Chemical Thermodynamics

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CHEMICAL

THERMODYN
AMICS
OBJECTIVES

• Predict the spontaneity of a process based on


entropy (STEM_GC11CT-IVa-b-140)
• Explain the second law of thermodynamics and
its significance (STEM_GC11CT-IVa-b-142)
• Use Gibbs’ free energy to determine the
direction of a reaction (STEM_GC11CT-IVa-b-143)
SPONTANEOUS
PROCESSES
Spontaneous: process that does
occur under a specific set of
conditions
Nonspontaneous: process that does
not occur under a specific set of
conditions
SPONTANEOUS
PROCESSES
Often spontaneous processes are
exothermic, but not always….
Methane gas burns spontaneously and is
exothermic
Ice melts spontaneously but this is an
endothermic process…
There is another quantity!
SPONTANEOUS PROCESSES
{Spontaneity}

Processes that
are spontaneous
in one direction
are
nonspontaneous
in the reverse
direction.
Processes that are spontaneous at one temperature may be
nonspontaneous at other temperatures.
Above 0C it is spontaneous for ice to melt.
Below 0C the reverse process is spontaneous.

Spontaneous @ T
< 0ºC
Is the
spontaneity of
melting ice
dependent on
anything?
Spontaneous @ T
> 0ºC
SPONTANEOUS VS
NONSPONTANEOUS
ENTROPY

entropy is simply a measure how much the


energy of atoms and molecules become more
spread out in a process
can be defined in terms of statistical
probabilities of a system or in terms of the
other thermodynamic quantities.
STANDARD ENTROPY

Standard entropy: absolute entropy of a


substance at 1 atm (typically at 25C)
What do you notice about entropy values for
elements and compounds?
Units: J/K·mol
ENTROPIES
TRENDS IN ENTROPY
Entropy for gas phase is greater than that of liquid or
solid of same substance
 I2 (g) has greater entropy than I2 (s)

More complex structures have greater entropy


 C2H6 (g) has greater entropy than CH4 (g)

Allotropes - more ordered forms have lower entropy


 Diamond has lower entropy than graphite
ENTROPY CHANGES IN A
SYSTEM QUALITATIVE
Ssolid < Sliquid
ENTROPY CHANGES IN A
SYSTEM QUALITATIVE

Sliquid < Svapor


ENTROPY CHANGES IN A
SYSTEM QUALITATIVE
Spure < Saqueous
ENTROPY CHANGES IN A
SYSTEM QUALITATIVE

Slower temp < Shigher temp


ENTROPY CHANGES IN A
SYSTEM QUALITATIVE
Sfewer moles < Smore moles
STANDARD ENTROPIES
Standard entropies tend to increase with increasing
molar mass.
Larger and more complex molecules have greater
entropies (greater ways to execute molecular
motions)

{*Entropy&MolecuarSize} {Entropy&Temp}C7H15 @ 500 K S=921J/nK vs, @ 200 K


ENTROPY CHANGES IN A
SYSTEM QUALITATIVE
Determine the sign of S for the following (qualitatively)
1. Liquid nitrogen evaporates
2. Two clear liquids are mixed and a solid
yellow precipitate forms
3. Liquid water is heated from 22.5 C to
55.8 C
CONCEPT CHECK

Predict the sign of S for each of the


following, and explain:
a) The evaporation of alcohol
b) The freezing of water
c) Compressing an ideal gas at constant
temperature
d) Heating an ideal gas at constant pressure
e) Dissolving NaCl in water
REVIEW
Predict whether the entropy change of the system in
each of the following is positive or negative.
N2 (g, 10 atm) —> N2 (g, 1atm).
6CO2(g) + 6H2O(g) —> C6H12O6(g) + 6O2(g).
2 H2 (g) + O2 (g) —> 2 H2O (l)
NH4Cl (s) —> NH3(g) + HCl (g)
THE SECOND AND THIRD LAWS
OF THERMODYNAMICS

System: the reaction


Surroundings: everything else

Both undergo changes in entropy during


physical and chemical processes
SECOND LAW OF
THERMODYNAMICS
Entropy of the universe increases in a
spontaneous process and remains
unchanged in an equilibrium process.

