Ch 20 :

Thermodynamics
20.1 : 2nd law -

Predicting Spontaneous Change

*
spontaneous does not mean instantaneous ,
it can take a long time but will happen on its own

ex .

rusting , ripening G aging

2 Concepts that DON'T Predict spontaneous Change :

i 1st Law law of energy conservation Internal energy of a system (E) the sum of kinetic
- -
.
,

& potential energies of its particles changes when heat ( g)

,
or work (WI are absorbed I released

DE =
g t W DE sys =
-
DE gurr or ( gt w)
sys
= -
(9 t w ) surr

first law accounts for energy but not the direction of a spontaneous change
-

2 .
The sign of DH does not predict spontaneous change
DH =
enthalpy change
-

spontaneous processes w/ DH CO : all freezing 4 condensing processes are exothermic and

spontaneous at certain conditions

Hill) - o Hill (s) D Him =

-
DH or.us = -

6.02 KU ( I atm ; T -
-
0°C)

•
the burning of methane 9 all other combustion

(Hy (g) t
202cg) -
b CO2 Cgl + 2h20 (g)

•
Oxidation of iron 4 other metals

2 Fe (s ) t
I 02cg) → Fe, O , ( s) DH rxn = -
826kV

•
Formation of Ionic compounds

Na Cs) t
Ich Cg) -
o
NaCl (s) Dttorxn = -

411kV

spontaneous DH SO all vaporization

processes with i
melting da processes are
-

endothermic G spontaneous at certain conditions

He 0 ( s) -0 H2O (l) DH an
=
DH r.us
= t 6.02kV

•
Most soluble salts dissolve endothermically

NaCl is) Nat lag) (I lag) D Hogan +3.9 KU

-

a + =

* Chemical entities -
atoms ,
molecules ,
10ns -
have more freedom of motion after the change

Phase Change solid -0

liquid

Dissolving a Salt crystalline solid +

liquid -0 10ns In solution

chemical Change crystalline solid -

o
gases
+
Ions in solution

* the dispersal of the energy of motion is a key factor for predicting direction

Microstate :(w) at any instant ,

the total energy of the system is disbursed throughout one micro state
 # of microstates ( no units )
¢

units ¥ → S = K In W *
a system w/ fewer microstates ( W ) has lower entropy ( s)
T
Bateman constant 11.38 '
10 K) * a system w/ more microstates ( W ) has higher entropy (s)

lower ( microstates ) higher entropy ( more microstates)

entropy fewer - a

*
entropy is a key factor in formation of solutions

Snore microstates
) S fewer microstates Change in
entropy of a system
:
Issy ,
=
Sf -

Si

The following increase the likelyhood that a reaction will be spontaneous

-

a gas is generated from a liquid

-

energy is released in the form of heat

a liquid Is generated from a solid

Entropy : a measure of the

energy dispersal of a system

2nd Law :
Energy Dispersal 4 Entropy
spontaneous processes resulted uniform distribution of matter
in or
energy
-

energy distributions can be translational rotational and vibrational energy States & electronic States
-

, ,

=
microstates

D Ssg, heat change for reversible process Dssys DI DH TDS E O

agree
= ← =
a -

→
T

* all real processes occur spontaneously in the direction that increases the entropy of universe

1) Sonu =
Dssys t DS sur .
7 O

DG E O =
DH -
TDS E O if C- I then it is not possible

as T increases ,
so increases , higher T results in more random motions

5 solid L so liquid L 5 gas

DSI.us L L DS Tap

entropy increases when

microstates increase solute dissolves in solvent
more
significantly
when liquid turns
to gas

Dsosowte t D S°sow t D8 solution

 5 increases as the molar mass increases .
Entropy has a O point di we can determine
absolute values by applying the 3rd law : a
site <
SoHo, c SH Br L soit , perfect crystal has zero entropy at abs O
T
particles are aligned flawlessly
A perfect crystal at absolute O ,
the particles have minimum
energy ,
so there is only one
microstate
W -
- I so S -
-
K In 1=0

When crystal is warmed to any temp above Ok ,

total energy increases = more than I micro state

W > I 4 In W > 0 so , s >O

°
We compare entropy values for substances at the temperature of interest in their desired States

I atm for gases , IM for solutions , pure substance in either solid or liquid

Standard Molar Entropy ( so) units :

m÷ ,
at 298k

Standard Molar Entropy is affected by :

temperature , Physica , Dissolution da , atomic

Temperature :
for
any substance so increases as T rises

Physical States da Phase Changes : so increases as the physical state of a substance changes from
solid to liquid to gas
 Dissolving a Solid or Liquid in Water :
entropy increases San > IS solute
t S solvent )

when water is the solvent , the entropy

*
may also depend on the nature of solute da solvent interactions
which can have 2 opposing effects

i. Ionic solutes :
when crystals dissolve in water they
have more freedom of motion & their energy
is dispersed into more microstates But water molecules become arranged around them
4 limit their motion

