Topic #1: Entropy and the 2nd Law of Thermodynamics

Reading: 20.1 pp. 895 - 897, 901

First Law of Thermodynamics

The total energy of the universe is constant
Einstein: E = mc2
E = energy
m = mass
c = speed of light
(The total mass and energy of the universe is constant)

Spontaneous Reaction
A process that occurs by itself, without an ongoing input of energy from outside the system
Exam burns to form: CO2 + H2O + heat ✓
The reverse of the reaction above is not spontaneous
Iron rusts ✓
The reverse of the reaction above is not spontaneous
Gases mix spontaneously ✓
Gases do no simply separate
Diamond turns to graphite ✓

Enthalpy (The symbol for enthalpy is H)

Exothermic process
Releases heat as a product
ΔH < 0
Many but not all exothermic reactions are spontaneous
Endothermic process
Uses heat as a reactant
ΔH > 0
Many endothermic processes do occur spontaneously
Enthalpy is not enough to determine whether a process is spontaneous or not
Requires another parameter: Entropy (S)

Entropy (S)
A quantitative measure of all the microstates in which energy can be spread
Microstates are all the different quantum states
Electronic states, vibrational states, translational and rotational states
Units of entropy are Joules/Kelvin
Boltzmann found that
S = k ln W
S = entropy in J/K
k = Boltzmann’s constant (k = ideal gas constant (8.314 K/mol x K) / (6.022 x 10 23 /
mol)
= 1.38 x 10-23 J/K
W = the number of microstates

Second Law of Thermodynamics

A process is spontaneous if it causes the entropy of the universe to increase
ΔSuniverse = ΔSsystem + ΔSsurroundings
The entropy of the universe is constantly increasing
The energy of a system will go from being concentrated to being diffused
Entropy is a quantitative measure of the number of microstates in a system
The higher the number of microstates, the more there are ways to distribute
energy, the higher the entropy
Factors That Affect Entropy
Phases of Matter
Solid: Highly dense? Structure in a small volume
Very little rotational and translational freedom
Low entropy
Liquid: More disordered still in a small volume
More rotational and translational freedom compared to the solid
Medium-low entropy
Gas: Completely disordered in a large volume
A large amount of rotational and translational freedom
High entropy
Sgas >>> Sliquid > Ssolid
Temperature
Entropy decreases as the temperature decreases
Amount of Material
Entropy increases with the amount of material
Expansion (Gases)
Expansion of a gas increases its entropy
Mixing (Gases)
If gases mix, entropy increases
Mixing increases Entropy (the exceptions are: when gas is dissolved in a liquid, dissolving
highly charged small ions in water, as H2O needs to rearrange themselves to create a
very organized hydration sphere around the ion)
Size and the Complexity of the Molecule
The higher the molecular mass, the higher the entropy
The more complex the molecules, the more entropy they have
Chemical Reactions that Increase the Number of Moles of Gas
Will always increase entropy

Third Law of Thermodynamics

The entropy of a perfect crystal at absolute zero (0K) is exactly 0 J/mol.

Spontaneous Reactions:
When ΔSuniverse > 0
ΔSuniverse = ΔSsystem + ΔSsurroundings
ΔSsystem: Two ways to calculate
Method 1: Use So formation of reactants and products
(Standard conditions: 298K, 1M, 1 atm)
S formation of a compound is the So reaction from its elements in the most
o

stable form under standard conditions

Sum of products - the sum of reactants
205(3) - 239(2) = 137 J/K x mol

Entropy is a state function that depends on the final state and the starting state but not on
the path of the reaction
Can calculate ΔS for a reaction from the ΔS of two or more other reactions that add
up to the one of interest

Gibbs
ΔG = -TΔSuniverse
G = Gibb’s free energy
ΔG = ΔH - TΔS
If the entropy of the universe is positive, then G must be negative for the reaction to
be spontaneous
If the entropy of the universe is negative, then G must be position and the reaction is
not spontaneous
If both values are equal to zero then the reaction is at equilibrium
2nd Law
At constant temperature and pressure, for a reaction to be spontaneous ΔG < 0
Require both ΔH and ΔS to predict whether or not a reaction is spontaneous

ΔH ΔS ΔG Spontaneity

- (Exothermic) + - at all T Spontaneous at all T

+ (Endothermic) - + at all T No reaction at all T

- - - at low T A reaction at low T

(Enthalpy Driven)

+ + - at high T A reaction at high T

(Entropy Driven)
G is a state function that depends on the state of the product and reactants but not on the
pathway
Under standard conditions: 1 atm, 1 M, and 25 Celcius
ΔG = ΔH - TΔS

By convention, ΔGformation for an element in its most stable form under standard conditions is
equal to 0 J/mol
ΔGO2 = O
ΔS > 0
ΔHformation > 0

At the melting point, there is both solids and liquids at equilibrium

Initially, ΔG is negative therefore making a spontaneous reaction

Reaction keeps going until you reach equilibrium, ΔG = 0
As the reaction progresses, ΔG increases until it reaches equilibrium
The relation between rate constant
Equilibrium (solution)
aA + bB ⇋ cC + dD
Equilibrium constant: K = ([D]d [C]c) / ([A]a [B]b)
Use concentrations at equilibrium
To determine in which direction the system shifts to get to equilibrium using the reaction
quotient

ΔG = -RT(lnK) (When calculating ΔG from K, the R-value is 8.314 J/mol x K)

Under standard conditions: ΔG @ 1M, 1 atm, 25 degrees Celcius

Q=1
Not under standard conditions
Q is not necessarily = 1
ΔG = ΔGo + RTlnQ
ΔGo: Gibb’s free energy under standard conditions
R: 8.314 J/mol x K
T: temp in Kelvin
Q: Reaction quotient
ΔGo = -RTlnK
ΔG = -RTlnK + RTlnQ
ΔG = RTln(Q/K)

Q/K ln(Q/K) ΔG

Q=K 1 0 0 Equilibrium

Q<K <1 <0 <0 Shifts Right

Q>K >1 >0 >0 Shifts Left

Equilibrium Constant depends on temperature
Exothermic process: heat is a product
aA + bB ⇋ cC + dD + heat
According to Le Chatelier’s principle, an increase of the temp: systems shifts
to the left. K decreases
Endothermic process: heat is a reactant
aA + bB +heat ⇋ cC + dD
According to Le Chatelier’s principle, an increase of the temp: systems shifts
to the right. K increases

ΔG = -RT lnK
ΔGo = ΔHo - TΔSo
lnK = (-ΔH0 / RT) + (ΔSo / R)
ln(K2/K1) = (ΔHo / RT1) - (ΔHo / RT2)
ln(K2/K1) = (ΔHo / R) (1/T1 - 1/T2) Van’t Hoff Equation
Van’t Hoff Equation is used for equilibrium constants vs T
Arrhenius Equation is used for rate constants vs T

S = klnW
k=R/NA
ΔSsurroundings = -ΔHsystem / T
ΔGsystem