Equilibrium process: caused to occur by


adding or removing energy from a
system that is at equilibrium
SECOND LAW OF
THERMODYNAMICS
Mathematically speaking:
Spontaneous process:
Suniverse = Ssystem + Ssurroundings > 0

Equilibrium process:
Suniverse = Ssystem + Ssurroundings = 0
ENTROPY CHANGES IN THE
SYSTEM

Entropy can be calculated from the table of


standard values just as enthalpy change was
calculated.

Srxn = nS products  mS reactants


STANDARD ENTROPY

Calculate the standard entropy change for


the following using the table of standard
values. (first, predict the sign for S
qualitatively)
SN2 = 191.5 J/mole K;
SH2 = 131 J/mole K;
SNH3 = 193 J/mole K
2NH3(g)  N2(g) + 3H2(g)
2NH3(g)  N2(g) + 3H2(g)

Srxn = nS products  mS reactants

=[(1)(191.5 J/K·mol)+(3)(131.0 J/K · mol)]


- [(2)(193.0 J/K · mol)]
= 584.5 J/K · mol - 386 J/K · mol
Srxn = 198.5 J/K · mol (Entropy increases)
(2 mol gas  4 mol gas)
Calculate the standard entropy change for
the following using the table of standard
values.
SH2O = 188.7 J/mole K;
SH2 = 131 J/mole K;
SO2 = 205 J/mole K
2H2(g) + O2(g)  2H2O (g)

S = -89.6
THERMODYNAMIC CHANGES IN


SYSTEMS (CHEM. REACTIONS)

Hrxn =  Hf (products) -  Hf (reactants)


So298   Soproducts   Soreactants

Grxn =  Gf (products)   Gf (reactants)


ENTROPY CHANGES IN THE
SURROUNDINGS
Change in entropy of surroundings is
directly proportional to the enthalpy of
the system.
Ssurroundings   Hsystem

Notice: exothermic process corresponds


to positive entropy change in
surroundings
ENTROPY CHANGES IN THE
SURROUNDINGS
Change in entropy of surroundings is
inversely proportional to temperature
Ssurroundings  1 / T
Combining the two expressions:

Hsys
Ssurr 
T
If the entropy change for a system is known
to be 187.5 J/Kmol and the enthalpy
change for a system is known to be 35.8
kJ/mol, is the reaction spontaneous?
Spontaneous if: Suniv= Ssys + Ssurr > 0

Hsys
Ssurr 
T
Is the reaction spontaneous?
35,800 J/mol
Ssys   120.0J/K  mol
298 K

Suniv= -187.5 + 120.0 < 0 so the reaction is


non-spontaneous
PROBLEM: CALCULATE THE SOUNIV FOR THE
SYNTHESIS OF AMMONIA @ 25 C.

N2 (G) + 3 H2 (G)  2 NH 3 (G)

H°RXN = - 92.6 KJ/MOL

SN2 = 191.5 J/mole K;


SH2 = 131 J/mole K;
SNH3 = 193 J/mole K
3. Is the reaction spontaneous at 25 C?
N2 (g) + 3 H2 (g) —> 2 NH3 (g)
ΔH°rxn = - 92.6 kJ/mol

N2 (g) + 3 H2 (g) —> 2 NH3 (g)


From the table, S°(J/K· mol):
192 131 193
THIRD LAW OF
THERMODYNAMICS
“The entropy of a perfect crystalline substance is zero
at the absolute zero of temperature.”
At absolute zero (T = 0 K= -273.15 oC), the entropy of
a perfect crystal is 0.
As the temperature increases, the freedom of motion
increases. The entropy of any substance at a
temperature above 0 K is greater than zero.
1. Determine ΔS for the reaction:
SO3(g) + H2O(l) —> H2SO4(l)
Given: S°(J/K·mol):
256.2 69.9 156.9
2. Calculate ΔS for the reaction
SO2(s) + NO2(g) —> SO3(g) + NO(g)
Given: S°(J/K·mol):
248.5 240.5 256.2 210.6
3. Calculate ∆S° for the following reaction:
2Na(s) + 2H2O(l) → 2NaOH(aq) + H2(g)

Given the following information:


S° (J/K·mol)
Na(s) 51
H2O(l) 70
NaOH(aq) 50
H2(g) 131
STANDARD FREE ENERGY
CHANGES

Free energy can be calculated from the table


of standard values just as enthalpy and
entropy changes.