-
in smaller , multiply charged 10ns , H2O molecules become so organized that energy of motion becomes
less dispersed

2. Molecular solutes :
entropy is much smaller b/c for solids such as glucose ,
there is no separation of
10ns , plus H bond hold them in place

Dissolving a Gas in a liquid :

entropy of a
gas in a liquid IS less than it would be by itself .

Atomic Size 4 Molecular Complexity :

difference in 5 values for a substance in the same phase is
determined by atomic size 4 molecular complexity

within a periodic group energy levels ,

become closer together for heavier atoms ,
so the # of
microstates ,
da molar entropy increases ,
same down a group
!

for diff forms of an element ( allotropes) , entropy is higher in the form that allows the atoms more
freedom of motion

-
for compounds , entropy increases w/ chemical complexity I # of atoms in the formula)

20.1 -

Predicting Relative Entropy Values

select substance w/ higher

entropy
a) I mot of 5021g) or l MOI OF SO , 19) -

entropy increases WI # of atoms

b) I mot of CO . 1st or I mot of CO2 (g) -

entropy is larger in a gas state ( more motion)

C) 3 mot 021g) or 2 mot of Oz (g) -

more microstates possible w/ 3 mot than 2 MOI

d) I mot K Br (s) or I mot of KBR lag) -

more entropy in ag state

e) seawater at 20 or at 23°C -

entropy increases with temperature

F) I mot of CF , Cgl or I mot of CCH (g) -

larger molecule has higher entropy ( molar mass more)

Calculating the Change in Entropy of a Reaction

* If the # OF moles of a gas increases D Soran Is positive ,

if the # decreases Dsorxn Is -

1) So E S products E Soreactonts
'
=
rxn M -
n

* If "

g
"

joules of heat are released reversibly when a substance is at a temp (t )

DS ←
the entropy of system decreases
ft
=
a since
-

syst
energy is released

* A reaction that results in an overall increase in # of

gas molecules has a Ct)
+ Dsrxn BI entropy of a substance in a
gas phase is much higher

DS univ
=
DS sys
t D S surr
70

as T T ,
so 9

Dissolution : DS Solute + DS solvent L DSO solution

•
when an Ionic compound dissolves # OF microstates B

some cations will become ordered by water which

will cause so to decrease only slightly so

overall 5 of system T

•
When size of cation is small dog charge is high
the ordering will become more significant 4 the
overall so will to

Q : Will so T or to when a gas dissolves in water ? It will be

Molar Mass : so T as molar mass T

this is due to smaller

energy difference for heavier molecules

smaller allows to disperse

energy diff molecules energy easier

SOHF L SoHo, C S Br
L Solti

Molecular complexity :

more atoms in a molecule =

larger 5

Q : choose higher 5 at lmol of NO Cg) or lmol Nz 04 Cg)

b) lmol of H2O Cgl or Imo I Hr Ocs)

c) I MOI Kells) or lmol KU Caa)

d) Milk att 4°C or 25°C

e) I mot of PF , or lmol Pls

 20.2 Calculating D8 of a Axn

Predicting sign of Dso

o
Amt ( mot) Gases have high molar entroples so ,
if moles
of a gas increases DS°r×n IS CH ,
If moles

decrease Dsorxn is t)

ex
Nz 191 D8
.

+ 3 Hi Ig) -0 2NH , (g) L O

4 moles to 2 moles

He (g) +
Iz Cs ) → ZHI Cgl D8 > O
w

( s) to (g)

Calculating Dsorxn from so

a Acg) t b Bcg) -
o
cccg) t DD Ig)

Hess 's Law :

DS°r×n = Em 5 products
-
E n so reactants

DS°r×n =
c Soc + d Soo -
( a Soa t b Sig )

ex
Nz Hull) Oz (g) N , Lg) 2h20 (g)
.

t -
o t Dso >O
2 moles 3 moles

DS°r×n =
(l ( 192) t 21188 ) ) -
( 121 t 205 )

DS°r×n =
+242 ¥m

Q :
calculate Entropy change

3. Fe O , ( s)
.
t CO Cg) -0 2 Fe , 04 (s) + (Oz ( g) Dso CO
4 moles 3 moles

Dsorxn =
( 21145.3) t 213.7 ] -
[3187.401-1 197.5]

