|
|
1st law of thermodynamics
|
in an isolated system energy can neither be created or destroyed; only transferred or converted, meaning E lost = negative E gained
|
2nd law of thermodynamics
|
entropy of an isolated system is never decreasing, only if it is in a 2 or more system
|
3rd law of thermodynamics
|
as temperature goes to zero, entropy approaches a constant value
|
G, S, H
|
S = entropy
G = Gibbs free energy
H = heat energy
|
entropy
|
degrees of freedom of a molecule
|
2nd law with entropy
|
as matter disperses, entropy increase, so, going from solid to liquid to gas would increase entropy, whilst going from gas to liquid to solid would decrease it
|
volumes proportionality with entropy
|
as V goes up, so does S
as the more temperature, the more energy, the mor entropy
|
delta S =
|
(sum of S products) - (sum of S reactants)
DO NOT FORGET TO ACCOUNT FOR THE MOLES IN THE REACTION!!!
|
what is Gibb's free energy
|
the energy of a system related to changes in enthalpy and entropy, at a constant temperature.
basically implies that the system is at 1 atm and using 1 M solutions.
|
how do you calculate Gibbs free energy
|
delta G = delta H - (T * delta S)
gibbs free energy = enthalpy - (temperature times entropy)
*note T is in kelvin, not Celsius
|
is H > 0 and S > 0
|
T = 500k
spontaneous, high temperature, T delta S is large
|
is H < 0 and S < 0
|
T=100k
spontaneous, low temperature, T delta S is small
|
is H < 0 and S > 0
|
spontaneous at all Temps, delta G <0
|
if a reaction is thermodynamically favorable
|
delta G and the energy of the product is lower than that of the reactants
1. G = negative = k>1; G = positive = k
|
if a reaction is kinetically favorable
|
it has k>1, relatively low activation energy
|
how K and G relate to each other
|
G = negative = k>1
G = positive = k<1
k is close to 1, G is close to zero
k is far from 1, G is far from zero
|
how a reaction that is thermodynamically unfavorable occur
|
a reaction can be coupled with a reaction that is favorable to push it forward
Examples:
- photosynthesis
- ATP
- Charging a battery with electricity
|
exergonic reaction
|
products have less energy than reactants, spontaneous, graph will end lower than it started
|
charging a battery vs using a battery
|
charging = non-spontaneous
using = spontaneous
|
voltage equation
|
V = IR
voltage = current (amps) * resistance (ohms)
|
galvanic cell
|
chemical energy is converted to electrical energy with spontaneous redox reaction
Voltage
consists of oxidizing agent in one compartment that pulls electrons through a wire from a reducing agent
|
anode
|
oxidation happens, losing electrons
|
cathode
|
reduction happens, gaining electrons
|
oxidation half-reaction
|
x --> X+ + e-
|
non-spontaneous is...
|
thermodynamically unfavorable
|
overall cell reaction
|
y + z --> Y+ + Z- (G<0)
|
cell potential, Ecell, electromotive force (emf)
|
1 joule of work / coulomb of charge transferred
J/C = units
|
galvanic cell vs electrolytic cell
|
galvanic = anode is negative and cathode is positive
electrolytic = anode is positive and cathode is negative
|
Cell potential equation
|
Ecell = E (cathode) - E (anode)
IMPORTANT: if the reaction gets reversed (in order to balance, sometimes it will need to be reversed), the sign of the Ecell must switch, however if it gets multiplied (in order to balance) IT REMAINS THE SAME!!
|