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14B Thermodynamics
Scerri's reader
46
Chemistry
Undergraduate 1
04/29/2008

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Term
thermodynamics
Definition
the study of heat and energy
Term
mechanical equivalent of heat
Definition
calorie -> energy
Term
what is heat?
Definition
not a mechanical object but a mechanism for the transfer of energy
Term
electrical current
Definition
flows if there is a difference in electrical potential
Term
heat flows
Definition
if there is a difference in thermal potential (thermal energy)
Term
chemical reactions occur
Definition
if there is a difference in chemical potential [dG]
Term
intensive property
Definition
independent of quantity [T,P, ...]
Term
extensive property
Definition
scales with quantity [E,V,mass]
Term
E=3/2 RT
Definition
for 1 mole of ideal gas
Term
Energy remains constant
Definition
provided that temp remains constant
Term
1st law of thermo
Definition
energy is neither created nor destroyed but only redistributed as heat or work.
dE = q + w
Term
How is constant Temp maintained?
Definition
Only if the heat entering the system is equal to the work done by he system
Term
what does dE not depend on?
Definition
How the change in E is made. [fast/slow]
Term
gradual change allows
Definition
the system to remain in equilibrium. It ensures that Pext = Psys
Term
state functions
Definition
energy, entropy, enthalpy, free energy
Term
entropy macroscopic equation
Definition
dS = qrev/T
Term
1st law can be applied to different experimental conditions -
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]
Term
Hess' Law
Definition
the enthalpy change for the direct process is equal to the sum of the enthalpy changes for all the indirect steps
Term
what direction does a spontaneous process occur
Definition
the direction that maximizes the associated number of microstates
Term
how can crystals exist if nature favors high disorder?
Definition
By minimizing energy through interatomic/intermolecular forces. There is a balance between minimizing energy and maximizing disorder.
Term
S = S1 + S2
Definition
entropy is an extensive property which must increase as the sum of the entropies of two or more systems
Term
W = W1 x W2
Definition
the number of microstates of the combined system must be given by the product of the number of microstates of the systems.
Term
why is dS>= q/T
Definition
q is less then q reversible because more work is done when the process is reversible
Term
phase changes
Definition
we are at equilibrium so we have reversibility
Term
phase changes
Definition
we are at equilibrium so we have reversibility
Term
change in enthalpy
Definition
q at constant pressure
Term
2nd law of thermo
Definition
entropy increases until a maximum is reached when equilibrium is attained
Term
spontaneous change and entropy of the universe
Definition
spontaneous change occurs only if the entropy of the universe increases
Term
dH - and dS +
Definition
always spontaneous
Term
dH + and dS -
Definition
never spontaneous
Term
dH and dS +
Definition
spontaenous at high temperature
Term
dH and dS -
Definition
spontaneous at low temp
Term
steric factor
Definition
p, denotes the fraction of molecules with correct orientation
Term
frequency factor
Definition
z, maximum rate of reactin cannot exceed frequency of collisions
Term
entropy increases why does dG decrease
Definition
dG =-TdS -- connected to dSuniv and the second law
Term
relationship between Go and K
Definition
dGo=-RTlnK
dG - k>1 products
dG + k<1 reactants
Term
3rd law of thermo
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
Term
speed of a rxn depends on
Definition
1. number of collisions/sec
2. energy/collision
3. proper orientation
Term
3 conditions for a succesful rxn
Definition
1. collision must occur
2. collisions must possess a minimum Ea
3. correct orientations must exist
Term
# of collisions/sec
Definition
maximized by high concenrations
Term
energy per collision
Definition
due to high temps
Term
proper orientation
Definition
governed by state of matter
Term
dependence of rate on concentrations
Definition
in general, the greater the conc of a substance, the larger the rate of rxn
Term
ex of 1st order process
Definition
radio active decay
Term
what is rate determined by
Definition
# of correctly oriented particles (a) and Ea
Term
catalyst
Definition
a catalyst increases the rate of reaction but not the yield, is not changed in the course of a reaction
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