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Definition
| the study of heat and energy |
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| mechanical equivalent of heat |
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| not a mechanical object but a mechanism for the transfer of energy |
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| flows if there is a difference in electrical potential |
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| if there is a difference in thermal potential (thermal energy) |
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| if there is a difference in chemical potential [dG] |
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| independent of quantity [T,P, ...] |
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| scales with quantity [E,V,mass] |
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| provided that temp remains constant |
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energy is neither created nor destroyed but only redistributed as heat or work.
dE = q + w |
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| How is constant Temp maintained? |
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Definition
| Only if the heat entering the system is equal to the work done by he system |
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| what does dE not depend on? |
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Definition
| How the change in E is made. [fast/slow] |
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Definition
| the system to remain in equilibrium. It ensures that Pext = Psys |
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Definition
| energy, entropy, enthalpy, free energy |
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| entropy macroscopic equation |
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| 1st law can be applied to different experimental conditions - |
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Definition
1. expansion or contraction at fixed P [dE=q-PdV]
2. if V is kept constant during some change in T or P or both [dE = q at constant V] |
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Definition
| the enthalpy change for the direct process is equal to the sum of the enthalpy changes for all the indirect steps |
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| what direction does a spontaneous process occur |
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Definition
| the direction that maximizes the associated number of microstates |
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| how can crystals exist if nature favors high disorder? |
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Definition
| By minimizing energy through interatomic/intermolecular forces. There is a balance between minimizing energy and maximizing disorder. |
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Definition
| entropy is an extensive property which must increase as the sum of the entropies of two or more systems |
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| the number of microstates of the combined system must be given by the product of the number of microstates of the systems. |
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| q is less then q reversible because more work is done when the process is reversible |
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| we are at equilibrium so we have reversibility |
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Definition
| we are at equilibrium so we have reversibility |
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| entropy increases until a maximum is reached when equilibrium is attained |
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| spontaneous change and entropy of the universe |
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Definition
| spontaneous change occurs only if the entropy of the universe increases |
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| spontaenous at high temperature |
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| p, denotes the fraction of molecules with correct orientation |
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| z, maximum rate of reactin cannot exceed frequency of collisions |
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| entropy increases why does dG decrease |
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Definition
| dG =-TdS -- connected to dSuniv and the second law |
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Term
| relationship between Go and K |
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Definition
dGo=-RTlnK
dG - k>1 products
dG + k<1 reactants |
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Term
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Definition
| the entropy of any pure substance approaches 0 at the absolute zero of temperature. the entropy of any pure substance is assumed to be zero at 0K |
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| speed of a rxn depends on |
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Definition
1. number of collisions/sec
2. energy/collision
3. proper orientation |
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Term
| 3 conditions for a succesful rxn |
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Definition
1. collision must occur
2. collisions must possess a minimum Ea
3. correct orientations must exist |
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Definition
| maximized by high concenrations |
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| governed by state of matter |
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| dependence of rate on concentrations |
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Definition
| in general, the greater the conc of a substance, the larger the rate of rxn |
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| what is rate determined by |
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| # of correctly oriented particles (a) and Ea |
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| a catalyst increases the rate of reaction but not the yield, is not changed in the course of a reaction |
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