consumed in a reversible process
• W(irrev)=W(rev)/n
18. The final temperature of the system after an adiabatic process is always______in an irreversible process.
• larger
• adiabatic compression - extra W converted to U
• adiabatic expansion - some energy remains in gas as U
19. Open energy balance
mass and energy transfer
20. Causes of enthalpy changes (4)
• temperature: sensible heat
• phase changes
• reactions
• mixing: compositional changes, solution formation
21. When does dH=CpdT apply?
• ideal gas processes
• incompressible fluids when dP is small
22. Cocurrent flow
two streams pass through a heat exchanger in the same direction
23. Sensible heat
Enthalpy change based solely on temperature different
24. Define symbols in Gibbs phase rule, F= 2-Pi+N
• F=dof
• pi=number of phases
• N=number of chemical species
25. phase
homogeneous region of matter
26. vapour
gas below the critical temperature, Tc, which can be condensed into a liquid
27. saturated steam
• water at the vapour pressure for a given temperature OR at the boiling point for that pressure
• mixture of liquid and vapour
• F=1
28. superheated steam
• dry steam above the vapour pressure at a given T OR above the boiling point at that pressure
• F=2 (define both T and P)
• useful for turbines - no water droplet damage
29. Why is there an enthalpy change during a phase change?
• H=U+PV
• U: bond breaking to change arrangement
• PV: volume change so work done
30. What assumption should be made for mixed flow streams?
ideal gas mixture ie. no interactions between streams (equivalent to ideal gas assumption)
31. Why does steam burn worse that boiling water?