DS ;×n = -
44.6 ¥m

Some spontaneous reactions have -

so b/c the increase in so of the

surroundings over weighs the so of system ( reaction )

ex . liquid freezing below its freezing point is spontaneous

liquid -0
solid ← so of system decreases

5 of surroundings increases due to exothermic process

9 sys
L O 9 surr SO Ssorr > O ← exothermic process releases
heat to the surroundings
 qsys 70
9 sur
LO Soir LO ← endothermic process aborts

Dsurr
-DHf# to T
-

9-sys Dsosorr
=
← Is
inversely proportional
T

ex .
Consider the combustion of propane gas . a) Calculate entropy change at 298K

b) Determine the sign of the entropy change for the system . c) Is rxn spontaneous?

C. Hoo Ig) t
50219)
→
3102191 +
4h20 Ig) DH = -

2044kV
6 moles 7 moles P
DS:µ= t exothermic rxn

Dsosurr =
-1-20441404 = 6.86 KI
298k K

* b/c Dsosurr 4 Dsosys are Lt) ,

the rxn will be spontaneous

-
tf universe entropy is it rxn will be spontaneous
⇐
If universe entropy is C-I rxn is non -

spontaneous

Q :
At 298K ,
formation of ammonia has a l I
-

Dsosys
Calculate Dsunw 4 determine if rxn is spontaneous at this temp .
DH : NH, =
-45.9

Nz ( g) t
3Hz (g) → 2MHz (9) DS°r×n =
-

197 VIK

DH rin =
21 45.9)
-
= -

91.8 Ku

Dssorr -1-91.8144
Dettsys 0.3081 DH sys Dttrxn
= o
k¥ =
-
- =

298k

Dsuinv =
D S sur
t DS sys = 308 I 01k .
t l 1974k )
-
= 111.1 VIK

D S univ
=
Ill ¥ ← since (t) rxn is spontaneous
 20.3 Gibbs Free Energy
Gibbs free energy is a state function that correlates enthalpy , entropy
{ temperature .
This allows us to see the spontaneity of the process easier

G =
H -
TS od IG sys = DH sys
-
TD Ssys

Combining the 2 you get

:
DG sys = -
T DS univ
← the change the
in
Gibbs free energy of
the system is related
D Sunn SO spontaneous to the change in the entropy
of the universe

D Sunn L O non -

spontaneous

D Sunn = O process is at equilibrium

IG sys
C O spontaneous

D Gsys SO non -

spontaneous

D Gsys =
0 at equilibrium

Q : Ex. A reaction has a standard enthalpy change, ΔH, of 10.00 kJ/mol at 298 K. The standard entropy change,
ΔS, for the same reaction is 10.00 J/mol⋅K. What is the value of ΔG for the reaction in kJ/mol?

DIG = D Ho -
TDS DG =
110 knot ) -
( 298K) ( 0.01 mouth )
DG -
-
7.02

Since free energy is a state function, ∆Gsys ( = ∆Grxn) can be calculated by a Hess's law-type formula.

DG°r×n= Em Gop ( products) -

En Gor (reactants)
.

Q : Calculate the standard free energy of the following reaction from standard free energies of formation.

2CO(g) + O2(g) → 2CO2(g)

G˚fCO(g) = –137.3 kJ/mol, G˚fO2(g) = 0 kJ/mol, G˚fCO2(g) = –394.4 kJ/mol

DG an
=
21 -
394.4 knot,) -
[ 21 137.3¥ )
-

,
+ O )
DG°r×n = -
514.2k¥

* If a
given reversible reaction has It ) values for both DH dy DS ,
the

value of DG will become more C-I as T T , da the formation of the

products will be increasingly favored .

 DG sys =
W max

20.4 Free Energy Equilibrium 4 Reaction Direction

Relationship Between Q da k: DG = RT In ( Qlk )

at standard state :

DG =
RT In Q -

RT Ink
at Std state , all concentrations

{ pressures = I ,
Q -
-
I

DG°= -
RT Ink

Small K -
-
reactant
Ctl : enao
favored
la la
"

DG 79.9kV K
-

= -
-
1.0×10

Hr 0111 E H lag) OH lag)

'
- -

+
-
down,Y, Uphill
& b doz ¥6 Uphill non -

spontaneous
shifted to left
P
gas constant

* When DG is It) K
will be really small

DG° k > I
"

C I
''

is -

favors products

DG° is O K -
-
I Q -
-
I DG =D GO

DO IS CH K Ll
''

favors reactants
"