Grxn = nG products  mG reactants


STANDARD FREE ENERGY
CHANGES
Calculate the standard free-energy change for the
following reaction.
2KClO3(s)  2KCl(s) + 3O2(g)
GKCl = 408.3 kJ/mol;
GO2 = 0
GKClO3 = 289.9 kJ/mol
Grxn = nG products  mG reactants
= [2(408.3 kJ/mol) + 3(0)]  [2(289.9 kJ/mol)]
= 816.6  (579.8) = 236.8 kJ/mol (spont)
Find the standard Gibbs energy change for the
reaction
CaCO3(s) → CaO(s)+ CO2(g)

The ΔGf° values for the three components of this


reaction system are
CaCO3(s): –1128 kJ/ mol
CaO(s): –603.5 kJ/mol
CO2(g): –137.2 kJ/mol
GIBBS FREE ENERGY

G = H – T S

The Gibbs free energy, expressed in


terms of enthalpy and entropy, refers
only to the system, yet can be used to
predict spontaneity.
GIBBS FREE ENERGY

If G < 0,negative, the forward reaction is


spontaneous.
If G = 0, the reaction is at equilibrium.
If G > 0, positive, the forward reaction
is nonspontaneous
EXAMPLE

Determine if this reaction is


spontaneous under standard conditions;
knowing that the reaction's change
in enthalpy is ΔH∘=−144 kJ, and its
change in entropy is ΔS∘=−36.8 J/K.
4KClO3(s)→3KClO4(s)+KCl(s)
EXAMPLE

What is the standard free energy change ΔG for the


following reaction at 25oC?
N2 + 3H2 → 2NH3
ΔHfo (KJ/mol) So (J/K mol) ΔGfo (KJ/mol)
N2 191.610
H2 130.684
NH3 -46.11 192.450 -16.45
Calculate ΔG at 25°C for the following reaction, will this
reaction be spontaneous at this temperature?
CH3CO2H (l) + 2 O2 (g) → 2 CO2 (g) + 2 H2O (g)

ΔH (KJ/mol)
CH3CO2H (l) + 2 O2 (g) → 2 CO2 (g) + 2 H2O (g)
(-484.5) (-393.5) (-241.8)
ΔS (J/K mol)
CH3CO2H (l) + 2 O2 (g) → 2 CO2 (g) + 2 H2O (g)
159.8 205.1 213.7 188.8
Calculate ΔG at 25°C for the following reaction,
will this reaction be spontaneous at this
temperature?
CH3CO2H (l) + 2 O2 (g) → 2 CO2 (g) + 2 H2O (g)

ΔG (KJ/mol)
CH3CO2H (l) + 2 O2 (g) → 2 CO2 (g) + 2 H2O (g)
-389.9 (-394.4) (-228.6)
PREDICTING TEMPERATURE
FROM GIBBS EQUATION

Set G = 0 (equilibrium condition)


0 = H – T S

Rearrange equation to solve for T- watch


for units!
This equation will also be useful to
calculate temperature of a phase
change.
EXAMPLE