Qsl DG > AGO

↳ rxn will proceed more

sponeous toward products

Free energy change under condition :

any AGL boo

O, > I
D G =
DO + RTINQ ↳ less
spontaneos toward
products
Ex A container filled with 0.500 atm of SO2, 0.0100 atm of O2, and 0.100 atm of SO3 at 25 C
.
̊ . What is the free
energy change, ∆G, under this condition?
2502cg) + Or Cg) -0
2503cg) Dci =
-
141.6 kulmol

'
Q = ( Pso )
-3 ,
Q =
-
0.01 Q = 4
10.50140011
( ( Psa)' ( Po )]
-

DG =
( -

141.6 kulmol ) t ( 8.3101mW -

K) ( 298k) In 14) DG =
145.0 ?
 * When a rxn is at equilibrium ,
the reaction quotient ,
Q, is always = K

& G = O
B Gol comp 1)i

DG°Ccomp2) -

D Gorxn

point of
equilibrium
-

DG = RT In ( ¥) ,
DG = 0 when Q = K i. e when
Qq
= I

Q What is the change in entropy when 0.380 mol of potassium freezes at 63.7°C?(ΔHfus = 2.39 kJ/mol)
:

so = ? n : 0.38 MOI K T, = 336.85K DH =

2.39 KOIMOI

at freezing DG = O ble at equilibrium DG -

-
DH -
TDS DS =
DI
T
DG -
-
O =
BHO -
TDs

DS = ( 0.380 mot) ( 2.39 "

Ymol) DS =
-

2.696 x 10-3
1336.8¥ 9
( l ble
- freezes

Q : According to advertisements, "a diamond is forever". Calculate ΔH o, ΔS o, and ΔG o at 298 K for the phase
change: diamond → graphite

Enthalpy ( DH) DH an ( ( Imd) ( BHO of

graphite )] ( ( Imo1) ( DH of dimond))
'
-
=

BHO =
Ill Moll ( O Kul molt] -
(( Im01111.896 Kul mot))

BHO = -

1.896 KOIMOI

( Dso ) ((Imo1115 graphite D [ limo1) ( 5 dimond))

Entropy DS = -

ran

Dso = (( lmol) ( 5.686M¥ )] .

-

( ( lmol ) ( 2.439 moi.kD

Dso = 3.247 VIK

Free Energy ( Bci ) Dci =

[ llmol ) ( Dci graphite)] -
(( lmolll DO diamond)]

DO =
(( Imd) ( O Koimoi)) -

[( Imo1) ( 2.866 kulmol))

DG
'
= -
2.866 KUI MOI

Q :
Find ΔSo for the formation of 1 mole of Cu2O(s) from its elements.
2 Cu ist t I 0191 - o
Cu O
,
1st

DS " -
Almo1) ( 93 .
I "YmoH) -
( ( 2 molt ( 33.1) t ( E mot) ( 205.01]

Dso =
93.1k¥ -

168.7k¥ DSO =
-75.6 I
K
Q :
Calculate the equilibrium PCO2 at 25°C for reaction below. Report your answer to three significant figures.
DG RT Ink
CaCO3(s) ⇌ CaO(s) + CO2(g)
= -

DG =
[l -
603.5 Koimoi) +
l 394.4 ))
- -

(( -
1128.8 Koimoi))

DG = -
997.9 Koimoi t 1128.8 kulmol

First find DG° -0 DG -

-
t
130.9 Koimoi

then plug into DG : -

RT Ink 130.9 KY moi = -
10.00831 not 11298k) In Kp

In Kp = -

52.83
52.86 - "

Kp Kp 1.13
-

=
e = x 10 atm

Q: Sulfur dioxide is released in the combustion of coal. Scrubbers use lime slurries of calcium hydroxide to remove
the SO2 from the flue gases.
Balanced Eg :
Ca ( OH) ,
1st +
5021g) - o Caso , 1st + H2O 111

Now, calculate the ΔS o at 298 K [S o of CaSO3(s) = 101.4 J/mol K].

DS
°
=
(( 101.44k -
moi ) t ( 69.94k -
))
moi
-
( ( 83.44k moi) - + ( 248.5 Y K moi
-
))

D8 -
-
-
160.64k

Q :

a) DG ( ( 2 mot) ( 1.3 kulmol)] [ ( O) O]

°
= - t

Dci =
2.6 ku

b) AGO =
( ( O) t 21 394.4 Koimoi))
-
-

( I -466.1 ) + 21 137.2))
-

DG = -
788.8 + 740.5

DG = -

48.3kV

c) DG :-( l 161 -
+ I 95.301]
- -

Cl 203.01)
-

DG = -

111.3+203.0

DG =
91.7 KU