For a reaction in which H = 125 kJ/mol and S =


325 J/Kmol, determine the temperature in
Celsius above which the reaction is spontaneous.

H 125 kJ/mol
T    385 K
S 0.325 kJ/K×mol
385 K  273 = 112C
FREE ENERGY AND
CHEMICAL EQUILIBRIUM
Reactions are almost always in
something other than their standard
states.
Free energy is needed to determine if a
reaction is spontaneous or not.
How does free energy change with
changes in concentration?
FREE ENERGY AND
EQUILIBRIUM
G = G° + RT ln Q
G = non-standard free energy
G° = standard free energy (from
tables)
R = 8.314 J/K·mole
T = temp in K
Q = reaction quotient
Consider the reaction,
H2(g) + Cl2(g)  2 HCl(g)
How does the value of G change when the
pressures of the gases are altered as follows at 25
C?
H2 = 0.25 atm; Cl2 = 0.45 atm; HCl = 0.30 atm
Gfo (KJ/mol)
H2(g) + Cl2(g)  2 HCl(g)
0 0 (-95.27)
FREE ENERGY AND
EQUILIBRIUM
First, calculate standard free energy:
H2(g) + Cl2(g)  2 HCl(g)
G° = [2(95.27 kJ/mol)]  [0 + 0] =
190.54 kJ/mol
Second, find Q:
(P )2 (0.30) 2
QP  HCl   0.80
(P ) (P ) (0.25) (0.45)
H Cl
2 2
FREE ENERGY AND
EQUILIBRIUM
Solve: G = G° + RT ln Q
G = 190,540 J/mol + (8.314J/K·mol)(298 K)
ln (0.80)

G =  191.09 kJ/mol (the reaction becomes more


spontaneous - free energy is more negative)
Consider the reaction,
O2(g) + 2CO(g)  2CO2(g)
How does the value of G change when the
pressures of the gases are altered as follows at 25
C?
O2 = 0.50 atm; CO = 0.30 atm; CO2 = 0.45 atm
ΔGfo
O2(g) + 2CO(g)  2CO2(g)
0 -137.168 -394.359
RELATIONSHIP BETWEEN G°
AND K

At equilibrium, G = 0 and Q = K
The equation becomes:
0 = G° + RT ln K
or
G° = – RT ln K

K=e -G°/RT
RELATIONSHIP BETWEEN G°
AND K
RELATIONSHIP BETWEEN G°
AND K

Using the table of standard free energies,


calculate the equilibrium constant, KP, for the
following reaction at 25 C.
2HCl(g) H2(g) + Cl2(g)
G° 95.27 kJ/mol 0 0
RELATIONSHIP BETWEEN G°
AND K
First, calculate the G°:
= [0 + 0]  [2(95.27 kJ/mol)]
= 190.54 kJ/mol (non-spontaneous)
Substitute into equation:
190.54 kJ/mol = (8.314 x 103 kJ/K·mol)
(298 K)lnKP
76.90 = ln KP = 3.98 x 1034
K < 1 reactants are favored
Calculate the value of the equilibrium constant, KP,
for the following reaction at 25 C.
2NO2(g) N2O4(g)

NO2(g) N2O4(g)
ΔGfo (KJ/mol) 51.31 97.89
PRACTICE

1. Calculate the entropy change for the following


reactions:
A. C3H8(g) + 5O2(g)  3CO2(g) + 4H2O(g)
S° 270.3 205.0 213.6 188.7 J/K mol
B. CO(g) + 2H2(g)  CH3OH(g)
S° 197.9 131.0 239.9 J/K mol
2. Calculate the Gibbs Free Energy for the following reactions:
A. N2(g) + 3H2(g)  2NH3(g) at 25 oC
∆Ho = -92 kJ and ∆ So = -199 J/K = -0.199 kJ/K
B. CH4(g) + H2O(g)  CO(g) + 3H2(g) at 25 oC
∆ Ho = 206 kJ and ∆ So = 216 J/K = 0.216 kJ/K
3. The old camera flash bulb used Mg metal sealed in a bulb
with oxygen. The reaction is:
Mg + ½ O2 —> MgO
S° J/K mol: 32.7 205.0 26.9
ΔHfo kJ/mol: 0 0 -601.2
4. At what temp will a reaction occur? Given the
following reaction and data:
N2(g) + O2 (g) —> 2 NO (g)

Δ S J/K mol: 192 205.0 211


ΔHfo kJ/mol: 0 0 90
5. Find the value for the equilibrium constant, K, at
25 °C (298 K) for the following reaction. The
standard free energy change, ΔG°, at 25 °C
equals –13.6 kJ.
2NH3 (g) + CO2 (g) → NH2CONH2 (aq) + H2O(l)

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